Professional Documents
Culture Documents
Supercapacitors
Scientific Fundamentals and
Technological Applications
Electrochemical
Supercapacitors
Scientific Fundamentals and
Technological Applications
8. E. Conway
Fellow of the Royal Society of Canada
University of Ottawa
Ottawa, Ontario, Canada
Conway, B. E.
ElectrochemIcal supercapacitors , scientific fundamentals and
technological applications I B.E. Conway.
p. cm.
Includes bibliographical references and index.
10987654321
A C.I.P. record for this book is available from the Library of Congress.
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted in
any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
To my son, Dr. Adrian
and his sons, Alexander and the "Little B"
Foreword
The first model for the distribution of ions near the surface of a metal electrode
was devised by Helmholtz in 1874. He envisaged two parallel sheets of charges
of opposite sign located one on the metal surface and the other on the solution
side, a few nanometers away, exactly as in the case of a parallel plate capacitor.
The rigidity of such a model was allowed for by Gouy and Chapman inde-
pendently, by considering that ions in solution are subject to thermal motion so
that their distribution from the metal surface turns out diffuse. Stern recognized
that ions in solution do not behave as point charges as in the Gouy-Chapman
treatment, and let the center of the ion charges reside at some distance from the
metal surface while the distribution was still governed by the Gouy-Chapman
view. Finally, in 1947, D. C. Grahame transferred the knowledge of the struc-
ture of electrolyte solutions into the model of a metal/solution interface, by en-
visaging different planes of closest approach to the electrode surface depending
on whether an ion is solvated or interacts directly with the solid wall. Thus, the
Gouy-Chapman-Stern-Grahame model of the so-called electrical double
layer was born, a model that is still qualitatively accepted, although theoreti-
cians have introduced a number of new parameters of which people were not
aware 50 years ago.
Irrespective of the structural details, it has long been accepted that a double
layer exists at the electrode/electrolyte solution boundary, which governs ad-
sorption phenomena and influences charge transfer reaction rates, and where
electrostatic energy is stored as in a capacitor a few molecular diameters thick.
Nevertheless, the existence of a double layer has always been inferred from in-
direct observations of related properties and quantities, but never directly
vii
viii Foreword
probed, so much that it was compared to the Arab Phoenix: "Everybody says it
exists, nobody knows where it is." This until recently, when it was realized that
the energy stored per unit surface area of an electrode is noticeable per se and
becomes technologically very interesting with the introduction of new materials
with an exceptionally extended active surface: especially treated carbons, some
transition metal oxides, electrosynthesized conducting polymers. The inter-
facial capacity is further increased if the purely capacitive charge is supple-
mented by a Faradaic charge related to bidimensional redox reactions or
tridimensional intercalation processes.
"Supercapacitors" are devices that store electrical energy on the basis of
the above phenomena and that can be discharged at a much higher rate than con-
ventional batteries. They have aroused interest for various applications, includ-
ing electric vehicles, in particular cars as well as trains. I should say that in spite
of our awareness of the principles, supercapacitors have appeared on the scien-
tific scene rather suddenly, or at least this has been the impression ofthose who
have realized that something was happening at the technological level. Of the
many examples we can produce of innovations developed in technology first
and then "discovered" from a fundamental point of view, supercapacitors fur-
nish an authoritative example ofthe reverse: a technological innovation pushed
by fundamental knOWledge.
The situation is now that fundamental researchers know everything of the
electrical double layer but ignore its application to supercapacitors, while engi-
neers know of supercapacitors but may ignore the fundamentals of their opera-
tion. This monograph comes at an opportune time to fill this gap, with a
balanced presentation of fundamentals aimed at applications, and applications
related to fundamental principles. B. E. Conway has worked for more than 50
years in almost all areas of electrochemistry, particularly interfacial electro-
chemistry. He is therefore a "veteran" in the field, being the first to realize the
potentialities of some materials for their double layer energy.
This volume offers what cannot be found in any other work for its compre-
hensiveness, exhaustiveness, and focus. For the first time a highly theoretical
topic, the electrical double layer at electrodes, is shown to manifest itself in
highly technological applications. It is with a real sense of pride that electro-
chemists in the near future will press the accelerator in their electric car knowing
that certain performances are possible only thanks to the discharge of the "so-
called" (but is it indeed there?) electrical double layer of which technologists
have long maintained "electrochemistry can do without it."
The content of this book is useful both for scientists working in fundamen-
tal research and technologists, in particular those interested in electrochemical
energy conversion and chemistry and physics of electrified interfaces, as well
as for engineers working in the field of electrochemical power sources and elec-
trical energy storing devices. They will find the book an invaluable source of in-
Foreword ix
formation and inspiration. For the way the topics are presented, people working
in the area of materials chemistry and physics will find this book of great general
interest in view of the typical dependence of the performance of supercapacitors
on the structure of materials.
xi
xii Preface
Finally, special thanks are due to Denise Angel, who typed, with great ef-
ficiency and accuracy, all the chapters of this volume in several drafts, exercis-
ing literacy and care that would be difficult to match. Grateful thanks are also
due to Eva Szabo for drafting most of the diagrams.
~ i
c:
!l
o·:J
III
:J
a.
:I:
~...
C'j'
e!.
'tI
3
- • ~I
Ic'
CD
·\r ~.!~ ·
"i.,~~
•
FIGURE 1.1. Photographs of various designs and arrangements of condensers (capacitor devices), including first the Leyden jar. (Reproduced from
Encyclopaedia Britannica, 1929 edition, with permission). (1) A Leyden jar, the simplest type of condenser. (2) A battery of Moscicki glass condenser
tubes-an improvement on the Leyden jar, introduced about 1904 by Moscicki. (3) The transmitter at one of the stations of the British Broadcasting
Corp., showing two air dielectric condensers in the lower compartment (center and right-hand side). (4) Ship's radio transmitter, showing mica dielectric
condenser on right side on shelf over generator. (5) Mica dielectric condenser of special construction for shortwave radio stations. (6) Condenser gallery
of the Rugby radio station of the British post office. (7) Interior of the bell box used with British office telephone instrument, showing paper dielectric
condenser (bottom of box). (8) Top row: several patterns of fixed condensers. Bottom row: several types of variable condensers commonly used as tuning
capacitors in old radios.
en
6 Chapter 1
The utilization of this principle to store electrical energy for practical pur-
poses, as in a cell or battery of cells seems to have been first proposed and
claimed as an original development in the patent granted to Becker in 1957.8
The patent described electrical energy storage by means of the charge held in
the interfacial double layer at a porous carbon material perfused with an aqueous
electrolyte. The principle involved was charging of the capacitance, Cd!> of the
double layer, which arises at all solid/electrolyte interfaces, such as metal, semi-
conductor, and colloid surfaces (and also at the phase boundary between two
immiscible electrolyte solutions9 ).
Carbon is an element almost uniquely suited for fabrication of electro-
chemical capacitors of the double-layer type. It exists in several, well-known al-
lotropic forms-diamond, the fullerenes, and graphite; the latter and glassy
carbon can be generated in the form of high-area fibers or felts. Amorphous car-
bons and carbon black are available as high specific-area powders. The fiber or
felt materials are particularly convenient for formation of electrode structures
having good mechanical integrity, while the high-area powders are more diffi-
cult to handle. However, glassy carbon, graphite, and carbon black materials are
convenient for forming high-area electrode structures, often on a support ma-
trix. From an electrochemical point of view, carbon is relatively, though not en-
tirely, unreactive and thus has a potential voltage range of almost ideal
polarizability (Chapters 6 and 7), approaching 1.0 V in aqueous solution and
possibly up to 3.5 V in nonaqueous media.
After Becker, the Sohio Corporation in Cleveland, Ohio, also utilized the
double-layer capacitance of high-area carbon materials, but in a nonaqueous
solvent containing a dissolved tetraalkylarnmonium salt electrolyte. Such sys-
tems provide higher operating voltages (3.4-4.0 V) owing to the greater decom-
position voltage of nonaqueous electrolytes than those for aqueous ones. Thus
they can accommodate higher charge densities and provide larger specific en-
ergy storage since the storable energy increases with the square of the voltage
attainable on charge.
A different principle, originating from ref. 14, was utilized and developed
in 1975 onward to 1981 by ConwaylO in Ottawa, under contract with Continen-
tal Group. This was based on the concept of D. Craig that was developed at
Hooker Corp. Here, in one type of system, the large, so-called "pseudocapaci-
tance," CIP' associated with the potential dependence of extents of electrochemi-
cal adsorption of H or monolayer levels of electrodeposition of some base
metals (Pb, Bi, Cu) at Pt or Au was used ll as a basis for an energy-storing ca-
pacitor. In another type of system, the pseudocapacitance associated with solid
oxide redox systems was used, especially that developed over some 1.4 V (prac-
tical range 1.2 V) in aqueous H 2S04 at RU02 filmsy-15 This system approaches
almost ideal capacitative behavior, with a large degree of reversibility between
charge and discharge, and multiple cyclability over some lOS cycles (see Chapter 11).
Introduction and Historical Perspective 7
Work on the latter type of system has been continued by Pinnacle Research
Corp., Cupertino (now at Los Gatos, California), in the former laboratories of
Continental Group. Useful military applications have been developed, but the
Ru materials required are too expensive for the development of a large-scale ca-
pacitor, e.g., for use in hybrid systems with batteries for electric-vehicle motive power.
Pseudocapacitance arises whenever, for thermodynamic reasons, there is
some continuous dependence of a charge, q, passed Faradaically in oxidation or
reduction, upon the electrode potential, V. Thus, a derivative dq/dV can arise
that corresponds to a pseudocapacitance that is directly measurable, or
utilizable, as a capacitance (Chapter 10).
The large capacitances (on the order of several or more farads per gram)
that can be developed with the RuOz film system and also with the carbon
double-layer-type capacitors led to the terms "supercapacitor" or "ultraca-
pacitor" being coined, respectively, for these two types of high specific ca-
pacitance devices. Recently it has been suggested that the more general term
"electrochemical capacitors" be used to refer to these systems. However,
this name should not be confused with "electrolytic capacitor," the latter
term referring to the well-known, moderately high-capacitance device (on the
order of tens of millifarads) that is based on a thin-film oxide dielectric formed
electrolytically with a gel electrolyte on such metals as Ta, Zr, Ti, or AI.
The key practical factor that allows very high capacitances, on the order of
farads or tens of farads rather than millifarads, to be achieved in a small volume,
say 1 cm3, is the utilization of high-area materials such as activated porous car-
bons for which real areas are up to 1000 to 2000 m 2 g-l. Similarly, with the
Ru02 pseudocapacitance system, the material, which is a hydrous oxide, has a
quasi-3-dimensional, electronically conducting structure, giving accessibility to
protons and electrons 15 that are involved in two or three (Chapter 11) succes-
sive, reversible oxidation or reduction steps in charge or discharge, respectiVely.
The continuous dependence of the extents of oxidation or reduction on electrode
potential (over 1.4 V), with corresponding passage of charge, leads to the high
specific redox pseudocapacitance of this material,16 which is usually coupled
with an appreciable double-layer capacitance component (see Chapter 11).
The use of high-area carbon or oxide redox systems has led to the commer-
cial production of practical high-capacitance electrochemical capacitor devices
such as that developed (the Gold Capacitor) by Matsushita Electric Industrial
Co. (Osaka, Japan) and by Pinnacle Research; the latter has been developed
mainly for military applications. The commercial products are designed to pro-
vide standby power for random access memory (RAM) devices or telephone
equipment, as power sources for operating activators, and as elements for long
time-constant circuits, etc. An attractive technology employing Ru02 in a thin
film applied to a Nafion membrane, or a powder treated with Nafion, has been
developed by Giner, Inc. (Waltham, Massachusetts) and gives high specific ca-
8 Chapter 1
1~. SCOPEOFTHEMONOGRAPH
REFERENCES
1. 1. J. Thomson, Phil. Mag., 5,346 (1903); see also J. J. Thomson, The Electron in Chemistry,
Franklin Institute Lectures, Chapman and Hall, London (1923).
2. W. Crookes (1879), quoted by S. Glasstone in Textbook of Physical Chemistry, Van Nostrand,
New York (1940).
3. R. A. Millikan, Phys. Rev., 2, 143 (1913).
4. 1. S. Townsend, Electricity in Gases (1879), quoted by Glasstone as in Ref. 2.
5. G. Johnstone Stoney, Phil. Mag.,ll, 381 (1881); Sci. Trans. Roy. Soc. Dublin, 4,583 (1891).
6. H. von Helmholtz, 1. Chern. Soc., Lond., 39, 277 (1881).
7. B. E. Conway, Ionic Hydration in Chemistry and Biophysics, Elsevier, Amsterdam (1981).
8. H. E. Becker, U.S. patent 2,800,616 (to General Electric Co.) (1957).
9. Z. Samec, 1. Electroanal. Chern., 103, I (1979).
10. B. E. Conway, 1. Electrochem. Soc., 138, 1539 (1991).
11. B. E. Conway and H. A. Kozlowska, Acct. Chern. Res., 14,49 (1981).
12. S. Hadzi-Jordanov, H. A. Kozlowska, M. Vukovic, and B. E. Conway, 1. Electrochem. Soc.,
125, 1471 (1978).
13. S. Hadzi-lordanov, B. E. Conway, and H. A. Kozlowska, 1. Electroanal. Chern., 60, 359
(1975).
14. S. Trasatti and G. Buzzanca, 1. Electroanal. Chern., 29, App. 1 (1971).
15. R. Galizzioli, F. Tantardini, and S. Trasatti, 1. Appl. Electrochem., 4, 57 (1974).
16. B. E. Conway, in Proc. Symp. on Electrochemical Capacitors, F. M. Delnick and M.
Tomkiewicz, eds., vol. 95-29, 15, Electrochem. Society, Pennington, N.J. (1996).
Chapter 2
2.1. INTRODUCTION
larger than that of fuel combustion systems, which are limited by thermody-
namic Carnot cycle considerations while electrochemical systems usually in-
volve more reversible processes, with direct conversion of potentially available
chemical energy to free (or Gibbs) energy, tJ.G.
ter). This is a major and characteristic difference between battery and capacitor
electrical energy storage systems.
It must be emphasized at the outset that there has never been an aim or pro-
jection of a possible substitution of batteries by supercapacitors; rather, oppor-
tunities arise for complementary operation of electrochemical capacitors that
are electrically coupled in discharge and recharge with batteries, while other
kinds of applications especially favor capacitor-type behavior, e.g., for backup
power systems. Also, there are stand-alone opportunities for using multiply re-
chargeable electrochemical capacitors in a variety of independent functions, as
briefly indicated in Chapter 1. General aspects of the electrochemistry and tech-
nology of batteries are to be found, for example, in Refs. 1 and 2.
In the early stages of the development of electrochemical capacitor tech-
nology and related fundamental work, there was some confusion in the electro-
chemical engineering field and at symposia about the differences between the
properties and operation of a battery and a supercapacitor, and what advantages
one might have over the other. This confusion may have been assisted by some
groups calling the capacitor devices "ultracapacitors" and others, "supercapaci-
tors," the latter as originated by the Ottawa group in 1975. The present preferred
name, proposed by Burke, as referred to in Chapter 1, is now more scientific and
generic, namely "electrochemical capacitors."
This chapter identifies and explains some of the similarities and differ-
ences between electrochemical capacitors and batteries in relation to the elec-
trochemical processes that are involved in their discharge and recharge cycling,
and in their potential uses as electrical energy storage devices. In particular, the
fundamentally different mechanisms of charge storage that are normally in-
volved will be emphasized, along with the consequent, usually different, rela-
tions between the extents of charge accommodated at the electrodes and the
electric potential differences (cell voltage) between pairs of electrodes having
conjugate, ±, polarities.
One of the main and kinetically significant differences between capacitors
and batteries is that the electrodes of the latter usually undergo substantial phase
changes during discharge and recharge (minimally though for the intercalation
systems), which lead to kinetic and thermodynamic irreversibility. On the other
hand, capacitors of the double-layer type require only electrostatic charge ac-
commodation with virtually no phase change, though some small but significant
reversible electrostriction of the electrolyte can arise upon charging.
2.2.1. Non-Faradaic
The charge accumulation is achieved electrostatically by positive and
negative charges residing on two interfaces separated by a vacuum or a molecu-
lar dielectric (the double layer or, e.g., a film of mica, a space of air or an oxide
film, as in electrolytic capacitors).
2.2.2. Faradaic
The charge storage is achieved by an electron transfer that produces chemi-
calor oxidation state changes in the electroactive materials according to Fara-
day's laws (hence the term) related to electrode potential. Pseudocapacitance
can arise in some cases. The energy storage is indirect and is analogous to that
in a battery.
In a battery cell, every electron charge is Faradaically neutralized by
charge transfer, resulting in a change of oxidation stage of some redox-
electroactive reagent, e.g.,
tubes (fluorescent lights). As has been explained earlier, devices of very large
capacitance are now available for storing electric energy in various applications.
Table 2.2 summarizes the types of batteries currently extant. 1,2 These are
generally classified as primary (nonrechargeable) or secondary (multiply re-
chargeable). The discharge or recharge mechanism is mainly Faradaic, although
all electrode interfaces exhibit a double-layer capacitance that is reversibly
chargeable. For batteries the latter mechanism accommodates about 2-5% of
the total charge accepted.
In a different class from the battery systems listed in Table 2.2 are fuel cells
in which the anode and cathode (02 or air) reactants are supplied on a continu-
ous basis from external reservoirs, and the electrode surfaces provide an inter-
face for either electrocatalytic oxidation or reduction of the reagents supplied.
The primary metal-air cells are operated as semi-fuel cells, but the "fuel" is an
easily oxidizable base metal and a gas-diffusion catalyzed air or O 2 cathode is
employed. Such cells using Al are not rechargeable except by mechanical re-
placement of the metal anodes. However, if Zn is used, electrochemical recharg-
ing is possible, but requires a bifunctional catalyzed counter electrode capable
of evolving H2 on recharge or reducing O2 (air) on discharge.
Chapters 14 and 16) to represent the electrical behavior of the internal surfaces
and the electrolyte-containing interstices.
As with batteries, bipolar electrode configurations can be fabricated for
higher voltage series combinations; these diminish the internal resistance of the
device, but require that the edges of the electrodes be carefully sealed to the case
in order to avoid shunt, i.e., leakage currents. Such systems optimize power den-
sity.
The equivalent circuit for most battery-type charge storage systems in-
volves simply a Faradaic resistance (R F ) that represents the potential depend-
ence of the reciprocal of the rate of the oxidation and reduction charge transfer
process; it is in parallel with (an always significant) double-layer capacitance,
Cdl • Under some high-rate discharge or recharge conditions, some diffusion
control may arise, in which case RF is in series with a so-called Warburg C-R
impedance element written as W. In addition, with some rechargeable battery
systems (e.g., of the intercalation type), a pseudocapacitance element may also
be required to represent the impedance behavior of the Faradaic process (Chap-
ters 10 and 17).
For both electrochemical capacitors and battery cells, a solution resistance
element, Rs' in series with the Faradaic impedance, ZF, is usually necessary in
order to fully represent the charging or discharging behavior. In fact, Rs is usu-
ally very important in the evaluation and performance of capacitors and batter-
ies for high-rate discharge applications, and is an important influence on the ac
impedance spectrum (see Chapters 16 and 17) of the device.
In the absence of self-discharge processes, or any parallel pseudocapaci-
tance, the macroequivalent circuit of an electrochemical capacitor involves only
a solution resistance (Rs) and a double-layer capacitance Cd1 • However, Rs and
Cd1 have distributed components in the microequivalent circuit in the case of
high-area, porous electrode materials, as treated in Chapter 14. The same applies
to battery electrodes fabricated in porous material configurations, a procedure
and design that are commonly adopted in battery technology; then complex mi-
croequivalent circuits also apply, but with the inclusion of the essential RF com-
ponents.
face, it is easily seen that the charge accommodated per atom will be 3011 0 15 f..lc.
This is equivalent to 30 x (10- 61105) x 6 x 1023110 15 electrons per atom where
105 and 6 x 1023 are taken approximately as the Faraday constant and
Avogadro's number, respectively. The above quotient works out to be 0.18
electrons per atom stored as a double-layer charge at 1 V for the example
chosen, but this is the average delocalized charge distribution associated
with conduction-band electrons.
By contrast, in most battery processes, redox reactions involving usually
one or two valence electron charges per atom (sometimes three for Al or Bi) or
molecule of electroactive reactant are involved. Thus, electrochemical capacitor
charge storage involves, per atom of active available surface area, only about 20
or 10% (respectively) of that involved (indirectly) or available with battery re-
dox materials. Hence the energy densities available with capacitors are usually
substantially smaller than those with batteries. This is a well-recognized limita-
tion, but it is usually compensated by much larger cyclability (cycle life) and
often better power density attainable from electrochemical capacitors. Of
course, because the energy density of a capacitor increases with the square of
the voltage on charge, a substantial improvement in energy density is attained
by using nonaqueous electrolytes instead of aqueous ones, in which the decom-
position voltage can be increased to 3 or 3.5 V or more per cell unit.
Elsewhere in this volume (Chapter 14) it will be shown that with large-area
carbon materials (e.g., 1000 m2 g-I), very large specific capacitances of 300 F
g-I can (theoretically) arise. It is then of interest to compare energy densities at-
tainable at double-layer capacitors with those realized in an Ni-Cd battery.
charged nickel oxide electrodes can approach higher values at low temperatures
and in strong aqueous KOH.)
For a working voltage of 1.2, the ideal energy density (~G = -zFE) will be
1.2 x 1 x 105/148 J g-I == 8.1 X 105 J kg-I = 810 kJ kg-I where 105 is approxi-
mately F, the Faraday constant in coulombs mole-I. With I Wh = 3600 J, the
(theoretical) energy density for Ni-Cd (electroactive materials alone) is then
225 Wh kg-I. Thus an electrochemical double-layer capacitor electrode
(charged to I V working potential) would have about 20% of the energy density
of an Ni-Cd battery electrode, both figures being based on ideal, theoretical per-
formance.
A double-layer capacitor based on nonaqueous electrolyte technology
would have a substantially larger energy density than that for I-V aqueous so-
lution charging. In an actual two-electrode capacitor device, with one electrode
worked against the other, the energy density will be about (112)2 smaller,
namely, about 10 Wh kg-I in aqueous electrolyte, since each electrode can be
discharged down to only about half its initial voltage following ± charging.
: State of
: charge indication
I
I
FIGURE 2.1. Difference of discharge and recharge relationships for a capacitor and a battery: po-
tential as a function of state of charge, Q.
rather than Q·ll2 M (or 1I2Y). This difference can be illustrated by the dis-
charge curves shown schematically in Fig. 2.1 where the voltage on the capaci-
tor declines linearly (for potential-independent Cdl ) with the extent of charge,
while that for an ideal battery remains constant* as long as two phases remain
and are in equilibrium (upper curves in Fig. 2.1).
The decline of the capacitor voltage arises formally and phenomenologi-
cally since C = QIVor V = QIC; therefore dVldQ = lie. The ideal battery cell
voltages on discharge and recharge, as a function of state of charge, are shown
as parallel lines of zero slope4 in the upper parts of the diagram. These two lines
differ as a result of any cathodic and anodic polarization (including so-called
ohmic IR potential drop due to internal or solution resistance) arising in the dis-
charge or recharge half-cycles. In the sloping discharge and recharge line for the
capacitor (Fig. 2.1), there will also be significant IR drop, depending on the dis-
charge or recharge rates, that is, the discharge line will actually be somewhat
separated from the recharge line by a voltage difference equal to 2IR.
The significance of the difference between the energy density for the ca-
pacitor and a battery cell charged to the same potential can be illustrated by ref-
*In practice, there is usually some decline ofvoJtage in a battery with increasing extent of discharge.
In certain battery systems e.g., LirriSz , Li/CoOz, and metal hydride anodes, this decline is larger
and occurs for fundamental thermodynamic reasons connected with the form of the sorption
isotherms.
22 Chapter 2
erence to the working diagram shown in Fig. 2.2. Here the voltage vs. charge
relations for a capacitor and an ideal (constant voltage) battery are compared. In
actuality, most batteries, with the exception of Li-SOCI2, do exhibit some de-
cline of voltage with decreasing state of charge, but this is for reasons quite dif-
ferent from that in the case of capacitor discharge.
The line VB is the voltage across the battery cell as a function of charge Q
held during a constant rate charge, Vc is the plot of voltage across a capacitor
being charged up to the same final voltage, VB' with accommodation of the same
accumulated charge, Q. However, since the line Vc is for capacitor charging, it
has a slope of lie (see Fig. 2.1).
The integrals VQ under the two lines of the working diagram correspond
J J
to the energy of charging. Thus it is seen that VC'dQ is half VB·dQ, i.e., the
energy of charging the capacitor to a terminal voltage VB with charge Q is half
that for charging the battery with the same charge also to VB' The superimposed
hatched and slashed areas in Fig. 2.2 correspond to this difference of energy
stored. As shown mathematically in Chapter 4, the factor of half in the charging
energy of a capacitor arises for the same reason that it enters into the Born equa-
tion for the self-energy of charging of spherical ions in vacuo or in a dielectric
(see Chapter 4).
VC=q/C ; Ec=tQV= ~ cf
~Battery ~ Capacitor
f
FIGURE 2.2. Working diagram illustrating storage of energy E = V·dQ for a battery at ideally
constant charging voltage V = VB, and for a capacitor with progressively changing voltage, V =
Vc, leading to EB =QVB or Ec =(t)QVc.
a) RU02 film
u;
..0
:::J 6.25
VI
N
IE
u
O~-+--+--r~--~-+--+--+--~-r~--;--+--r----
<t
-
E
........
c ~ 6.25
~ 0
'- 0
:::J J:
UI-
'"
U
POTENTIAL/V, RHE
0.2 0.6 1.0 1.4
•
b) Pb/PbCI 2
I.f)
o
33.2
<t
........
r
z
w
a:: o~~
-0.717
__~~~L-~~-=~~L-____-0.317 -0.217
- L____~~
a::
::::> POTENTIAL/V, RHE
U 8
U 33.2
0
0
z
« ----+PbCI 2
66 .4
:I
FIGURE 2.3. (a) Cyclic voltammogram for RU02 in 1 M aqueous H2S04 (298 K) showing mir-
ror-image symmetry and responses to successive switching along the scanned potential range. (b)
Cyclic voltammogram for Pb-PbCIz battery electrode showing typical irreversibility arising with
3-dimensional materials undergoing chemical phase changes.
Supercapacitors and Batteries 25
age of that for negative, discharging, currents and switching the direction of
sweep during the potential scan produces an almost immediate reversal of di-
rection of current. This behavior is also characteristic of a reversible, capacita-
tive charge and discharge process (compare the theoretically calculated curves
in Chapter 10, Fig. 10.1).
Another characteristic feature of the behavior of this Ru02 example is that
over a wide range of sweep rates, s, the current response, I, at any potential
across the scanned range is linear in s. Since I = Cs, this means that C is inde-
pendent of sweep rate and virtually pure capacitative behavior is exhibited; it is
actually mainly pseudocapacitative (see Chapter lIon RU02) when the RU02
has been formed in a hydrous state, e.g., by an electrochemical procedure.?
Figure 2.3(b) shows, by contrast, the behavior of oxidation and reduction
at Pb-PbClz, a battery-type electrode (Pb + 2cr ~ PbC12 + 2e). The voltam-
mogram indicates a completely irreversible process: the potential range for for-
mation of PbCl 2 from Pb is widely different from that for the reverse process,
reduction of PbCl2 back to Pb. Also, switching the direction of sweep during the
voltammetric trace does not immediately reverse the sign of current at that
switching potential, contrary to behavior observed with a capacitance.
In this system, which is typical for a battery-type reaction (Pb-PbS0 4 is
similar), overvoltages are required in both directions of the reaction in order to
pass significant currents. Hence the current response profiles for each of the di-
rections of reaction lie wide apart, on each side of the reversible potential, along
the electrode potential axis of Fig. 2.3(b). The reversible potential corresponds
approximately to the potential at which the current profile I(E) crosses the po-
tential axis, i.e., where I(E) = O.
Returning to the situation of a reversible process, it should be mentioned
here that if such a reaction is diffusion controlled, then the cyclic voltammo-
gram is again not of the mirror-image type, the potential for the anodic peak cur-
rent being more positive than that for the cathodic one. This is because, even if
the reaction is reversible, different potentials are required on the anodic
sweep from those on the cathodic one to establish given concentration
gradients in the boundary diffusion layer that lead to the same (equal but
opposite) diffusion-controlled currents. If such a reversible reaction is
conducted in a thin-layer cell where the solution thickness is less than the
width of the boundary diffusion layer, then the voltammogram tends to acquire
mirror-image symmetry like that for a reversible surface film process.
host cathode materials, e.g., MoS 2, TiS 2, V60 13 , and C00 2 . 8•9 Normally these
cathode materials, coupled with an Li anode or a Li-C anode, would be regarded
as battery cathode materials. 1.2 However, the forms of the charge and discharge
curves and associated pseudocapacitance, and even the cyclic voltammetry pro-
files, are similar to those for 2-dimensional electrosorption (underpotential
deposition, UPD) (see Chapter 10). Hence this class of materials exhibits prop-
4 b)
.... -, Li/TiS 2
!/V
3
I
> I. ~
..... /
/ \
, ....
\
xl> 2 I
I
<3<1
I
I - _-.... .......
I I
I
FIGURE 2.4. (a) Discharge curve for Li+ intercalation into TiS2 as a function of extent of dis-
charge. X. expressed as a stoichiometric factor in LixTiS2 (solid line, calculated relation 8 ). (b) Dif-
ferential coefficient of the curve for discharge of Li+ into TiS2 as in Fig. 3(a). (From Haering and
MacKinnon 8 .)
Supercapacitors and Batteries 27
also exhibit a small but significant pseudocapacitance. This appears to arise be-
cause of electrochemically active redox functionalities (Chapter 9) that exist on
the surfaces of high-area carbon powders and felts, depending on the conditions
of their pretreatment.
(2.3)
preciable toward the end of the charging half-cycle of a capacitor, there will be
a corresponding appreciable Faradaic self-discharge current following termina-
tion of charging when i is cut to zero, until the generated overvoltage has de-
cayed. In practice, self-discharge down to lower voltages often continues (see
the discussion in Chapter 18). Once overcharge sets in, the efficiency of further
charging to higher interelectrode potentials across the capacitor rapidly dimin-
ishes owing to the "Tafel" character of the potential dependence of the iF com-
ponent (Chapter 3).
Disadvantages
Limited energy density
Poor volume energy density
Low working voltages (compared with electrolytics; satisfactory compared with batteries)
Aq. voltage range 0 - 1.4 V; nonaq. to 4.5 V. In practice, 3.5 V.
Nonaq. embodiments require pure, H20-free materials; more expensive.
Requires stacking for high potential operation (electric vehicles)
Hence, good matching of cell units is necessary
30 Chapter 2
REFERENCES
1. D. Linden, ed., Handbook of Batteries, 2nd ed., McGraw-Hill, New York (1995).
2. H. A. Kiehne, Battery Technology Handbook, Marcel Dekker, New York (1989).
3. W. Lorenz and G. Salie, Zeit. Phys. Chern., N.F. 29,390,408 (196\).
4. J. W. Schultze and F. D. Koppitz, Electrochim. Acta, 21, 327, 337 (1976).
5. B. E. Conway, H. A. Kozlowska, and W. B. A. Sharpe, Zeit. Phys. Chem., N.F., 98, 61 (1975).
6. S. Sarangapani, B. V. Tilak, and C.-P. Chen, J. Electrochem. Soc., 143, 3791 (1996).
7. S. Hadzi-Jordanov, H. Angerstein-Kozlowska, and B. E. Conway, 1. Electrochem Soc., 125,
1473 (1978).
8. R. R. Haering and R. MacKinnon, in Modem Aspects of Electrochemistry, B. E. Conway,
lO'M. Bockris, and R. White, eds., vol. 15, Chapter 4, Plenum, New York (1981).
9. B. E. Conway, Electrochim. Acta, 38, 1249 (1993).
3.1. INTRODUCTION
On the basis of the assumption that this volume will be read not only by special-
ists in electrochemistry but also by electrochemical engineers and technologists,
as well as materials scientists, it has been considered desirable to include a brief
chapter on the basic aspects of charge transfer at electrode interfaces, especially
their energetics and kinetics. Some notes on the requirements for experimental
measurements on capacitor and battery electrodes are also included.
Ideally, the behavior of capacitative charge or energy storage devices, un-
like the situation with batteries, would not involve any excursions into, or ap-
plications of electrode kinetics. This statement is predicated on the assumption
that the charging or discharging of a capacitor device involves only electrostatic
processes and not any electrode processes of the Faradaic kind, the kinetics and
energetics of which, if significant, would lead to deviations from pure capacita-
tive behavior.
However, electrode kinetic effects do come into play whenever a capacitor
electrode ceases (practically) to be any longer ideally polarizable (Chapters 6
and 7). This can happen on overcharge when solution decomposition sets in
and/or when Faradaic self-discharge processes occur owing to the presence of
oxidizable or reducible impurities or reactive functional groups at carbon sur-
faces. Thus, in the case of electrochemical capacitors, some indirect or, in some
cases, direct involvement of Faradaic electrode processes can occur as follows:
33
34 Chapter 3
The electrode processes that are the subject of this chapter are of the so-
called "Faradaic" type involving electrolytic charge transfer of electrons be-
tween electrode interfaces and ions or molecules in solution; hence the origin of
the term, which is named after Michael Faraday's work, especially that on elec-
trolytic decomposition of solutions. However, it should be mentioned that at the
time (from 1834 onward) of this work, the details of such charge transfer proc-
esses involving electricity and chemistry I.2 were far from being understood. It
remained for Crookes and for J. J. Thomson (1897) to demonstrate much later
the common involvement of electrons in matter and their characterization in
terms of their charge/mass ratio and charge (by Millikan in 1909 and 1913). As
noted in Chapter 1, Faraday's laws implied an atomic unit of electricity, now
called the electron. However, it still took many years for it to be understood how
electrons became involved in electrochemical charge transfer processes. A
fuller understanding had to await: (1) knowledge about the electronic states and
their energy levels in atoms and molecules, a topic dependent on interpretation
of spectroscopic and ionization phenomena by Bohr and Sommerfeld and (2)
knowledge of the state(s) of free and bound electrons, their number density in
metals and semiconductors (by Fermi and Bloch), and their thermal (Richard-
son) and photoemission (Einstein) characteristics in relation to the so-called
"electronic work function" (t/J) for emission of electrons from metals.
The important conclusion from this work was that electrons are ubiqui-
tously present in all metals, with relatively high concentrations being free, mo-
bile, and delocalized-about one per atom; they are thus available for exchange
with ions or molecules across the metal's interface. Later, the somewhat differ-
ent states of electrons, (or deficiencies thereof, i.e., holes) at much lower con-
centrations in semiconductors became understood.
Energetics and Elements of the Kinetics of Electrode Processes 35
At the same time, the energetic states of ions (or molecules) in solutions in
polar solvents had to be understood since the elementary act of an electrode
process is the transfer of an electron to (cathodic) or from (anodic) a reactant in
solution and from or to the electrode.
A basic factor in such electron transfer processes began to be understood
in a fundamental way in the 1930s and in more detail in the 1940s and 1950s;
it was that electrochemical electron transfer processes occur in a so-called "ra-
diationless" manner, i.e., with no photochemical absorption or emission of light
(radiation) quanta. This means that there must be selective adjustment of elec-
tron energy levels in the electrode, relative to those in a reducible or oxidizable
reactant, so that the transfer of electrons takes place between levels that are
equal in energy. The solvation energy of the reactant ions or molecules in such
electron transfer processes is a major factor 3- 6 in determining the condition for
radiationless electron transfer and the rates of such reactions.
The general basis of this concept originated in papers by Gurney,7 Gurney
and Fowler,8 and Butler,9 was followed in more detail by the important paper
by Weiss,3 and later developed in a series of papers by Marcus 4•5 and Bockris
and Parsons. 6 The principal concepts are as follows:
1. The electrons involved in a Faradaic redox process are transferred from
(in a cathodic process) or to (in an anodic process) the Fermi level of the delo-
calized conduction-band electrons of the metal electrode. The electrons in the
metal obey the so-called "Fermi-Dirac statistics," and the upper level of half-
occupancy (the probability of the occupancy of that level being 0.5 at finite tem-
peratures) is designated the "Fermi level." Electrons at this level differ in energy
from those in a vacuum with zero kinetic energy by a quantity, CP, the electronic
work function of the metal. <l> varies from about 2 eV (ca. 46 kcal mol-lor 184
kJ mol-I) for the alkali metals to about 5 e V or more for Pt and other noble met-
als. The value of cP for a given metal also depends appreciably on the orientation
of the crystal face at which the electron is exchanged. cP can be regarded as the
negative of the electron affinity ofthe bulk metal through its surface and is thus
related in a general way to the electronegativity of the metal forming the elec-
trode material, and to its surface structure and ionization potential.
The energy required to remove an electron in a cathodic process is com-
pensated by the energy gained when it has been transferred to an electron ac-
ceptor (oxidant, "Ox," reactant) and vice versa for an anodic process, from a
reductant, "Red."
2. The reactants that are electron acceptors, "Ox," or electron donors,
"Red," in solution are "solvated" by the electrolyte solvent (hydrated in the case
when the solvent is water). The transfer of an electron to or from such an Ox or
Red ion in solution is associated with a major change in the solvation energy of
the ion and also involves the energy of ionization 10 (see later discussion). When
molecular reactants are involved, the electron transfer usually results in the for-
36 Chapter 3
mation of an ion, or an ion radical, or a radical, with a corresponding large sol va-
tion energy or with coupled generation or consumption of a proton in order to
achieve an overall charge balance in the reaction.
The overall energy changes in a simple electrode reaction can be usefully
represented by means ofan energy cycle (a Born-Haber cycle) based on the first
law of thermodynamics, which is related to the principle of conservation of en-
ergy. For example, for electron transfer involved in the reduction of a ferric to
a ferrous ion in aqueous solution at a metal electrode M (a single electrode re-
action), we can write the energy cycle as:
+ e (M) ------+~ Fe 2+
!l.G aq
from which the overalll1G for this half-cell electrode redox process is
(3.1)
Here Gs quantities are the Gibbs energies of solvation (hydration) of the ions
Fe3+ and Fe2+, and both are large negative energy quantities; J is the ionization
energy of the Fe 2+ ion in the gas phase to form Fe3+ in the gas phase, and IPM is
the electronic work function of the electrode metal M. The I1G quantities are
preferably expressed as the standard-state values, I1Go or GO, for a unit activity
or fugacity of the species in solution and in the gas phase.
The G, J, and IPM quantities in Eq. (3.1) are each relatively large, having
magnitudes of ca. tens or a few hundreds of kilocalories or kilojoules per mole.
However, their values with different signs add up algebraically to relatively
small numbers of 0 to ±lOO kJ mol-I. A similar situation arises for the I1Go val-
ues and corresponding acidity constant (pKa) values for acid ionization proc-
esses in aqueous solutions where solvation and bond energies determine the
2.3 RT(pKa) or I1Go values.
In the example treated earlier it is seen that the work function of the metal
M enters directly into the determination of the I1G or I1Go value for the half-cell
process and hence into its hypothetical electrode potential E = -I1G/zF. How-
ever, since a single half-cell potential can never be measured, only the I1E (i.e.,
the potential difference between two single electrodes) is experimentally acces-
sible. In this case the work functions of the respective two electrode metals do
not enter into the experimentally measured emf of the cell since their difference
Energetics and Elements of the Kinetics of Electrode Processes 37
(3.2)
38 Chapter 3
Vac--r---.
Redox reoction
o 0+ e(M)+ R
R
(non - matching energy levels)
(a)
Vac --.--,,-
o 0+ e(M) ..... R
R
at electrode potential V (matching energy levels)
FIGURE 3.1. Conditions for energy mismatching (a) and energy matching (b) at the electrode
Fermi level for facile electron transfer to occur in a radiationless process (based on Ref. 3 and later
representations by Gerischer).
for the redox process Ox + e ~ Red; flG s in Eq. (3.2) is positive for a decrease
of net charge.
When the result of electron transfer is the production of an intermediate
chemisorbed with energy A (A being negative), condition (3.1) becomes9
N
IE
u
8
------=- •••
Ti
.Nb
AI Bi
.Mo
,TO
Mo
__;'w
Cu
AQ,W-eF
.Au
0
3.5 4.0 4.5 5.0 5.5
Work function, ¢/eV
FIGURE 3.2. Empirical plots of log of exchange current-density values, io, for the H2 evolution
reaction at various cathode metals plotted against the electron work function, rp, in electron volts.
(From Conway and Bockris. 13 Reprinted with permission from J. Chern. Phys., 26, 532. Copyright
1957 American Institute of Physics.)
40 Chapter 3
-3
+160 o -160
FIGURE 3.3. Theoretical relation of Parsons for dependence oflog io for the HER on the standard
Gibbs energy, LlC:ds.H. for chemisorption of H at the electrode metal. (From Parsons. 12 Copyright
1958 Royal Society of Chemistry.)
11; this must be the energy of adsorption (AH) of H at the metal. The apparent
relation to (j) arises because AH usually depends on (j),13 e.g., for the initial heats
of chemisorption at low coverage.
Parsons 12 derived a theoretical relation for the dependence of log io on the
standard Gibbs energy (LlG~) for chemisorption of H at the metal, and its form
is as shown in Fig. 3.3. A maximum arises in log io when LlG~ is zero, because
log io is dependent on the coverage product, ~(1 - BID1-a, which is determined
=
by LlG~. This function has an obvious maximum when BH 0.5 and a 0.5, the =
transfer coefficient, and gives rise to the so-called "volcano relation" illustrated
in Fig. 3.3. Thus, volcano relations can occur in electrocatalysis for reasons
~imilar to those for regular heterogeneous reactions, as was discussed in classi-
cal catalytic work e.g., by Balandin. 14 An experimental plot of log io for the
HER vs. heat of adsorption of H based on critically selected data was given by
Trasatti 15 and is replotted in Fig. 3.4.
Only for those metals that have a strong affinity for some electro sorbed
species (e.g., H at Pt, Rh, Ru, Ir or Pb or Bi atoms at Au or Ag) does UPD occur
or alternatively, in the OPD potential range, when a desorption step is rate
determining, does appreciable potential-dependent surface coverage of the
electrosorbed species occur. Then, for such conditions, adsorption pseudoca-
pacitance (Chapter 10) arises. Thus, the energetics and kinetics of charge trans-
fer processes that lead to an adsorbed, discharged (or partially discharged)
species (see Ref. 16) are of major importance in determining which and what
Energetics and Elements of the Kinetics of Electrode Processes 41
3
cr:
ill
I
....
.E 5
~
E
u
«
--
~
0)
0
7
.Q
,
9
30 50 70 90
M-H Bond Strength (kcal mol· 1 )
FIGURE 3.4. Volcano plot for log io values for the HER at various cathode metals against heat
of adsorption of H (MH bond energy) as given by Trasatti 15 based on critically selected data.
i=zFv (3.4)
where v is the reaction velocity in mole s-1 cm- 2 and z is the number of faradays
passed per mole of reactants. The current density i is related to the current J pass-
ing at the available electrode area A by
42 Chapter 3
i =I1A (3.5)
Equation (3.4) applies to a given electrode process only if its current effi-
ciency is 100%; otherwise a current efficiency factor <1 must be applied. For
example, in the cathodic electrodeposition of Zn from Zn 2+ or ZnO~- ions in
aqueous solution, significant co-deposition of H, with H2 evolution, takes place,
so Eq. (3.4) applies properly only to either the partial current density for Zn
deposition or to the partial current density for H2 evolution. The relative propor-
tions must be analytically evaluated.
The primary feature of the kinetics of electrode processes, distinguishing
them from kinetics of regular chemical reactions, is their dependence on the po-
tential, V, of the electrode, which is usually referred to that of some reference
electrode in contact with the electrolyte solution.
This dependence on V arises energetically, as explained earlier, because of
the dependence of the electron work function (/J on V: (/Jy = (/Jy=o ± e V. Since
the electron is a reactant in the electrode process, changes of its energy in the
metal relative to that in vacuum modify the activation energy for the charge
transfer process and hence the rate constant of the electrode reaction.
Thus if the energy of the initial state of the reactant ion or molecule, plus
the electron in the metal, is changed by ±eV or ±VF per mole of electrons
(96,500 coulombs) then the activation energy is normally changed by some
fraction, p, of ±VF. p is commonly around 0.5 ± 0.1 for many electron charge
transfer processes, and is called the "barrier symmetry factor." It is analogous!?
to the Brj/lnsted coefficient for a series of related homogeneous proton transfer
processes which proportionates their Gibbs energies of activation to the stand-
ard overall Gibbs energies of the respective protonation reactions.
The significance of the effect of change of VF in relation to p can be illus-
trated in the schematic energy diagram of Fig. 3.5, which shows the effect on
the activation energy AE* (or ilC* for the Gibbs energy) that is involved in the
rate equation. It is found that
ilG*y = ilG*Y=o-
+ PVF (3.6)
over an appreciable range of change of V. P= 0.5 when the energy curves for
the course of the electrode reaction (e.g., discharge of H from an H30+ ion or
from water) along its reaction coordinate, d (Fig. 3.5) cross one another sym-
metrically, i.e. (numerically) with the same slopes dG/dd at and near the cross-
ing point corresponding to the transition state (activated state) of the electron
transfer reaction. For the discharge of H30+ or solvated metal (M) ions, the im-
mediate product of the electron transfer step is an adsorbed atom (H) or adion
of M at the electrode surface.
Energetics and Elements of the Kinetics of Electrode Processes 43
I
I
____________ J
, ,,
\
.
INITIAL STATE
REACTION COORDINATE, d •
FIGURE 3.5. Significance of effect of change of electrode potential, as VF, on energy of activa-
tion, till*, of an electron transfer reaction in relation to the barrier symmetry factor, p. (Equivalent
to an electrochemical Br¢nsted relation. 17)
The basic kinetic equation for such processes is as follows (Ref. 11 and
General Reading refs.), taking the H deposition case as the example:
(3.9)
(3.10)
The reciprocal of this derivative is called the "Tafel slope," and is denoted by b,
so that
with In i expressed as 2.3 log i; then b is written empirically in the Tafel equa-
tion:
tl = a + b log i (3.13)
after Tafel's work (1905) on the HER, which arose originally from his research
on the electrochemical reduction of strychnine. Various Tafel slope values (b)
can arise for the HER, depending on the rate-controlling mechanism that obtains
or the H coverage conditions (eH « 1 and potential dependent, or eH ~ 1 and
thus independent of tl).
More generally Eq. (3.7) can be written in the form
~ ~ (3.14)
ilzF =KCH:s(1- eH ) exp -[PtlFIRT] - K() H exp[(1- P)tlF1RT]
or equivalently in terms of the exchange current density, io , passing reversibly
at the equilibrium potential (tl = 0):
where the two terms on the right-hand side (rhs) ofEq. (3.14) or (3.15) represent
the forward and backward rates of the reaction, both of which are significant
near (within 10-15 m V) the reversible potential. Equations (3.14) or (3.15) are
called the "Butler-Volmer equation."
When the forward direction is predominant at appreciable values of 11,
i = io exp[-pl1FIRT], (3.16)
A comparison with Eq. (3.13), the empirical Tafel relation, reveals that
11 =PF og lo-PF og
2.3RT I . 2.3RT I .
1
(3.18)
so that
Note that 11 becomes more negative (for a cathodic process) as i or log i in-
creases. The increase of 11 logarithmically in i is characteristic of kinetic (in con-
trast to diffusion) or so-called "activation" control of an electrode reaction.
(3.20)
(3.22)
46 Chapter 3
Note that in Eq. (3.15) a negative sign is taken for the cathodic tT in the HER.
This latter relation (3.23) is useful for characterizing the dynamics of the
electrode reaction in terms of:
"~ Log I
----
OVERPOTENTIAL, Tj,+VE
Log I
~I \"~ Log io
TAFEL
FIGURE 3.6. The anodic and cathodic current components of the potential dependence of an
electrode reaction rate near its reversible potential: graphical representation of the Butler-Volmer
relation (Eq. 3.15) illustrating the dependence of the net current density, i =ia - ie, on overpotential
around the reversible potential (linear micropolarization relation) and the significance of the ex-
change current density, io.
The second significant point is that both curves intercept the axis of i val-
ues at +io for the anodic curve and -io for the cathodic curve. The distance be-
tween the intercepts in terms of current density is two times i o .
With increasing negative '7, the ic becomes progressively larger than ia un-
til ic » ia and Tafel behavior applies, i.e., ic then increases exponentially with
-'7. On the other side of the curve, for positive polarization, ia behaves similarly
with positively increasing '7. On logarithmic Tafel plots (i.e., for log ic or log
ia plotted against appreciable negative or positive '7 values), the intercepts oflog
ic or log ia on the '7 axis give the log of the exchange current density. This is one
of the standard procedures for experimental determination of log io or i o.
If the net current density, i = ic - ia (see the Butler-Volmer relation in the
form ofEq. 3.20), is plotted along with the individual component's partial ic and
48 Chapter 3
FIGURE 3.7. Onset of diffusion control in a current density vs. potential relation for the kinetics
of an electrode potential, at high current density or low reactant concentration. The effect of stirring
or electrode rotation is also shown.
the geometry of a disk with the rotation axis normal to its surface. Such experi-
ments can be conducted quite easily with modern rotated-disk electrode equip-
ment so that the role of diffusion limitation can be quantitatively characterized
and, for appropriate conditions, the diffusion constant of the reactive species de-
termined. However, this procedure is inapplicable for porous electrodes.
50 Chapter 3
Equations (3.7) or (3.14) have been written for a simple discharge reaction
exemplified by the first step of the hydrogen evolution reaction (HER) or by the
forward direction, or both directions of the H underpotential deposition (UPD)
process. It should be mentioned that other steps in the HER may be rate deter-
mining, such as electrochemical atom-ion desorption of H forming H 2, or the
chemical desorption of two adsorbed H atoms by catalytic recombination to H 2.
Such steps are represented by electrochemical rate equations different from
(3.7) or (3.14). However, the details are not relevant to the material treated in
this volume but may be found worked out at length in the General Reading Refs.
3,4, and 5. The case actually examined here illustrates the general principles and
energetics of electrode process kinetics involving electron transfer and overvol-
tage.
When a step subsequent to that of the initial electron transfer in the
cathodic direction of the HER, Tafel slope values (b) can be different from those
usually observed, namely, 2.3RTlPF with p:::: 0.5. They then depend on (1) the
type of desorption step involved, i.e., whether it is of the electrochemical kind
(with a further electron transfer event) or of the chemical kind, e.g., discharged
radical recombination or dissociation (as for H2 formation in the HER or involv-
ing CH3COO- and CH3 in the Kolbe reaction that produces C 2H 6 from dis-
charge of acetate); and (2) on the extent of coverage by the electrosorbed
intermediate, i.e., whether the fractional coverage (J is «1 and then potential
dependent or whether at elevated overvoltages (J--+ 1 and is then virtually inde-
pendent of potential.
The Tafel slopes that arise are then generally of the form 2.3RTI(n + P)F
or 2.3RTlmF where n or m are integers; the former arises when desorption of an
adsorbed intermediate is rate controlling via a further electron transfer and the
coverage by the intermediate is potential dependent according to some quasi-
equilibrium electrosorption isotherm (Fig. 3.8); the latter arises for a nonelec-
trochemical desorption step involving, for example, recombination of adsorbed
radicals (m :::: 2) (Fig. 3.8) or dissociation of a radical (m :::: 1), e.g., CH3COO".
Values of nor m are usually the integers 1 or 2, but for more complex sequences
(e.g., in anodic O 2 evolution), n can be 2 or m 4. 19
e,
When the coverage, by an adsorbed intermediate (e.g., H) as a function
of potential is known or can be assumed, the Tafel slope, b, takes the useful gen-
eral form:
(3.24)
Energetics and Elements of the Kinetics of Electrode Processes 51
w
.
C)
«
~
o
>
a:
w
o>
FIGURE 3.8. Schematic Tafel relations for alternative rate-controlling stages and chemisorption
conditions (OH« I or OH ~ I) in the HER: (a) rate-controlling H+ discharge; (b) rate-controlling
H desorption by a second H+ discharge; (c) rate-controlling H desorption by catalytic H + H recom-
bination (Tafel's mechanism).
where the first term on the rhs ofEq. (3.24) is the logarithmic derivative ofthe
adsorption isotherm, O(V) (e.g., for H in the H2 evolution reaction), and the sec-
ond term arises from the potential dependence of the electron charge transfer
rate through the barrier symmetry factor (fJ =:: 0.5) or electrochemical Brjijnsted
factor. 16 Special cases arise when d In OldV =FIRT or d In OldV =0 (0 ~ 1).
In the case of underpotential deposition (e.g. of H), no continuous Faradaic
currents pass (i.e., fJFIRT = 0 in Eq. 3.24), and adsorption pseudocapacitance
arises because 0 (e.g., 0H) is a thermodynamic function of V over some defined
potential range, about 0.05 to 0.35 V, depending on the substrate metal, which
is usually a noble one.
In the kinetic equation (Eq. 3.9) for i, the term for concentration ofthe re-
acting species (for example, H+ discharge) was written as CH,+s' the concentra-
tion of the reacting proton (or some other ionic reactive species). In terms of the
structure of the double layer at the electrode interface (Chapter 6), the local con-
centration of reacting cation (here aqueous H+) has to be expressed in terms of
the bulk concentration of that species CH,+b' From the theory of ion distribution
in the double layer (Chapter 6), the local concentration at the outer Helmholtz
plane is given by
52 Chapter 3
(3.25)
where IfIl is the potential at the inner limit of the diffuse double layer (i.e., at the
Helmholtz compact layer) relative to the potential in the bulk of the solution in
the absence of net ionic currents that could lead to an ohmic iR drop. This is the
potential that is derived from the theory of the diffuse double layer according to
Gouy and to Chapman (Chapter 6, references 7 and 9, respectively). (In the case
where the ions are significantly chemisorbed [usually anions at positively
charged electrode surfaces or near the potential of zero charge, pzc, at nega-
tively charged surfaces as well], the potentiallfll is appreciably modified.)
In the kinetic equation (Eq. 3.9), CH,+s must be substituted according to Eq.
(3.25). In addition, in Eq. 3.7, when double-layer effects are to be properly in-
cluded in the rate equation for i, account must be taken of the fact that it is the
local interfacial potential difference V - 1fIl> rather than V (or 11), that has to be
written in the rate equation. When these two effects are included (in the absence
of specific chemisorption of the reacting ions), the full electrode kinetic rate
equation for the example of proton discharge becomes from Eq. (3.7):
In dilute solutions, the theory for ion distribution in the region near and up to
the compact Helmholtz layer of the double layer formally gives an approximate
solution for the ionic concentration dependence of IfIl for dilute solutions (ionic
strength < ca. 0.1 M) as:
(3.27)
Note that for a cathodic process (i.e., one involving discharge of cations), IfIl is
a negative potential (relative to the bulk solution potential) that becomes nu-
merically smaller with increasing ionic strength. The effective thickness of the
diffuse double layer (the Debye length) becomes smaller in proportion, approxi-
mately, to the log of the ionic strength at relatively low ionic concentrations.
The basis of double-layer effects in electrode kinetics was thoroughly
worked out by Frumkin and his school in the 1930s and by Gierst in more spe-
cialized ways in the 1950s and 1960s (see Refs. 11 and 20). For the case of spe-
cific (chemisorbed) ions in the double layer, usually polarizable and
electron-donative anions, the double-layer effects cannot be treated in a gener-
alized way, i.e., without individual evaluations of their adsorption behavior and
their effects on the local potential difference across the compact Helmholtz
Energetics and Elements of the Kinetics of Electrode Processes 53
C=~q/~V (3.28)
*The term interphase is distinguished from interface in order to recognize the 3-dimensional nature
of the former as a region of finite thickness residing on the 2-dimensional interface defined by the
boundary of the electrode surface with the solution.
54 Chapter 3
and
Aq =f i·dt (3.29)
over some time interval At. Equation (3.30), as written, applies if the capaci-
tance, C, is constant with potential. Often experimentally it is not, so AV devi-
ates from a linear dependence on time at constant current. C is thus obtained as
the reciprocal of the slope of the relation between AV and At (Fig. 3.9), the time
elapsed to some point on the AV vs. At curve or differentially, at some point on
it, as (dAV I dtr l when C is not constant with AV. The measurable dependence
of AVon time at a constant current (i.e., on charge passed) is commonly referred
to as the "charging curve."
This applies to a so-called "ideally polarizable" electrode (see Chapter 6)
where the current i simply passes charge into the interface without any Faradaic
processes of transfer of charge across the double layer taking place, leading to
chemical change at the electrode surface. As long as that condition obtains, the
electrode interface remains ideally polarizable and i is purely a double-layer
charging current, i dl .
However, in practice, the charging current may be maintained in a voltage
range across the interface where Faradaic decomposition of the solution begins
to take place at that electrode (and then also at the counter electrode). The dou-
FIGURE 3.9. Constant current charging curve for an electrode interface having a double-layer
capacitance C.
Energetics and Elements of the Kinetics of Electrode Processes 55
ble layer continues to be increasingly charged with the rise of Ll V, but the current
i then becomes divided into two components, i d1 and iF, where iF is the Faradaic
current, which increases exponentially with Ll V when Ll V exceeds a value cor-
responding to a thermodynamic reversible potential for solution decomposition
(e.g., H2 evolution) at that electrode. This increase of iF follows a Tafel relation
in the overpotential, Yf, involved, as discussed earlier and represented by Eq.
(3.13). Then the charging situation can be written as
i = C(dVldt) + iF (3.31)
where C(dVldt) = i d1 and iF has the form i F = io exp [aYfFIR1J, which is the Tafel
equation in exponential form (Eq. 3.7), with a the transfer coefficient.
The charging curve then has the form shown in Fig. 3.9 (for constant C)
and as Ll V increases beyond its value corresponding to solution decomposition,
the Ll V vs. Lll relation increasingly deviates from linearity as the iF component
of i becomes progressively larger, i.e., a greater leakage current across the dou-
ble layer passes until the Faradaic process is the main charge-carrying compo-
nent, iF» i d1 • Then the electrode is behaving in a nonideally polarizable way.
The situation of transition from double-layer charging to mainly Faradaic de-
composition of the electrolyte as the potential is raised is illustrated in Fig. 3.9.
Region ab is for pure double-layer charging; region bc includes an increasing
component of the passage of charge in a parallel Faradaic reaction. ab is the re-
gion of ideal polarizability of the interface, prior to decomposition of the solu-
tion over region bc. Figure 3.10 shows schematically the relative values of the
l
LL
o
onset of non-ideal
~
UJ polarizability, iF 0
Z
oc...
---:....-
o==
o
!Z
UJ
a::
T
Constant i
= idl+ iF
a::
;:)
o
POTENTIAL
FIGURE 3.10. Components of the constant charging current of Fig. 3.9 at an electrode interface
when a Faradaic partial current, iF, passes in parallel with the double-layer charging current, idl.
56 Chapter 3
°
tial beyond the solution decomposition limit. Eventually, a steady state is
reached where iF ---t i as dVldt ---t and then i d1 ---t 0, i.e., the charge transfer is
entirely Faradaic at a sufficiently high steady potential or overvoltage for the
Faradaic reaction. The double layer can also be charged potentiostatically in a
potential step or potentiodynamically in a linear voltage sweep as described
later.
2. In a sequence of potential steps, JV, the charge, Jq, flows into the inter-
face to an extent determined by CJV where C is the capacitance over the poten-
tial range JV. A current transient it is generated (Fig. 3.11) by the pulse JV over
a small but finite response time and Jq is the integral of it over that time interval.
The capacitance can be calculated from the recorded Jq response for the pulse
JV, or the sum of Jqs over a sum of sequential JVs. In electroanalysis, this pro-
cedure is known as chronoamperometry. As in the first case of constant-current
charging (chronopotentiometry), as potential is increased toward and through
the solution decomposition limit or if a large-amplitude potential step, AV, is ap-
plied, the transient current response it contains transient components of double-
layer charging current and of Faradaic current. The response time, Jr, in which
the transient current it passes, is ideally very short but in practice it can be tens
of microseconds or some milliseconds, depending on the impedance charac-
teristics of the cell and the measurement system.
The time integral of the current-response transient, itr, in Fig. 3.11 gives the
charge that has flowed into the electrode interface as a result of the application
of the potential step, JV or AV. If the potential step covers some range of poten-
tial where a Faradaic current, iF, also flows (upper curve in Fig. 3.11), then the
charge passed by this parallel current component must be allowed for in calcu-
lating the charge entering the double-layer capacitance.
In some types of electrode-process measurements, a double-pulse proce-
dure developed by Gerischer is employed, first to charge up the double layer
quickly and then to observe the kinetic response of an electrode reaction to a sec-
ond, subsequent pulse.
3. In a so-called linear potential-sweep (potentiodynamic) experiment, the
applied potential (measured with respect to a reference electrode) is varied line-
Energetics and Elements of the Kinetics of Electrode Processes 57
Potential- step
w
I V2
(J)
z
oD.. • ..J
(J)
W
a::
§
I:!!
tzw oD..
a::
a::
;:)
o v, "" , iF>O
,,
"-
',iF"O
......
o
TIME (order of !IS or ms)
FIGURE 3.11. Current-response transient for charging an electrode interface under the influence
of a step of potential from VI to V2.
arly with time in a three-electrode cell and the resulting time-dependent re-
sponse current (Fig. 3.12) is registered by an analog (X-Y recorder or oscillo-
scope) or digital (transient recorder, computer, or digital oscilloscope)
recording instrument.
In such a voltage sweep experiment at a sweep rate s = dVldt (= constant),
the capacitative charging current, i, is
i = C (dVldt) = Cs (3.32)
or
C=ils (3.33)
In a sweep-reversal experiment (cyclic voltammetry) at constant is, the current
response profile is ideally a rectangle along the time-potential axis when C is
constant (Fig. 3.12, line a) or if it is not, then the differential profile of C is gen-
erated, often with a peaked structure (line b in Fig. 3.12).
4. In a self-discharge experiment through a load resistance, R, the time
dependence of potential is (see Chapter 18)
u
.
VI
II·exs)
.!!.. u i ~
H
:.0 I
0
c i
t-" ct I i
Z I
w + t
a:: i
a:: i
I
I
::J
--
U I VI IV2
0
w
CJ)
I __ POTENTIAL,V I
Z I I time) 1.::EILl
•
0 I -...... I
a..
-
.-_ t
CJ) u
:c0 >1 l~
....
w Sweep - signal
--
vO) _ - '0
a:: .&;.
I
1%
"0 I ,0
... ..... -"
U I
-!
oil( I
t~
,ILl
U
..
VI .~
'C
0
b
....
II C
ct
~
w
a::
a::
=>
U
0
POTENTIAL, V
w ( time)
V>
Z
0
a.. u
V>
w :c0
a:: .&;.
0
u
and ideally the real component Z' is infinity for an ideally polarizable electrode,
Most capacitor systems, especially those of the electrochemical type, have
a complex R-C equivalent circuit of distributed Rand C due to porosity (see
Chapter 14) and/or complex electrochemical reactions, and hence do not have
a simple impedance behavior as a function of frequency, In some cases, the im-
Energetics and Elements of the Kinetics of Electrode Processes 59
pedance behaves like that of a transmission line having a 45° phase angle over
a wide frequency range instead of 90° for ideal capacitance. Finite or significant
R limits power output performance as discussed in Chapter 15.
Ref.
± -
iii I.
1:1 I-
~ Plate-type cell
I in plastic frame
I (Schematic)
I J)
I
I
I
Ii ~ ~
"I I ~ I 1111
~separator
FIGURE 3.14. Plate-type test cell with arrangement allowing insertion of a reference electrode
probe.
3.10.2. Instruments
FUNCTION
POTENTIOSTAT - GENERATOR (5)
R C~ W
~
-
;;;;,CELl
I ,
-'V"",.N'y \ C I ,,- .....
',/ 'R'
(
\., //--'"
'\ \ " I
~
I / ~
{, W f
) , , .I
x- y -
'--
1-0 RECORDER
9 - POTENTIOMETER r--
REFERENCES
1. L. Pearce Williams, Michnel Faraday: A Biography, Chapman and Hall, London (1965).
2. B. E. Conway, in Electrochemistry, Past and Present, Chapter II, ACS Symposium Series
390, American Chemical Society, Washington, D.C. (1989).
3. 1. Weiss, Proc. Roy. Soc., London A222, 128 (1954).
4. R. A. Marcus, 1. Chem. Phys., 24, 966 (1956).
5. R. A. Marcus, Ann. Rev. Phys. Chem., 15, 15 (1964).
6. R. Parsons, and 1. O'M. Bockris, Trans. Faraday Soc., 47, 914 (1951).
7. R. W. Gurney, Proc. Roy. Soc., London, AI34, 137 (1931); A138, 378 (1932).
8. F. P. Bowden, Trans. Faraday Soc., 28, 368 (1932).
9. 1. A. V. Butler, Proc. Roy. Soc., London, A157, 423 (1936).
10. B. E. Conway, Ionic Hydration in Chemistry and Biophysics, Chapter 13, p. 260, Elsevier,
Amsterdam (1981).
11. B. E. Conway, Theory and Principles ofElectrode Processes, Ronald Press, New York (1964).
12. R. Parsons, Trans. Faraday Soc., 341053 (1958).
13. B. E. Conway and 1. O'M. Bockris, 1. Chem. Phys., 26, 532 (1957).
14. A. A. Balandin, Z. Phys. Chem., B2, 289 (1929).
15. S. Trasatti, 1. Electroanal. Chem., 39, 183 (1977).
16. 1. W. Schultze and F. D. Koppitz, Electrochim. Acta, 21, 327, 337 (1976).
17. B. E. Conway, in Progress in Reaction Kinetics, G. Porter, ed., vol. 4, Chapter 10, Pergamon,
Oxford (1967).
18. B. Losev, quoted by L. Antropov, Theoretical Electrochemistry, p. 395, Mir Pub!., Moscow,
1972.
19. K. 1. Vetter, Electrochemical Kinetics, Springer-Verlag, Berlin (1965).
20. L. Gierst, in Electrochemical Society Symposium on Electrode Processes, E. Yeager and P.
Delahay, eds., Electrochemical Society, Pennington, N.J. (1961).
21. D. C. Grahame, Chem. Rev., 41, 441 (1947).
22. H. Angerstein-Kozlowska, in Comprehensive Treatise of Electrochemistry, E. Yeager, J.
O'M. Bockris, B. E. Conway, and S. Sarangapani, eds., vol. 9, Chapter 2, Plenum, New York
(1984).
4.1. INTRODUCTION
The electrochemistry of double layers, and the ions and solvent molecules con-
stituting them, involves the electrostatic energies and molecular or ionic distri-
butions of these species in high interphasial fields. At charged electrode
interphases in double layers, the electric fields can become as high as 107 V
cm- 1, and similarly in the solvation shells of ions. The electrostatics of such
interphases are concerned with:
67
68 Chapter 4
Magnetic interactions are much weaker and are only important in spectroscopy,
in some solids, and in transition metal ion properties.
When a charged electrode interface is in contact with an ionic solution,
there is an accumulation of ions of one sign or the other, forming a double layer
(Chapter 6) and causing an orientation of dipoles of the solvent. Since ions in
the double layer are normally situated in a liquid solvent in contact with the elec-
trodes, the electric polarization of the medium will also be involved in determin-
ing the properties of the charged particles at or near an electrode interface. In
order to provide a basis for discussing the details of such questions in the theory
of the double layer and electrochemical capacitors, we present in this chapter
some elementary principles of electrostatics.
4.2.1. Coulomb's Law: Electric Potential and Field, and the Significance
of the Dielectric Constant
Perhaps the two most basic laws in physics and chemistry that determine
the short-range properties of substances are Coulomb's law of electrostatic
force, F, between two charges q1 and qz, distant r from one another, and the cor-
responding law of interaction that determines the force between two magnetic
dipoles. A third basic relation is the Pauli exclusion principle, which places re-
strictions on quantized energy states in assemblies of electrons in atoms or
molecules and is hence fundamental in defining interatomic forces arising from
electronic interactions in molecules. Analogous effects occur in metals, giving
rise to their band structure.
Coulomb's law has been experimentally verified as an inverse square law
like that for gravitation. The general relation for the force F between two
charges in a vacuum, is given by
(4.1)
where F is an attractive force when q1 and qz are of opposite sign and a repulsive
one when they are of like sign. The constant k depends on the units in which the
charges and distance are expressed and the force F is also dependent on the elec-
trical properties of the medium in which the charges q1 and qz are situated when
it is not a vacuum.
4.2.1.1. Units
In the electrostatic system of units, the unit charge is defined by Coulomb's
law as that charge which repels a like charge I cm distant from it in vacuo with
Treatment of Double Layers and Ions 69
k = 1I4nKo (4.2)
In some texts the symbol eo is used for the permittivity of free space, but
the symbol Ko is preferred here in order to avoid confusion with the static (zero
frequency) dielectric constant of a medium, also usually denoted by eo or eO. KO
is also sometimes referred to as the diabattivity of free space.
Electrostatic calculations in the rationalized units system thus depend on
forces calculated from Fr=QIQzI4nKoe,z or Ur=QIQ2/4nKoBr from corre-
sponding energies. The charges are written QI, Qz here in coulombs to distin-
guish them from q], q2 in Eq. (4.1), where the units are to be taken in esu.1t is
often, however, simpler to perform such calculations in the esu system with e
then taken simply as the dielectric constant (see later discussion) of the medium;
then forces appear as dynes and energies as ergs per particle. Conversion to
joules mol- I is easily achieved by multiplying by NAil 07 , where NA is
Avogadro's number, noting that 107 ergs = 1 joule. Itis obvious that the two sys-
tems must give the same results with the appropriate interconversion of units.
Thus a unit charge in coulombs is 3 x 109 times that in esu, or 1 C = 3 X 109 esu.
The conversion factor 3 x 109 (actually more exactly 2.998 x J09) originates
from the speed oflight in a vacuum, 2.998 x 1010 cm S-I, and is 1110 of this fig-
ure, corresponding to the coulomb being a practical unit that is 1110 of the value
of the absolute electromagnetic unit of charge, which is itself defined in terms
of the magnetic field produced in a circular coil of one turn having a radius of
1 cm, when a unit charge per second (current) is flowing.
70 Chapter 4
(4.4)
Therefore, equating the result in joules from the two systems, it is seen that
or
10-16
KO =-10-
- 7 /9 x 4n = 8.85435 x 10- 12 farad m- 1 (4.7)
qx1 (4.8)
-F(x)=--
eX2
(4.9)
Hence field varies as the inverse square of a distance x from a charge while po-
tential varies as the inverse first power of this distance (Fig. 4.1). From the form
of Coulomb's law, it is evident that the force on a charge q' in the field of q is
given by
F=_lxq' (4.12)
eX2
i.e., force is the product of the charge multiplied by the field due to another (or
other) charge(s). This formula provides the basis for the definition of the unit
charge given earlier.
72 Chapter 4
Potential cp
Distance x
FIGURE 4.1. Relation between electric potential and electric field as functions of distance, x,
from an ionic charge (schematic).
(b)
q2
Field Resultant E,.z.~ =E1 + EZ+IE3
FIGURE 4.2. (a) Scalar summation of potentials due to a distribution of charges at various dis-
tances dl. d2. d3 from point A. (b) Vectorial summation of fields to derive resultant field at a given
point due to the distribution of charges shown in (a).
Field intensity gives a measure of the so-called "force" associated with the
action of the field on a unit charge. One "line" per square centimeter is defined
as existing in classical electrostatics for each dyne per esu of field strength.
Lines of forces correspond to the tangential force experienced by a charge in the
field at the particular point concerned. Density of lines of force corresponds to
the flux and electrification. The concept of lines of force originated with Fara-
day.
The force at ron a unit charge due to q is q/r2 (8 = 1), i.e., the field intensity.
This field can be represented by drawing q/r2lines of force per square centime-
74 Chapter 4
ter at r. The total of such lines at a distance is the line density multiplied by the
total cross-section at r, i.e.,
A(J A Ae
C=--=-or-- (4.14)
4n(Jd 4nd 4nd
FIGURE 4.3. Model for discussion of the basis of Gauss's theorem in terms of normal induction
across an element of sectional surface "S through a surface Be at distance r from a charge q.
Let q be the enclosed charge and the flux of induction will be In . ds, and this
will be I cos e·ds and be equal to the field (q/?-) X (the shaded circle area, BM).
However ,the area BM/?- measures the solid angle Je. Then the flux of induc-
tion across the area Be is qde. Hence the total flux is
E= -4nq/e (4.17)
which is a form of Gauss's theorem. If the plate has two surfaces (i.e., it is not
a bulk conductor on one side), the result is E = -2nq/e.
the field components d¢Jldx, d¢Jldy, or d¢Jldz, increase or decrease in the various
orthogonal directions of the Cartesian coordinate system. In terms of p and the
dielectric constant I'. of the medium in which the space charge resides, Poisson's
equation is written
In terms of the x, y, Z coordinate system, and for the case where I'. is not depend-
ent on the field components d¢Jldx, d¢Jldy or d¢Jldz, the above equation is written
in terms of the partial field derivatives
(4.19)
(4.20)
The idea that a charge is associated with an energy is less familiar than the
concept of field or potential due to a charge. As with all energy quantities, it is
necessary to specify with respect to what reference state the energy is measured.
In the case of a charge, the energy originates from the work associated with
building up that charge (e.g., q) by adding elements of charge Jq brought from
infinity. Hence the "energy of the charge" is the work done in the building up
of that charge from an initial value of zero to its final value q, with increments
of charge, Jq, transported from reference distance 00 where the potential due to
the charge built up at any stage in the charging process is zero.
Let Aq be the charge established at a given stage of the charging of the in-
itially uncharged particle, where A is a fraction 0 < A < 1. The electrical work
done, oWe, in bringing up the next element of charge oq is (Aq·Jq)la if a is the
radius of the particle being charged. The total work done, We' for transfer of all
the charges Jq (i.e., from A =0 to A = 1) is given by
Treatment of Double Layers and Ions 77
q
W =f Aq·dq (4.21)
e a
o
The integral is evaluated by regarding the fraction A. as being progressively in-
creased from 0 to 1, so that the integration is made with respect to A. rather than
q, i.e., because,jq can be written as q.,j A.. Then
1 1
Aq·qdA. n 2 f (4.22)
We= f -a-=~ A·dA. =q2/2a
o 0
The same result may also be obtained by considering the charging energy
(1I2)C(11¢J)2 of a spherical particle treated as a conductor having a capacitance
C equal to its radius, a.
If the charging is carried out in a medium of dielectric constant, e.
(4.23)
W'=('8~)Ad (4.24)
where E is the field 11¢J/d. Ad is the volume of dielectric in the capacitor so that
eE2/Sn: must be the electric pressure or really the internal tension associated
with the field E, which follows from considering the units of the left- and right-
hand sides of Eq. (4.24). Equation (4.24) also provides a way of evaluating the
self-energy of an ion by integrating the P·dV work experienced by the dielectric
from the ion's periphery at a to 00. Thus
=f-
~
eW (4.25)
W
e Sn:
. 4n:r2 . dr =q2/2ea
a
o
Induced dipole
moment fL i-et
(4.27)
This work, Wi' is done on the atom or molecule; hence the positive sign for
Wi' The induced dipole, fli, however, interacts with the field E that produced it
with an energy -fl iE or -aeE2. Hence the total energy of induced polarization is
-aeE212.
Field direction
8 ------------------------.~ (t)
ILl
1-'= cose
Force -eE
Field E
Force ~eE
---
b
FIGURE 4.5. Interaction of a permanent dipole of moment, fl., with an electric field E: (a) Inter-
action energy with the field, fl.E cos O. (b) Torque resulting in orientation.
(b)
e Field direction E9 e Field direction 6)
Field E
Field E
(0 )
FIGURE 4.6. Vectorial addition of induced moment. !li. to permanent moment.!l. giving moment
!lR.
4.10.1. Dielectrics
Insofar as the physical influence of electric fields on a chemical substance
is concerned, the substance is referred to as a "dielectric." The material existing
between the plates of a capacitor in a material medium is also called the "dielec-
tric." The so-called "dielectric constant" of such a substance is a measure of the
susceptibility of the substance to undergo electrical interaction with, and suffer
electric "polarization" by, an applied field. More exact definitions and discus-
sions of these quantities are given in Chapter 5 on dielectric polarization phe-
nomena, including the relation of e to molecular and electronic properties of
solvent molecules such as a e and /1.
These three effects are significant in the very high fields obtaining in double lay-
ers and also in the solvation shells of ions populating double layers.
I~C"
Cf
fJ-/1/9~
: Ct
ce
I
1
and
The Sp3 geometry of each molecule is such that 3flcCl cos t/J =flcc! and 3flcH
cos t/J = flCH. Rence the molecules should have the same overall dipole moment.
This is not the case: flCHC! 3 = 1.1 D; flCH 3C! = 1.85 D [lD (debye) = 10- 18 esu].
The discrepancy could arise because the tetrahedral angle is not exactly main-
tained in chloroform due to repulsion of the CI atoms and/or because there is
some depolarization among the C-CI bonds, making them have lower bond mo-
ments than the single C-CI bond in CRCI 3; the latter effect is the main one.
In flexible polyatomic molecules, such as conducting polymers, the overall
dipole moment will depend on the conformation the molecule may adopt. For
Treatment of Double Layers and Ions 83
example, dioxane may exist in a boat (I) or chair (II) conformation. Structure I
has the higher dipole moment and will be preferred in the high fields near ions
or in double layers at electrode surfaces; it may also be preferred due to inter-
molecular H bonding by water.
Aq
dG=-·dq (4.29)
C
but dq = q·dA. Hence the energy G of charging (a Gibbs energy) is
q 1
G = f dG = f ~ . qdA (4.30)
o 0
=~·fA.dA (4.31)
o
1 1
=_q2/C=- CV 2 (4.32)
2 2
recalling that always C = q/V. C contains the dielectric constant, e (>1) of the
dielectric medium between the plates; e = 1 for vacuum, hence CCe) > CCe = 1).
This implies that a greater energy is stored in a capacitor constructed with a di-
electric having e > 1 than in one in a vacuum by the factor e. The extra energy
over that in a vacuum when e > 1 and geometrical dimensions of the capacitor
are the same is stored within the dielectric medium as an energy ofpolarization
of the dielectric, as explained in Section 4.4.7 concerning polarization of solvent
by an ionic charge, and especially in Chapter 5.
It is interesting that the calculation of electrical energy stored in a charged
capacitor can be conducted (as above) in a way closely similar to the derivation
of the "self-energy" of the charge on a chemical ion, i, due to Born l (1920). This
self-energy (a Gibbs electrostatic energy) is given (Eq. 4.23) by
(4.33)
where ri is the radius of the ion in vacuum, rie is its effective radius in the di-
electric solvent medium, and Zie is its charge. Note that these G i quantities de-
pend on half the square of the ionic charge, Zie, like the result in q2/2C for energy
in the case of capacitor charging. Then, by analogy between these two cases, it
is seen that C is equivalent to ri for a spherical ion. That is, the capacity of a con-
ducting sphere is equal to its radius, a principle in classical electrostatics.
Another aspect of electrochemical and physicochemical interest is that
since the stored energy of a capacitor is a Gibbs energy, it has an entropy com-
Treatment of Double Layers and Ions 85
ponent S == -dGldT, the temperature derivative of that energy. Other things re-
maining constant, the only quantity involving temperature dependence is the di-
electric constant of the dielectric medium determining C in the relation C =
Au.old (see Eq. 4.14 and the text following that equation). Hence the entropy of
charging is given (for B > 1) by
(4.35)
(4.36)
(4.37)
Since de/dT is normally a negative quantity for most if not all dielectric materi-
als, it is seen that the entropy of charging a capacitor having B > 1 is negative.
This is due to the electric polarization of the dielectric that is established in the
field between the plates of the capacitor. It is analogous to the entropy of mag-
netic polarization in magnetized paramagnetic or ferromagnetic metals. Analo-
gously also, if one could switch off the electric polarization instantaneously,
then an adiabatic dielectric depolarization cooling effect would arise which
might have practical technological value. However, in a double-layer electro-
chemical type of capacitor, such an effect would tend to be reversed owing to
the internal joule heating effect associated with the discharging current required
to transport accumulated ionic charges away from the two electrode interfaces
into solution when the two double layers were discharged, i.e., when V and q ~
O. In a double-layer capacitor, this entropy is associated mainly with solvent di-
pole orientation in the double layer and coupled ion accumulation at the capaci-
tor plate interfaces.
The distribution of charge on conducting capacitor plates is another matter
of interest: the distribution tends to be uniform except for edge effects. The elec-
tronic charge (±) on the conducting plates is a delocalized charge of conduction-
band electrons: an excess or deficiency of surface charge density compared with
the situation at two uncharged plates.
At the surfaces of an electrochemical double-layer type of capacitor, the
situation can be somewhat different because the charges in the solution, com-
plementary to the plus or minus electronic charge densities, are composed of
discretely charged ions of finite sizes; also, the distance of closest approach of
86 Chapter 4
REFERENCES
5.1. INTRODUCTION
or
where Ko is the permittivity of free space (see later discussion), sometimes sym-
bolized by BO' In the presence of a dielectric medium between the plates, C is
increased (cf. Eq. 4.14) to
C=Asl4nd (5.3)
Behavior of Dielectrics in Capacitors and Theories of Dielectric Polarization 89
or
C=AK/d (5.4)
(5.5)
proximately equal to the square of the refractive index, arising from electronic
and atomic polarization. For polar but non-H-bonded liquids, it has values
around 6 to 40, while for H-bonded liquids, it can attain much higher values,
e.g., 78 for water or 113 for HCN at ordinary temperatures. Some oxide mate-
rials can have relatively large t: values of several hundred. This is important for
fabrication of so-called "electrolytic" capacitors in which a thin oxide film is the
dielectric.
It is seen that C scales with t:, other conditions being constant. This is re-
lated to the involvement ofthe dielectric constant in Coulomb's law, where the
repulsive or attractive force between two charges, ql and q2, in a vacuum (Chap-
ter 4),
(5.8)
(5.9)
(5.10)
or
(5.11)
i.e., they are attenuated by the factor lit: if they are situated in a dielectric me-
dium having t: > 1. Similarly, capacitance of a given geometrical configuration
of plate electrodes is enhanced by the factor t: (> 1) over that for a vacuum (t: =
1) and correspondingly more (free) energy can be stored for a given applied
voltage, Ll V, when t: > 1, the energy being 112 CCLl V)2 (Chapter 2).
For two capacitors having identical geometries, the difference of stored
free energy for t: > 1 (real dielectric) and t: = 1 (vacuum) is
(5.12)
1. The first involves treatments in which the dielectric and its polarization
are examined in terms of bulk properties.
2. The second involves treatments in which such bulk properties are
evaluated by modeling at the molecular or molecular-assembly level.
This latter treatment involves principles of statistical mechanics in or-
der to relate averaged molecular properties in assemblies to bulk-phase
behavior at finite temperatures.
inverse "log" law in time usually applies or a "parabolic" law for some condi-
tions; see Ref. 3.)
The situation with double-layer capacitors is different since at each of the
capacitor ± electrodes a double layer exists across which there is a drop in po-
tential (see Fig. 6.3, Chapter 6) between the electrode plate and the electrolyte
solution; the dielectric of this double molecular capacitor is composed of only
one or two molecular layers of solvent, including solvated anions or cations in
that solvent layer, and it is polarized by the field associated with the differences
in potential between the metal and solution, especially that part which falls
across the first 0.3 to 0.6 nm (Helmholtz layer) of the solution near the electrode
surface. Interfacial dielectric properties of this very thin film have to be formu-
lated (see Chapter 7) to account for the magnitude of the double-layer capaci-
tance (16 to 50 JiF cm- 2) and its dependence on electrode potential, the sign of
the charge of the electrode plate, and the nature of the solvent and the electrolyte
solute.
Some of the principal aspects of the molecular and ionic modeling of the
double layer and its effective average dielectric properties are given in Chapters
6 and 7. In order to provide the background for the discussion in those Chapters,
we return now to the more general theory of bulk dielectrics in order to explain
the concepts of polarization and polarizability more completely, and their rela-
tion to experimentally measurable dielectric constants and molar polarizabili-
ties. These are fundamental matters that lie at the bases of capacitance behavior
in electrostatics, and in the phenomenology of double-layer capacitance and
electrical behavior of supercapacitors.
Apart from the invention and use of the Leyden jar (Chapter 1), Faraday
was the first to consider the state of dielectrics in charged capacitors. In fact it
was in correspondence with the polymath, Whewell of Cambridge, that the term
"dielectric" was suggested (December 1836) and it has remained in use ever
since. Faraday! initiated ideas of "polarization" due to electric fields and recog-
nized the induction of electric charges,with polarization being induced by one
polarized or polar particle into or onto another. He also recognized concepts
such as specific inductive capacity (8), lines of inductive force, and the strain in-
troduced in an electrified dielectric medium by an imposed field. Thus Faraday
recognized some of the properties of dielectrics and the nature of electric induc-
tive polarization before the middle of the nineteenth century. Of course, it was
many years later before these ideas became more exactly and mathematically
formulated by workers such as Mosotti, Clausius, Coulomb, Frohlich, Debye,
and Kirkwood in terms of molecular polar models. Unfortunately, as is well
Behavior of Dielectrics in Capacitors and Theories of Dielectric Polarization 93
known, 1 despite his depth of scientific perception and his inventiveness, Fara-
day never developed his concepts and interpretations of physical phenomena in
mathematical terms.
The electrostatic behavior of two identical configurations of capacitor
plates is considered here. One capacitor [Fig. 5.1(a)] has a vacuum dielectric,
the other [Fig. 5.1 (b)] a real dielectric medium having 8 > 1. An external field
Eo is applied and is operative between the plates generating or arising from plus
and minus charge densities on the plates, equally and oppositely. For a given
voltage difference, ~ V, between the plates or a corresponding field ~ Vld, charge
= =
densities 0'1 ±qtfA or 0'2 ±q21A appear, respectively, on the plates of the two
capacitors. 0'1 and 0'2 differ on account of the difference in 8 for the two cases;
81 = 1; 82 > 1. This difference corresponds to an induced charge density ±p,
which appears at the plates, changing the original a value [Fig. 5.1(b)]. When
the dielectric medium is present [Fig. 5.1(b)], the field between the plates is re-
duced from the vacuum value, Eo, to a diminished value E.
(0) +
Field Eo +
.-
Field Eo
~
- Field E~
+
+
+ Vacuum
+
...
+CT -CT
Dielectric
(b) / .......... ....---
/--
'......--"......- ,
-"""-,
,, Field E«E o)
,,..---"',/" "" ,
External field
--,- -,
Eo
1/--
. . . . . /,/"
,
I
t
Eo
+p -p
FIGURE 5.1. Fields E between charged capacitor plates: (a) in vacuum; (b) in the presence of a
dielectrically polarizable medium. Original charge density ±a; induced charge density ±p.
94 ChapterS
a
+
+
+
+
+
+
+
b p
+
+
1 cm2
+ - -.....~E---...••
The origins of the polarization thus induced in the dielectric are fourfold:
.....
Field E
8+-8-
fL~
.
..
..
fJ-i = a E
FIGURE 5.3. Redistribution of electronic charge density in a polarizable molecule in an electric
field (induced polarity).
96 ChapterS
Average moment.. ~
,,/ \
-----
, . Field E
-- - -.. ~ ~
• Field E
•
---
-IfI' -.. ---.. --- ~
-,/.-- •
(0) (b)
~E<kT ~E.» kT
(Normal polarization ( Dielectric saturation
experiment) e.o. at ions or
electrode interfaces)
FIGURE 5.4. (a) Orientational polarization of intrinsically polar molecules in a small electric
field. (Effect is additional to the induced electronic polarization in Fig. 5.3.) (b) Approach to full
orientation of solvent dipoles in the very strong field (p.FJkT» 1) of the double layer (dielectric
saturation condition).
From the point of view of choice of dielectric solvents for double-layer ca-
pacitors (see Chapters 8 and 13), the use of H-bonded solvents, though giving
high e values, has the disadvantage of relatively low decomposition voltages in
the range 1.23-1.5 V and rather high melting points. Higher operating voltages,
per cell, for double-layer capacitors therefore require so-called "aprotic"
nonaqueous solvents (Chapter 8) for their electrolytes (e.g., tetraalkylam-
monium salts) since such solvents, which do not have electrolytically active
(i.e., electrolytically depositable) H or other atoms, have substantially higher
decomposition voltages, e.g., 3.4 to 4.0 V. Useful practical examples are ace-
tonitrile, benzonitrile, N,N-dimethylformamide, propylene carbonate, di-
methoxyethane, and the tetrahydrofurans. Such solvents are also preferred
media for construction of nonaqueous lithium battery systems operating at 3-
3.S V per cell. Here the requirement is of course that the very base metal, Li not
discharge H2 from any "active" H atoms in functional groups of the solvent
Behavior of Dielectrics in Capacitors and Theories of Dielectric Polarization 97
molecule. "Active" H atoms in a solvent are usually those that are acidic and
participate in intermolecular hydrogen bonding. However, as is shown in Table
8.1, Chapter 8, a number of aprotic solvents do have quite high dielectric con-
stants (20-30), but since they are not H-bonded do not exhibit the strong coop-
erative polarization behavior that is found for such associated liquids as H 20,
CH30H, CH3 ·COOH, etc. Hence they have lower dielectric constants.
In terms of the diagrams in Figs. 5.2 and 5.4, a vector quantity P is defined
as the dielectric polarization, which is equivalent to a dipole moment per unit
volume [Fig. 5.2(b)]. P is thus equivalent to a charge p (per square centimeter)
induced at the plates of the capacitor multiplied by a unit length of 1 cm, i.e., a
dipole moment per unit (1 cm3 ) volume. p is sometimes written as ai, the in-
duced a diminishing the original a value.
In the absence of a polarizable medium (8 = 1), the field due to a surface
charge density a per square centimeter is [Fig. 5.1(a)] Eo =4na (Gauss's rela-
tion), which is also referred to as the dielectric displacement, D. Owing to the
presence of the dielectric, the field Eo, which in the absence of a dielectric is due
to a, becoming reduced (see Coulomb's law, E = -qI8?-) by 4np [which is re-
lated to the induced charge density p, Fig. 5.1(b)], so that
D=E+4np (5.14)
so that
The induced dipole moment, Ili' is proportional to the field for low or mod-
erate fields (i.e., Ili = aE where a is the distortional polarizability), mainly ow-
ing to redistribution of electron density in the molecules. It has the dimensions
of volume and magnitude on the order of 10- 24, i.e., - (10- 8)3 or angstroms
cubed (nm3 x 10- 3).
For a dilute gas, the effective polarizing field is the external field, Eo. If M
is its molecular weight and p its density, MIp is the molar volume (here p is the
density) or MINAP is the molecular volume (NA =Avogadro's or Loschmidt's
number) and the induced polarization, Pi is
NAP (5.17)
=-(a~)
M
(5.18)
Then from Eq. (5.18) defining Ili' and using Eq. (5.15)
If the dielectric is not a gas but a condensed phase in which molecular in-
teractions are considerable and short range, the influence of the molecular sur-
roundings on a given dielectric molecule has to be taken into account: a given
dipole in a hypothetical molecular-sized cavity in the medium induces charge
density on the walls of that cavity which then generates an opposing (induced)
local field, the reaction field. Then the effective field Ef becomes related to E
and P in a relatively complex way, leading to
(5.20)
,ui=a(E+ ~n p) (5.21)
(5.22)
and this refers still to induced dipoles through,ui' This last equation was derived
by Mosotti5 and also independently (see Ref. 9, p. 199) by Clausius. It is now a
classical relation in dielectric theory and is referred to as the Clausius-Mosotti
equation. Actually, since a is a polarizability, PM also has the units of po-
larizability, i.e., of molar volume.
~ = coth (,uE)_ kT
,u l kT ,uE
(5.23)
Ii =(,u2/3kT) E (5.24)
(5.25)
a relation derived by Debye with the aid of the Langevin function for "ji/f1 above
(Eq.5.23).
(5.26)
where ()ij depends only on the coupled orientations of the i th andjth molecules,
each with z nearest neighbors.
Another relation is the Kirkwood-Frohlich equation:
(5.28)
where z is the average number of neighbors in the first coordination shell and e
is the HOH bond angle in water, about 105°. The value of z can be derived from
X-ray diffraction data. Other general and more detailed aspects of dielectric po-
larization are treated in Refs. 9, 10, and 11, the monograph volumes by Frohlich,
Smyth, and Bottcher.
The correlation factor will also be important in the orientation polari-
zation and its contribution to the local dielectric constant of the interphasial
double layer where solvent dipole orientation occurs in response to that part
of the metal-solution potential difference at an electrode/solution interphase
across the compact Helmholtz region. The interaction energy factor in the
treatment of interphasial solvent dipole orientation is of major importance in
defining the approach to dielectric saturation in the double layer at electrodes as
treated in a paper by Bockris, Devanathan, and Miiller I2 and in several recent
papers by Marshall and Conway.13,14 In particular, some minimum strength of
dipolar interaction is required to avoid a "catastrophe"J3,I4 in the values calcu-
lated for the contribution of dipole orientation to the double-layer capacitance
arising from the reciprocal dependence of the orientation surface-potential con-
tribution I2 on the electrode surface charge density at a polarized electrode. This
difficulty arises in the two-state orientation model (Ising-type model in mag-
netic polarization) first considered for the double layer. 12 In more sophisticated
three-state or cluster models for interphasial water polarization, these difficul-
ties are avoided (see Chapter 7).
Using the treatment by Booth l5 (see Chapter 7), Conwayl6, Bockris and
Ammar 17, and Grahame l8 made the first calculations of the local dielectric co-
efficient of water in the diffuse and compact parts of the double layer at elec-
trodes in aqueous media. Much more is now known about the state of the water
dielectric in the double layer, e.g., see Chapter 7 and Ref. 19. The calculations
indicate that the e for water is lowered appreciably from its normal bulk (zero-
field) value of78 at 298 K in the diffuse layer and more so in the compact Helm-
holtz layer, where its value can descend to about 10-20, depending on the
electrode/solution potential difference. More recent estimates 10 indicate a mini-
mum value of around 6. The various treatments of high-field effects on the di-
electric constant of water, including experimental attempts to detect a lowering
at high fields (but much less than those in double layers), are summarized by
Smyth in Ref. 9, Chapter 3, p. 88.
The types of calculation referred to here are really based on bulk models
of the water dielectric. These cannot, however, be expected to reliably represent
the behavior of a lattice of water molecules only two or three molecular diame-
ters wide at the electrode interface, not to mention the local solvational influ-
ence of the ions that also occupy an appreciable volume fraction of the compact
layer comprising this thin film of interphasial solvent molecules. In fact, de-
pending on the electrolyte and the electrode/solution potential difference, some
30-40% of the interphasial water molecules can be electrostatically influenced
by the high radial fields of neighboring cations or anions. 2o Under such condi-
tions, the bulk dielectric saturation theories of high-field polarization must be
Onset of dielectric
!z saturation
w
C3
ii:
u..
w
8
o
cr
t
~
w
c .-- Optical dielectric
--- ~~~t~nt.-rr- -------------------------
o 5 6 ' 7
FIGURE 5.5. Variation of dielectric coefficient of a solvent (e,g" water) (Refs, 15, 17) in an in-
creasing electrostatic field (log scale), toward the dielectric saturation limit (schematic),
104 ChapterS
REFERENCES
1. L. Pearce Williams, Michael Faraday: A Biography, Chapman and Hall, London (1965).
2. B. E. Conway, Electrochernical Data, Elsevier, Amsterdam (1952).
3. N. F. Mott and B. Cabrera, Rept. Prog. Physics, 12, 163 (1949).
4. P. Debye, Phys. Zeit., 13, 97 (1912); see also P. Langevin, 1. Phys., 4 (4), 678 (1905).
5. O. F. Mosotti, Mern. di Mathern. e Fisica, Modena, 24 (II) 49 (1850).
6. R. Clausius, Die rneclwnische Wiinne theorie /I, p. 62, Braunschweig (1879).
7. J. G. Kirkwood, 1. Chern. Phys., 7, 911 (1936).
8. J. G. Kirkwood and G. Oster, 1. Chern. Phys., 11, 175 (1943).
9. C. P. Smyth, Dielectric Behavior and Structure, McGraw-Hill, New York (1938).
10. H. Frohlich, Theory of Dielectrics, Oxford University Press, Oxford (1949).
11. C. J. F. Bottcher, The Theory of Electric Polarization, Elsevier, Amsterdam (1952).
12. 1. O'M. Bockris, M. A. V. Devanathan, and K. Miiller, Proc. Roy. Soc., Lond., A274, 55
(1963).
13. S. Marshall and B. E. Conway, 1. Electroanal. Chern., 337, 1 (1992).
14. S. Marshall and B. E. Conway, 1. Electroanal. Chern., 337,19 (1992).
15. F. Booth, 1. Chern. Phys., 19, 391, 327, 1451 (1951).
16. B. E. Conway, Ph.D. thesis, University of London (1949).
17. B. E. Conway, J. O'M. Bockris, and I. A. Ammar, Trans. Faraday Soc., 47, 756 (1951).
18. D. C. Grahame, 1. Chern. Phys., 18, 903 (1950).
19. Symposium on the Structure of the Electrified Interface, D. J. Henderson and O. R. Melroy,
eds., Electrochirn. Acta, 36, 1659-1894 (1991).
20. B. E. Conway, 1. Electroanal. Chern., 123, 81 (1981).
21. G. M. Torrie and G. N. Patey, Electrochirn. Acta, 36, 1677 (1991).
22. A. M. Brodsky, M. Watanabe, and W. P. Reinhardt, Electrochirn. Acta, 36, 1695 (1991).
Chapter 6
6.1. INTRODUCTION
negatively) with respect to the electrolyte solution, with a separator (as in a bat-
tery cell) usually being arranged between the two electrodes. The two-electrode,
two-interface system in a single capacitor cell is illustrated in Fig. 6.1(a).
While the capacitative behavior of individual electrode interfaces can be
studied experimentally, the electrical circuitry must always include a second
(counter) electrode and also preferably a separate reference electrode with re-
spect to which the potential measurements can be independently scaled and con-
trolled. Similarly, a double-layer capacitor device must always involve (at least)
two electrodes. This is an unavoidable requirement of all electrode interface
measurements and all constructions of electrochemical devices, e.g., capacitors
and battery cells. If the electrochemical behavior of each of the pair of electrodes
is to be examined, then a third, reference, electrode is required.
In the charged condition there are two interphasial drops in potential across
the capacitor cell, one across each double layer [Fig. 6. 1(a)]. Upon discharge,
there is also a current-dependent, ohmic IR potential drop within the solution,
and the opposite on recharge [Fig. 6.1(b)].
Since one of the main technological directions of electrochemical capaci-
tor development is in the field of the double-layer type of capacitor, this Chapter
is devoted to a somewhat detailed description of the structure of the double layer
and the origin of the capacitance associated with it. A detailed understanding of
the properties and structures of double layers is essential for a full understanding
of the operation of double-layer capacitors and the capacitance values that are
achievable per square centimeter, or per cubic centimeter of active porous ma-
terial in various systems. This will also require the mathematical representation
of the properties of the double layer related to the nature of the electrolyte and
solvent on the solution side of the electrode-materiaVsolution interface and to
the properties of the electrode itself. The theoretical treatment and modeling of
the double layer are discussed in Chapter 7.
Determinations of the double-layer capacitance and its potential depend-
ence provide detailed information for examining the behavior and structure of
electrified interfaces. This is mainly because the dependence of the charge, q,
held on each side of the electrode interface (electron density on the metal and
ion density on the solution side) on the measured electrode potential, E (which
is equivalent to the Fermi level of electron energy states in the metal) is directly
determinable as a differential quantity, Cd!> dq/dE; such types of quantities al-
ways give more resolved information than corresponding integral relations, e.g.,
total charge q plotted vs. the electrode potential E at which it has been accumu-
lated, or q divided by E at a given electrode potential. That is why cyclic vol-
tammetry and ac impedance measurements are especially valuable and
preferred in studies of the double layer and the resulting electrochemical capaci-
tor devices; they both give differential information. A typical relation between
The Double Layer at Capacitor Electrode Interfaces 107
a Electrolyte
/ ~
- ;,-+ +-+- + - + -- -
- ~+ - -+- - +- - + -
- ~ +- +-+ + - + -- -
-~ ++ +-+ -+-+- -
-~ +- +-+ +-+-+-
-~ ++ +-+ -+- - - -
-:/+ -+ - +- -+-+--
-~ + -+ - +- +-+-
-~ + -+ - +- - +- - -
.;
Porous Porous
electrode Separator electrode
Configuration of an electrochemical
capacitor requiring two electrodes
and thus two double-layers
b Electrolyte
,/ ~
+
+
+
+
+
+
+
+
+
Separator
capacitor on discharge
f( y)
\
y J,/f(dY/dX)
\
\
\
\
\
"....
x
FIGURE 6.2. The relation between arbitrary integral signal curve x,y, (e.g., for a double-layer
charge as a function of potential) and its differential coefficient, dyldx (e.g., for differential capaci-
tance).
an arbitrary integral curve and its differential, illustrating this point, is shown
schematically in Fig. 6.2.
It is appropriate first to describe the structure of the double layer, i.e., of
the interphasial region of the metal/solution boundary. The term interphasial re-
gion! is deliberately chosen over the word "interfacial" (see Chapter 3, section
3.8) since the boundary region is really a 3-dimensional one, albeit very thin,
some 0.3 to 0.5 nm in thickness, rather than the 2-dimensional one implied if
the term "interfacial" were used. This means that the concepts of 3-dimensional
phases can be used to describe the double layer, such as surface concentration
or surface excesses, e.g., of ions of the electrolyte and solvent molecules.!,2
It is logical to describe these models in the order in which they were his-
torically proposed in the literature, which is also the order of their progressive
approach toward a correct description of the structure of the interphase at elec-
trode surfaces.
The concept of a double layer corresponds to a model consisting of two ar-
ray layers of opposite charges, separated by a small distance having atomic di-
mensions, and facing each other, as on the plates of a two-plate hardware
capacitor. This model was adopted by von Helmholtz3 to describe his perception
of the distribution of opposite charges, quasi-2-dimensionally, first at the inter-
face of colloidal particles. It is illustrated in Fig. 6.3(a), which shows its compact
structure, and is referred to as the Helmholtz double-layer mode1. 3,4
The Double Layer at Capacitor Electrode Interfaces 109
IT.. =8-
0-- HELMHOLTZ LAYER
FIGURE 6.3. Models of the double layer: (a) Helmholtz model, (b) Gouy point-charge model
(specific charges a per unit area as indicated for anions and cations as an example), (c) Stem model
for finite ion size with thermal distribution, combining Helmholtz and Gouy models.
In the original model for colloid interfaces, the charges on the surface side
of the double layer arise either from acid-base ionization, as with proteins or
polyelectrolytes, or on account of the adsorption of ions, as at lyophobic col-
loids. On the solution side of the double layer, counterions of opposite sign of
charge accumulate to balance the charge on the colloid, forming a double-layer
array of positive and negative charges.
The Helmholtz model was later adapted to the case of electrode interfaces
where, on the metal side, a controllable surface density of excess negative or
positive charge can arise that corresponds to an excess or deficiency of electron
charges of the delocalized electron plasma of the metal. Owing to the high free
electron (e) density in the metal (approximately 1 e per atom), any net charge
density of electrons at the surface is strongly screened, so the gradient of elec-
tron density at a charged metal interface is highly localized over a distance of
only 0.05 to 0.2 nm, the so-called Thomas-Fermi screening distance (Fig. 6.4).
Because the wave function amplitudes of the conduction-band electrons retain
significant but diminishing magnitudes outside the formal electrode surface
plane, there is significant spillover of electron density into the double layer on
the solution side of the interface5,6 and the effect is potential dependent.
In the case of p- or n-semiconductors, the charge-carrier (hole or electron)
densities are, however, very much smaller than in metals by a factor varying
from about 10-4 to 10-15. As a consequence, there is a distribution of the charge
carriers away from the interface (Fig. 6.5) but extending into the bulk of the
semiconductor over a relatively large distance that is inversely related to the
charge-carrier density (cf. the situation for ion distribution in an electrolyte in
the solution side of the interface, Section 6.3). This distribution of charge carri-
ers within semiconductors, near their interfaces, follows mathematically exactly
110 Chapter 6
Thomas - Fermi
Appro)!.. 1e
..
screening distance
~
per atom in
bulk
Free electron density
--- distribution
METAL SOLUTION
\,/Electran overspill
I
.... - - - - to zero
I
t
Locus of
~Nominol surface
plane
atomic
nuclei
1
0
cr
~
9
----- ~9>
n space - charge
/ region e
/ /
SEMICONDUCTOR IONIC SOLUTION
FIGURE 6.5. A space charge distribution of charge carriers within an n-type semiconductor near
its surface that is like ion distribution in the diffuse layer in solution.
The Double Layer at Capacitor Electrode Interfaces 111
the same form as for ion distribution in the diffuse layer on the solution side
(Gouy-Chapman theory for dilute ionic solutions).
Some time after von Helmholtz's model was proposed, it became realized
that ions on the solution side of the double layer would not remain static in a
compact array as in Fig. 6.3(a) but would be subject to the effects of thermal
fluctuation 7 according to the Boltzmann principle. 8 This latter effect would de-
pend on the extent to which the electrostatic energy Ue (together with any
chemisorption energy Uc ) of the ions' interactions with the charged metal sur-
face exceeded, or were exceeded by, the average thermal energy, kT, at tempera-
ture, T, K, i.e., the ratio (Ue + UJlkT.
Gouy7 introduced this thermal fluctuation factor into a modified repre-
sentation of the double layer in which the counterions conjugate to the metal
surface's electron charge were envisaged as a 3-dimensional diffusely distrib-
uted population of cations and anions [Fig. 6.3(b)] of the electrolyte having a
net charge density equal and opposite to the virtually 2-dimensional electron ex-
cess or deficit charge on the metal surface.
In this model, the ions were assumed to be point charges. Historically, this
was an important restriction since it led to a failure of Gouy' s model on account
of (1) an incorrect potential profile and local field near the electrode surface and
(2) consequently a too-large capacitance being predicted, that quantity being de-
fined as the rate of change of net ionic charge on the solution side with the
change of metal-solution potential difference across the interphase. The inter-
phasial capacitance associated with this model is commonly referred to as the
"diffuse" double-layer capacitance.
A full mathematical treatment of the Gouy diffuse-layer model was given
in some detail by Chapman in 1913 9 (see Section 6.3), based on the combined
application of Boltzmann's energy distribution equationS and Poisson's equa-
tion lO for the relation between ionic space charge density in the interphasial re-
gion to the second derivative of electric potential, IJI, with respect to distance
from the electrode surface. It is interesting to note that the mathematics and prin-
ciples used by Chapman anticipated the approach taken by Debye and Huckel
in 1923 11 in determining ion distribution in three dimensions around a given ion
in their treatment of activity coefficients and conductance of electrolytes. Later
it was used by Onsager,12 in an improved treatment of the conductivity of elec-
trolytes.
In both Chapman's and Debye and Huckel' s treatments of ionic charge dis-
tribution, the key equation resulting from the combination of Boltzmann's en-
ergy distribution function and Poisson's electrostatic equation lO has been
referred to as the "Poisson-Boltzmann" equation. It is also utilized in the treat-
ment of band profiles and space charge effects in semiconductors. 13
The serious problem with the Gouy-Chapman treatment, overestimation
of the double-layer capacitance, was overcome by Stern in 1924 14 in the next
112 Chapter 6
stage of development of the theory of double layers. In his model and calcula-
tions it was recognized that the inner region of the ion distribution could be
treated in terms of an adsorption process according to Langmuir's adsorption
isotherm, and the region beyond this inner layer, into the solution, could be val-
idly treated in terms of a diffuse region of distributed ionic charge [Fig. 6.3(b)]
as treated by Gouy 7 and by Chapman. 9 In addition, if the ions were recognized
as having finite size, including the annular thickness of their hydration shells
(their so-called Gurney cosphere radii 15 ), it was easy to define a geometrical
limit to the compact region of adsorption of ions at the electrode surface [Fig.
6.3(c)]. This is taken to correspond to a Helmholtz type of compact double layer
having a capacitance CH , while the remaining ionic charge density beyond this
compact ion array is referred to as the "diffuse" region of the double layer, hav-
ing a capacitance Cdiff . Cdiff and CH are conjugate components of the overall
double-layer capacitance, Cd], related by the equation
1 1 1 (6.1)
-=-+--
Cd! CH Cdiff
-----II I I 1-1- -
On account of the reciprocal form of the terms of Eq. (6.1), it will be seen
that the Cd! will be determined by the smaller of the two components, CH and
Cdiff . This is of considerable importance in determining the properties of the
double layer and its capacitance as a function of electrode potential and ionic
concentration of the solution.
The original paper by Stern!4 in Zeitschrift for Elektrochemie (1924) is
somewhat obscurely written, but Parsons, in an important article in 1954,4 pre-
sented a much clearer version of this treatment in which the limit for a distinc-
tion between the Helmholtz compact layer and the diffuse layer beyond it [Fig.
6.3(c)] can be understood in terms of the distance of closest approach of counter
anions or counter cations to the metal electrode surface.
By introducing a distance of closest approach of finite-sized ions and thus
geometrically defining a compact Helmholtz inner region of the double layer,
the problem of a far too high capacitance that arises in the Gouy-Chapman
treatment is automatically avoided. This difficulty arises since the capacitance
of two separated arrays of charges increases inversely as their separation dis-
tance, so very large capacitance values would arise in the limit of infinitesimally
small (point charge) ions very closely approaching the electrode surface.
The Double Layer at Capacitor Electrode Interfaces 113
The Stern theory of the double layer remained a good basis for general in-
terpretations of electrode interface phenomena, including double-layer effects
in electrode kinetics 16 until the detailed work of Grahame in the 1940s on the
double layer capacitance at the mercury electrode in aqueous electrolyte solu-
tions reported in various papers, particularly in the seminal source review paper
in Chemical Reviews in 1947.17 Its semicentenary was celebrated at a special an-
niversary Electrochemical Society symposium in May 1997.
Grahame's work emphasized the great significance of the specificity of
double-layer capacitance behavior at Hg to the nature of the cations and anions
of the electrolyte, particularly the size, polarizability, and electron-pair donor
properties of the anions of the electrolyte.
This led Grahame to make an important distinction between an inner and
an outer Helmholtz layer in the interphase which correspond to the different dis-
tances of closest approach that can arise for anions vis a vis cations at the elec-
trode surface. This difference of distance of closest approach is mainly caused
by the fact that most common cations are smaller than common anions (Table
6.1) and retain solvation shells due to strong ion-solvent dipole interac-
tion.1O·18.23 Thus, the Gfahame model (Fig. 6.6) consists of three distinguishable
regions: the inner Helmholtz layer. the outer Helmholtz layer, and always a dif-
fuse ion distribution region. At extremes of polarization (i.e., for high positive
or high negative charge densities), one or the other of the Helmholtz layer re-
gions dominates, with a population of anions or cations, corresponding to such
polarizations. Because anion distances of closest approach are usually smaller
than hydrated cation distances of closest approach, the inner layer capacitance
at positively charged electrode surfaces is usually about twice that at a corre-
sponding negatively charged surface, (16-25 f.1,F cm- 2), though this depends on
the metal and the ions of the electrolyte, and the solvent. These aspects of dou-
ble-layer capacitance behavior are of great significance for understanding the
properties of double-layer supercapacitors and the magnitude of capacitance
that can be achieved per square centimeter over various ranges of potential and
at various electrode materials.
TABLE 6.1. Pauling Crystal Ionic Radii of Alkali and Halide Ions (nm)
Li+ 0.060 F 0.136
Na+ 0.095 Cl- 0.181
K+ 0.133 Br- 0.195
Rb+ 0.148 [- 0.216
Cs+ 0.169
NH! 0.139
H30+ 0.138
Notes: See Ref. 10 for other scales of ionic radii.
Source: Reprinted with permission from f. Am. Chern. Soc., 49, 771 (1972). Copyright American Chemical
Society.
114 Chapter 6
GOUY-CHAPMAN
I NEUTRAL
I MOLECULE
I
I
I1//~
1. /
1 c..OUTER'HELMHOLTZ LAYER
t"-----lNNER ....
:2.
FIGURE 6.6. General representation of the structure of the double layer showing different re-
gions for adsorption of hydrated cations and less hydrated anions (Grahame model!?), together with
solvent molecules and an adsorbed neutral molecule.
30 X 10-6 20 X 10-6 .
+ - - - - or - 1.11 x 10 15 ' respectIvely,
1.11 x 1015
and thus to
relatively concentrated aqueous acid (H 2S04) or base (KOH) solutions that are
used as electrolytes for a number of electrochemical capacitor embodiments, it
is clear that there must be very little free water in the interphase that is not in-
fluenced by the ions either in the bulk electrolyte or in the Helmholtz layer. 19
This is an important but little realized aspect of double~layer modeling and has
significant practical consequences, in that there may be local changes of solvent
activity and balance during charging or discharging processes.
Double-
layer
I" .\
Bulk
electron density
~tozero
METAL SOLUTION
tt Nom;nol metal
surface plane
LOCus of centers
of metal surface
atoms
FIGURE 6.7. Schematic profiles of emergent electron density at a metal at three potentials: one
positive (1), one negative (3) to the potential-of-zero charge, and one (2) at the potential-of-zero
charge. (After Lang and Kohn ref. 5).
vent molecules in the compact region of the double layer. This model has been
envisaged and treated by Lang and Kohn,5 and more recently by Amokrane and
Badiali. 6 More details are discussed in Chapter 7.
The variation of the locus of the electron density overspill with changing
electrode potential is important for modeling such processes as solvent-dipole
adsorption and orientation, and the chemisorption of ions, especially anions,
each of which factors determines, among others, the capacitance of conduc-
tor/solution interfaces as in a double-layer supercapacitor.
In energy terms, this modification of surface-region electron density by a
changing potential corresponds to effective changes of the electronic work func-
tion, cP, of the metal (when it is an electrode) or its electron affinity (-cP), which
is one of the bases of the effects of changing potential on the kinetics of elec-
trode processes l8 (Chapter 3) and on the chemisorption of ions.
The overall structure of the electrode/solution interphase is seen to be quite
complex. Its construction in terms of surface-chemical, ion hydration, and dou-
ble-layer aspects is illustrated schematically in Fig. 6.8.
The Double Layer at Capacitor Electrode Interfaces 119
METAL/ELECTROLYTE INTERFACE
_ _ _ _ .--------OUTER HELMHOLTZ LAYE.R
DIFFUSE LAV'ER
•
FIGURE 6.8. Overall construction of the electrode/solution interphase illustrating its surface-
chemical and double-layer aspects. XM and Xd are the intrinsic surface potentials of the metal and
adsorbed dipoles, respectively.
for a double-layer thickness of 3.8 A (0.38 nm). The latter figure corresponds
to the distance of closest approach of simple hydrated cations, e.g., Na+. The ac-
tual value of the thickness of the double layer will depend on the crystal ionic
radius of the ion and the thickness of its time-average hydration or solvation
shell.
120 Chapter 6
From this it is seen that E has a very high value-some 2.9 x 107 V cm- I .
Sometimes nonelectrochemists are puzzled as to how such enormous fields can
exist without electrical breakdown. Thus, in an ordinary capacitor, e.g., with a
polystyrene dielectric, fields cannot be sustained beyond ca. 5000 Vern-I. How-
ever, in the double layer, the behavior is quite different since there is no bulk
dielectric in the normal sense associated with dielectrics in regular capacitors.
Only the water of hydration of the ions and the monolayer film of adsorbed sol-
vent water at the electrode interface (Fig. 6.6) constitute the dielectric of the
double-layer capacitance.
The situation is analogous to that on the atomic scale in, e.g., a molecular
dipole such as HCl or H 20 where the internal, interatomic field is also on the
order of 107 Vern-I. Similarly, the interion (±) local fields in an ionic crystal
are of about the same magnitude. No charge transfer breakdown by passage of
charges between the ions can occur since they are very stable in their regular
ionic states, Na+ and Cl-, e.g., in a rock-salt crystal. In the double layer, leakage
currents across it can arise only when thermodynamically and kinetically, elec-
tron charge transfer processes are allowed beyond certain critical potentials and
corresponding interphasial fields, as outlined earlier.
The interphasial field, E, across the double layer can also be calculated in
a different way by employing the electrostatic equation of Gauss for the field
generated normal to a metal plate charged to a density of q charges per square
centimeter.
E=-4nq/e (6.3)
where e is the dielectric constant (coefficient) ofthe medium in which the field
is established by the charge density q. In the double layer, e is probably on the
order 6 but varies with the field.
Earlier we showed that the maximum charge density sustainable at an Hg
electrode in aqueous electrolyte is about 0.17 e/atom of the surface. The electron
charge is 4.8 x 10- 10 electrostatic units (esu, see Chapter 4). Then we find
where the factor 3 x 1015 is approximately the number of metal atoms per square
centimeter in a close-packed Hg surface. Thus E =5 x 105 esu cm-I. In practical
units of V cm- 1, E is then found to be 5 x 105 X 300 V cm- 1, the factor 300 being
from the definition 1 V = 1 esu/300. The resulting figure for E, depending on
the value to be assigned for e, is seen to be of the same magnitude as that derived
above by dividing a typical potential difference value across the double layer by
an appropriate thickness value d. A very high value for E again results and of
The Double Layer at Capacitor Electrode Interfaces 121
course has to be consistent with the first approximate way of estimating the
field. The agreement or disagreement obviously depends on the value chosen
for e in Eq. (6.4). More sophisticated calculations ofE would take into account
the microscopic distribution of charges of ions and associated solvent dipoles,
and the electron overspill from the metal toward the solution side of the inter-
face in the whole interphasial region (Fig. 6.8) constituting the double layer.
(6.5)
followed by
is very poor (exchange current density, io = 10- 13 A cm-2) so that significant cur-
rents for Faradaic charge transfer across the double layer (corresponding to a
leakage current across the interphase) do not begin to pass until potentials more
negative (vs. RHE or SHE) than ca. -0.9 to -1.0 V are attained. Then between
+0.23 V and ca. -0.9 V, only double-layer charging currents effectively pass so
that within that range the interphase approaches ideal polarizability with an al-
most ideal nonleaky double-layer capacitance being then manifested which can
be experimentally characterized by means of transient charging curves or ac im-
pedance. The electrode interphase is then capacitorlike in its electrical behavior,
so that charging energy can be stored.
Gold is another metal that exhibits almost ideal polarizability over a certain
range of potentials: in this case between -0.2 V and + 1.30 V in aqueous H 2S04
solution. Beyond + 1.30 V, surface oxidation begins, eventually leading to O 2
evolution on a gold-oxide film while below ca. -0.2 V, H2 evolution leakage
currents become significant (> 10-5 A cm- 2). Within the above limits, the elec-
trode interphase behaves like an almost ideal capacitor but with significantly po-
tential-dependent capacitance, as is also the case at Hg. 4 ,17
It should be noted that with excursions of potential, positively or nega-
tively, beyond the potential limits for solvent-electrolyte decomposition, fur-
ther double-layer charging (or discharging) still occurs so that the total current
density passing is then the sum of a double-layer charging component, idb and
The Double Layer at Capacitor Electrode Interfaces 123
Cdl
The behaviors of equivalent circuits (a) and (b) are easily distinguished by the
difference between their impedance spectra with variation of frequency; thus (a)
is purely capacitative while (b) has a maximum capacitative impedance for a
given value of Cdl and RF (for a particular potential) at a certain frequency.
124 ChapterS
The Faradaic leakage resistance, RFo in circuit b is very important as the ba-
sis of self-discharge (see Chapter 18) in electrochemical capacitors and in bat-
tery cells. Its role will be analyzed in Chapter 18.
In the case of electrodes that are base metals, nonideal polarizability usu-
ally occurs because of the possibility of anodic corrosion or oxide film forma-
tion at potentials already near the H2 reversible potential; this leads to Faradaic
leakage currents in parallel with double-layer charging. In addition, such metals
usually have larger exchange current density for H2 evolution from water, so
they cannot be polarized very far cathodically to the RHE or SHE potentials
without appreciable H2 evolution currents arising.
REFERENCES
1. E. A. Guggenheim, J. Chern. Phys., 4, 689 (1936).
2. N. K. Adam, The Physics and Chemistry of Surfaces, 3rd ed., Chapter 3, p. 107, Oxford
University Press, Oxford (1941).
3. H. von Helmholtz, Ann. Phys. (Leipzig), 89, 211 (1853).
4. R. Parsons, Chapter 4 in Modem Aspects of Electrochemistry, J. O'M. Bockris and B. E.
Conway, eds., vol. 1, Chapter 4, Butterworths, London (1954).
5. N. D. Lang and W. Kohn, Phys. Rev., Bl, 4555 (1970); B3, 1215 (1971).
6. S. Amokrane and J. P. Badiali, in Modem Aspects of Electrochemistry, J. O'M. Bockris, B. E.
Conway, and R. White, eds., vol. 22, Chapter 1, Plenum, New York (1992).
7. G. Gouy, Ann. Phys., Paris, 7, 129 (1917); J. de Phys., 9, 457 (1910).
8. R. H. Fowler and E. A. Guggenheim, Statistical Thermodynamics, p. 77, Cambridge
University Press (1939).
9. D. L. Chapman, Phil. Mag., 25, 475 (1913).
10. B. E. Conway, Ionic Hydration in Chemistry and Biophysics, Chapter 10, Elsevier,
Amsterdam (1981).
11. P. Debye and E. Hiickel, Phys. Zeit., 24, 185 (1923).
12. L. Onsager, Phys. Zeit., 27, 388 (1926); 28, 277 (1928).
13. M. Green, in Modem Aspects of Electrochemistry, J. O'M. Bockris, ed., vol. 2, Chapter 5, p.
343, Butterworths, London (1961).
14. O. Stem, Zeit. Elektrochem., 30, 508 (1924).
15. R. W. Gurney, Ionic Processes in Solution, Dover, New York (1940).
16. A. N. Frumkin, Zeit. Phys. Chem., AI64, 121 (1933); Acta Physicochim., USSR, 6, 502 (1937).
17. D. C. Grahame, Chem. Rev., 41, 441 (1947).
18. J. A. V. Butler, Proc. Roy. Soc. Lond.,A 157, 423 (1936).
19. B. E. Conway, J. Electroanal. Chem., 123, 81 (1981)
20. B. E. Conway, Theory and Principles of Electrode Processes, Ronald Press, New York (1964).
21. F. P. Bowden and E. K. Ridea1, Proc. Roy. Soc., Lond., AI07, 486 (1925); A114, 103 (1927);
A119, 680; 686 (1928).
22. J. A. V. Butler, Electrocapillarity, Methuen, London (1940).
23. J. D. Bernal and R. H. Fowler, J. Chem. Phys., 1, 515 (1933).
Chapter 7
In order to provide a fundamental basis for understanding the properties and be-
havior of double-layer types of capacitor devices, this chapter gives a broad ac-
count of the theoretical treatments of the structure and capacitance of the double
layer at electrode interfaces. This topic has been one of major activity and inter-
est in electrochemistry for about a hundred years, and has now found substantial
technological applications. In 1997, the Electrochemical Society Sponsored a
major symposium on the double-layer to recognize the 50th anniversary of Gra-
hame's seminal paper! in Chemical Reviews (1947).
Electrostatic and thermodynamic treatments of the double layer are based
on a model in which the interphasial region between an electrode and an ionic
solution is ideally polarizable (Chapter 6), i.e., a potential difference can be es-
tablished between a metal electrode surface and the inner boundary of an elec-
trolyte solution without Faradaic charge transfer processes taking place. The
interphase is then ideally capacitative and the electrode is referred to! as an
ideally polarizable one. The interphase then has a pure double-layer capaci-
tance that ideally is frequency independent in an ac evaluation of that capaci-
tance. This is the ideal requirement for an electrochemical capacitor device.
In practice, some frequency dependence is commonly observed, i.e., the
phase angle for the double-layer capacitance may not have the ideal value of 90°
at all frequencies, and potential-dependent dc leakage can also occur (Chapter
18). Deviations from ideal capacitative behavior can arise when there is some
125
126 Chapter 7
dielectric loss associated with the solvent orientation polarization in the double-
layer dielectric (at very high frequencies) and/or when there are some slow an-
ionic chemisorption processes that lead to lower frequency losses. In either case,
there is energy dissipation in the charging and discharging cycles at an incom-
pletely polarizable electrode interface. Another source of nonideal behavior is
distribution of the double-layer capacitance over a porous electrode surface
(Chapter 14). In a practical electrochemical capacitor device, frequency depend-
ence of the overall capacitance is generally observed and is due, in addition to
the "porous electrode" effect, to coupling with other equivalent series resistance
(esr) components.
As emphasized by Grahame, l the double layer at an ideally polarizable
electrode is in a state of electrostatic equilibrium, in contrast to other types of
electrode interphases across which free charge transfer takes place (nonpo-
larizable interphases). This corresponds to an electrochemical thermodynamic
equilibrium, ideally of a Nernstian kind.
Theoretical treatments of the structure (Chapter 6) and properties of the
double layer can be conveniently considered in a hierarchy of four sections:
1. The first is the diffuse part of the double layer [Fig. 6.3(b), Chapter 6],
beyond (toward the solution) the inner contact layer of ions (solvated or
otherwise) that defines the so-called "Helmholtz layer" [Fig. 6.3(a),
Chapter 6]. Historically, this was the first theoretical examination of
double-layer properties in work by Gouy and by Chapman. 2,3
2. The second is the compact or Helmholtz layer,4 which became treated
in terms of adsorption of ions as part of Stem's combination5 of the
Helmholtz and Gouy models, taking into account the finite sizes of the
ions of the electrolyte, which determine their distances of closest ap-
proach to the electrode surface [Fig. 6.3(c), Chapter 6].
Later, Grahame 1 treated the compact region in terms of two layers,
one for anions located at their distances of closest approach to the elec-
trode metal, and the other for hydrated cations located at their somewhat
longer distances of closest approach, which are determined by their hy-
dration (or solvation) radii, as shown in Chapter 6. The two regions dis-
tinguished by Grahame are referred to as the "inner Helmholtz layer"
(or plane) and the "outer Helmholtz layer," (or plane), respectively.
3. Work on the two classically distinguished regions of the double layer
in (1) and (2), was followed by important treatments of the role of ad-
sorbed solvent dipoles and their potential (field)-dependent orientation
in the compact regions of the double layer6- 9 in determining the capaci-
tance.
4. Finally, in relatively recent years, attention has been paid to the poten-
tial-dependent spillover of electron density from the formal surface of
The Double Layer at Electrode Interfaces 127
the metal toward (or away from) the solution and compact layers, de-
pending on the sign of charge of the electrode metal, and its influence
on the interphasial capacitance of the electrode. 10-12
For completeness and for historical reasons, in discussing the models of the
double layer, we first outline the electrostatic statistical treatment of the diffuse
part of the double layer. In practice, however, the behavior of the diffuse-layer
capacitance is of less significance for the properties of electrochemical capaci-
tors than is that of the inner layer since the latter dominates the overall inter-
facial properties at the high concentrations of electrolyte commonly employed
in capacitors to minimize equivalent series resistance or internal pore resistance.
However, treatments of the diffuse part of the double layer have formed a cor-
nerstone in our understanding of double-layer properties, and an accurate theory
of diffuse-layer capacitance is an essential requirement for evaluating compact
layer capacitance. This latter mainly determines the capacitance of double-
layer-type devices, through application of the reciprocal sum relationship (Eqs.
7.11 and 7.12) to experimental data on overall capacity. Direct theoretical treat-
ment of the inner layer itself, although included in Stern's paper,5 has been slow
to develop in reliable form, owing to the complexity of the modeling involved
(see later discussion).
The treatment of the diffuse-layer ion distribution [Fig. 6.3(b), Chapter 6]
and its dependence on the surface charge density, qM, on the metal, which is re-
lated to the latter's electrode potential relative to the potential at which the elec-
trode bears a zero charge (the potential-of-zero charge), proceeds in the
following way: Poisson's electrostatic equation is used in conjunction with the
Boltzmann distribution law4 and applied to the electrostatic energy experienced
by both cations and anions owing to the interaction of their charges with the po-
tential that results from the electrode surface charge or, more particularly, to the
gradient of the electric field near the electrode.
If IfIr is the potential at a distance r from the electrode surface, the local con-
centration of cations and anions, c+ and c, at r will be4
128 Chapter 7
(7.1)
_
Pr - 4 ed?-
J 4 kTe/flr] + z_ec_ eX1-
eX1- 0 J z_e/flr]
kT (7.2)
(7.3)
(7.4)
(7.5)
in Eq. (7.4), and integrating with Br ='ii, a mean constant value of the dielectric
constant B in the double layer (since B is not very sensitive to variation of r ex-
cept very close to the electrode surface), gives
(7.6)
for the boundary conditions d/flr1dr -7 0, r -7 00; and /fir -7 /fIs, the potential in
the bulk of the solution where Pr =O. The term -1 in the braces in Eq. (7.6)
arises from the integration constant, i.e., when r -7 00 , exp[(/fIr - /fIs)lkT] = 1 for
d/flr1dr=0.
The Double Layer at Electrode Interfaces 129
At this point in the treatment of the diffuse double layer it is assumed that
Gauss's relation
(7.7)
can be applied near the electrode surface bearing the charge density, qM, at the
distance of closest approach, a, of the ions to the electrode surface. Sa is the local
value of the dielectric constant, s, in that region. Sa is taken as a mean value e,
though Sa may depend on potential (field 13 ) and will probably have a different
mean value on each side of the pzc.
Also, solvent dipole orientation (cf. dielectric saturation effects) at the
electrode surface6- 9 leads to a lower value of S in the region r::e a than further
away from the electrode. From Egs. (7.6) and (7.7), qM is obtained with the
above assumptions as
(7.8)
If the ions are point charges as considered by Gouy, If/a becomes identical
with <PM, the potential of the metal with respect to the solution, and distribution
ofthe ions continues right up to the metal surface, a = o. By Eg. (7.9), aguantity
dqMlo( If/a - If/s) can be evaluated as
which may be identified with the differential double-layer capacity, C, that is as-
sociated with the ionic atmosphere charge distribution dependent on afllrlar and
hence on qM' This capacitance will be referred to as Cdiff.
A comparison of values of the capacity calculated from Eq. (7.10) with
those measured experimentally from the dependence of surface charge (qM), at
the metal on electrode potential E, indicates, however, a major discrepancy with
regard to the rate of change of C with ¢JM - fils and the absolute magnitude of C
at values of ¢JM - fils> ca. 0.1 V. Only near the potential at which qM = 0 (the
pzc) is the experimental behavior numerically comparable with that predicted
by Eq. (7.10).
The principal reason for the failure of this relation lies in the assumption
that the ions are point charges so that the ionic charge distribution can be con-
tinuous up to the electrode surface. This allows a large space charge to arise very
near the electrode, and hence an anomalously large capacitance is calculated. If,
however, the ions have a finite size (e.g., as determined by their crystallographic
or, more appropriately, their primary hydration radii, a,), the continuous charge
distribution must be cut off at r =a, and the potential-distance relation near the
electrode is then discontinuous as in Fig. 6.1 (c) in Chapter 6.
The importance of the distance of closest approach a for ions of finite size,
referred to earlier, was discussed by Grahame l but was recognized by Stern5 and
was mentioned by Gouy in regard to an effective thickness of the double layer.
The overall potential difference, ¢JM - fils, between the metal and the solu-
tion can then be regarded as made up of two parts ¢JM - fill and fill - fils where
fill is the mean potential at r = a, i.e., fila == fill' fill is referred to as a mean poten-
tial since the potential in the double layer will fluctuate laterally across the in-
terphasial region because of the discreteness of the ionic charges involved. The
symbol fill is used to maintain conformity with the earlier Russian literature, but
¢J2 has been used as the symbol for this quantity in some later publications. Both
these contributions can be dependent on qM so that
(7.11)
The first term is the reciprocal of the overall capacity C mentioned earlier, and
the other terms have a similar nature, so that Eq. (7.11) can be written
1 1 1
-=-+- (7.12)
C Cl C2
where C l and C2 are obviously defined by comparison with the two terms on the
right-hand side ofEq. (7.11). Equation (7.12) also implies that C l and C2 are ad-
ditive in a series combination. C l is the Helmholtz compact layer capacity and
The Double Layer at Electrode Interfaces 131
(7.13)
For small deviations of potential around the pzc, this function for C is
mainly determined by C2 and increases approximately exponentially with '1/1 -
'l/s on each side of the pzc.
Itis seen that when C 1 » C2> C= C2 (fromEq. 7.10 with 'l/a= '1/1), or when
C2 » Cj, C = C 1; the first inequality is valid when '1/1 - 'l/s is quite small, and
the second when it is large. It is important to note that it is the value of the
smaller capacity contribution that mainly determines the overall value of C
since the two contributions are in a series relationship (Eq. 7.12), as discussed
in Chapter 6 (Eq. 6.1).
Apart from giving a quite accurate representation of the diffuse-layer ca-
pacitance, the Gouy-Chapman theory is important because it provides the
means of evaluating the inner-layer capacitance, C 1, which is of greater interest,
from the overall C measured, through Eq. (7.12). In fact, at the rather high con-
centrations of electrolytes employed in aqueous double-layer capacitors, it is the
compact or Helmholtz layer capacitance that mainly determines the capacitance
of a double-layer electrochemical capacitor device.
Equation (7.13) represents the data for capacitance at the mercury/solution
interface (e.g., for a KCI solution!), if C 1 = 18 f1F cm-2 is assumed when cations
preferentially popUlate the interface region (l/JM - 'l/s negative) and C, = 38 f1F
cm- 2 when the anions dominate in the double layer (l/JM - 'l/s positive). Typical
capacity-potential profiles for a mercury electrode are shown in Fig. 7.1 (from
Ref. 1). The capacity contribution C 1 is referred to as the capacity of the Helm-
holtz layer and C2 is that of the diffuse layer or ionic atmosphere region. Further
divisions of C! into contributions from the inner or the outer Helmholtz layers,'
referred to earlier, will be discussed later.
In Eq. (7.13) it will not generally be validl,15 to assume that the same po-
tential '1/1 applies to the position of closest approach for anions and for cations.
Owing to the more polarizable nature of anions and their specific affinity as ad-
sorbed surface ligands for some metal surfaces, anions may approach more
closely than hydrated cations at a given potential, so that '1/1 will not have quite
the same significance for anions as for cations. It is convenient to call this po-
tential'l/2 for the region of closer approach and specific adsorption, i.e., chemi-
sorption associated with anions. This matter is now examined in more detail
according to the theory developed by Stern5 and reviewed by Parsons. 15
132 Chapter 7
NoF NaGI
46
0.1 M
Hump
28
20
0.001 M
12
~Influence of
N
Ie
u Cditt.
LL.
::i...
....... 4
W
U
Z 0.8 0.4 a -0.4 -0.8 -1.2 -1.6 -20
<t
l-
e:::;
a:
<t O.IM
U Nol 42 1M NoNO:;
a:: 80
w 1M
~
.-l
I 34
W 60
.-l
CD
::>
0 26
0
40
O.IM
18
20
10 10
0.4 0 -0.4 -0.8 -1.2 -1.6 0.8 0.4 0 -0.4 -0.8 -1.2 -1.6
FIGURE 7.1. Differential capacitance of the Hglaqueous solution interface at 298 K in foure1ec-
trolytes: NaF, NaCl, NaI, and NaND3. Concentrations indicated. Reprinted with permission from
Chem. Rev., 41, 441 (1947). Copyright American Chemical Society.
The Double Layer at Electrode Interfaces 133
(7.14)
The charge qz will be given by Eq. (7.8) with tJlz as the relevant potential, i.e.,
tJla = tJl2' The charge ql was obtained by Stern in terms of site-fraction statistics
for solution and surface phases by applying a form of the Langmuir isotherm
with an electrochemical Gibbs energy of adsorption determining the extent of
adsorption as a function of solution concentration of the ions.
Stern's derivation for the quantity tJlz was unnecessarily involved, and Par-
sons l5 has given a useful clarification of the calculation which need not be re-
peated here. The result of applying the Langmuir isotherm is
[1 + e-~-p-[L1-V-~-lk-T-]1
(7.15)
ql = eQ (l/Xs) ::P[SU±lkT] + -l-+-(-l/-X-s-)
where L1C; are the standard electrochemical Gibbs energies of adsorption of the
indicated cations or anions, i.e., the L1C; terms normally contain both electrical
and chemical Gibbs energy contributions, the latter defined for some standard
state concentration or mole fraction Xs of salt in the bulk solution. The term Q
is defined as the number of sites per square centimeter available for adsorption
at the electrode interface. It is assumed that this number is the same for cations
and anions, and that the adsorbed ion can freely replace solvent molecules,
which are also necessarily adsorbed at the surface, with a relative fractional cov-
erage depending on coverage by chemisorbed anions.
Reference has been made earlier to the fact that the L1C; terms in Eq. (7.15)
are electrochemical Gibbs energies of adsorption; following Stern's assump-
tions, they may be written for convenience in the form
134 Chapter 7
(7.16)
where ~G~ terms are the chemical standard Gibbs energies of adsorption of the
indicated ions (±), and 1f/2 is the mean potential in the plane of specifically ad-
sorbed ions. Experimentally, however, it will not usually be possible to separate
the ~G~ terms into their component chemical and electrical contributions.
An explicit mathematical expression for the inner-layer capacitance, C1, in
Eq. (7.12) corresponding to aqM/a(¢M-lf/d in Eq. (7.11) or dq1td(ifJM - If/l) in
Eq. (7.15), is not easy to obtain directly, though the electric potential is implicit
in the ~G~ terms. Hence, in practice, experimental data for the overall C are
split, reciprocally, into C I and C2 components by calculating the theoretical C2
diffuse-layer capacitance for a given concentration and electrode potential, and
combining it reciprocally with the experimentally measured C: lIC I = lIC -
lIC2·
In most cases only one type of ion is specifically adsorbed (the anion, ex-
cept in cases of organic electrolytes such as tetraalkylammonium salts), so that
Eq. (7.15) could be written for anions as
(7.17)
since usually for dilute solutions, (lIXs) expLl.G;lkT» 1. It is clear that qltz-e
is the number nl of ions in the adsorbed layer and that nltQ is the relative cov-
e
erage lot .
f hese IOns, 15·
I.e.,
(7.18)
form of the isotherm written as Eq. (7.18) may in fact be physically the more
reasonable one.
Stern expressed the integral capacity Kl of the double layer as
(7.19)
and assumed that !fI2 = !fib which enables values of!fll to be calculated as a func-
tion of ¢M, the potential of the metal, for known Kl and solution concentrations
in the absence of specific adsorption. (Usually this evaluation is most conven-
iently performed numerically by choosing !fIl values and obtaining ¢M as the de-
pendent variable, since !fIl enters the arguments of exponentials in Q2') The term
Kl is the integral capacity of the region between the metal surface and the plane
of centers of the adsorbed ions. The assumptions !fI2 = !fIl and AC; = 0 are
equivalent to taking ql =0, i.e., when specific adsorption is absent. Stern did not
distinguish, however, between !fI2 and !fIl for the case of specific adsorption, and
this distinction constituted an important element of Grahame's treatment l re-
ferred to earlier.
As mentioned several times before, the inner-layer capacitance cannot be
properly interpreted, especially with regard to its substantially differing values
on the positive and negative sides of the pzc at Hg (Fig. 7.1) or Au, withoutrec-
ognizing different values of the closest approach distance, a, for positively and
negatively charged electrode surfaces. This situation corresponds to different
effective radii of anions and cations, owing to their usually differing hydration
and crystallographic radii, and because anions tend to be more strongly chemi-
sorbed (owing to their greater lone-pair electron donicities) than corresponding
isoelectronic cations, e.g., Na+-P-, K+-CI-, Rb+-Br-. Other factors (such as hy-
drophobicity) are involved in the adsorption of large organic cations (e.g.,
Et4N+, n-Bu4N+), which have major effects on the interphasial capacitance of
electrodes. These ions are important in nonaqueous solution capacitors, where
they often form the electrolyte with co-anions such as PF6, BF.;, CI04, and are
adsorbed at carbon powder or fiber surfaces.
The recognition of the importance of different distances of clos~st ap-
proach for cations and anions, and the corresponding distinction between inner
Helmholtz and outer Helmholtz planes for the description of the compact layer,
was one of Grahame's major contributions,l complementing his detailed treat-
ment of the thermodynamics of the interphase at the ideal polarized electrode.
where m and n are the inner coordination solvation (S) numbers of anions A-in
solution and in the adsorbed state, respectively. A-adsorption is usually en-
hanced when the metal surfaces, M, is positively charged, i.e., when its Lewis
acidity is increased.
The conjugate relation between A-and M shown here is usually also de-
pendent on the electronic properties of M. This is an important factor that deter-
mines the dependence of double-layer capacitance in various electrolytes on the
substrate electrode material.
7.5.1. General
In the field of double-layer electrochemical capacitors, major interest has
developed in the use of nonaqueous electrolyte solutions, rather than aqueous
ones, owing to the substantially higher operating potentials that can be achieved,
as has been noted earlier. In addition, the capacitance behavior as a function of
electrode potential usually differs in a major way from that for water and has
therefore attracted interest for theoretical and computational modeling.
U ntiI about 1961, much of the classical work on the capacitance of the dou-
ble layer had ignored the fact that solvent molecules largely populate the double
layer. However, several important exceptions led the way toward more com-
plete recognition of the role of the solvent in double-layer properties and mo-
lecular-model treatments. First, the papers of the present author 13,l4 and of
Grahame l6 considered the field dependence (i.e., dielectric saturation) of the ef-
fective dielectric permittivity of the solvent medium constituting the dielectric
of the double layer in its inner region. Later Macdonald l7 took into account both
the field dependence of the dielectric polarization and the associated self-com-
pression of the solvent dielectric in an inhomogeneous field, referred to as elec-
trostriction. Also, implicitly, the properties of solvent water at electrode
interfaces were taken into account in simple dielectric polarization models of
the potential dependence of adsorption of organic molecules at electrode sur-
faces in well-known papers by Frumkin l8 and Butler. l9
The Double Layer at Electrode Interfaces 137
In parallel with this theoretical work were new (in the 1960s) experimental
studies by Hills and Payne20- 23 on the properties of the double layer at Hg in
nonaqueous solvents, the electric polarization properties of which are substan-
tially different from those ofliquid water. 24
Also to be noted is the fact that ions (cations or anions, depending on the
electrode potential relative to the pzc) populating the compact (Helmholtz) re-
gion of the double layer are usually substantially hydrated (especially cations 24 )
and hence locally influence the orientation and state of polarization of the water
molecules that also always populate the double layer. 6- 8 Thus the structure of
the double layer at the molecular level is quite complex.
The energies of solvation of ions in nonaqueous solvents are usually sub-
stantially less than in water (hence the lower solubilities of many salts in such
solvents), so that the tendency for ions, especially anions, to become chemisor-
bed at electrodes is greater in aprotic media than in water. This leads to an indi-
rect effect of the solvent type on double-layer capacitance.
water and hence can contain small but significant quantities of impurities that
can be either electrochemically reduced or oxidized, leading to self-discharge.
(2) Because of their usually smaller solvating power for ions, ion adsorption at
electrode interfaces can be stronger, modifying the double-layer capacitance be-
havior. (3) Because their dielectric constants are usually lower than that of
water, specific double-layer capacitances tend to be lower than in aqueous so-
lutions. Also, (4) because of these lower dielectric constants, the specific resis-
tivities of their solutions of electrolytes are usually less. This tends to raise
equivalent series resistance values in nonaqueous solution capacitors, leading to
diminished power densities (see Chapters 15 and 17).
For aprotic solvents, the polarity is often measured by their bulk dielectric
constants. However, in evaluating local intermolecular interactions, and inter-
actions with charged surfaces and ions, the individual dipole moment and/or the
donicity of unshared electron pairs are usually found to be the more significant
quantities. In fact, as Table 13.1 in Chapter 13 shows, the dielectric constant is
little related to the lone-pair doni city numbers (based on heats of complexation
of the solvent to a Lewis acid such as SbF5). The behavior of the metal/solution
double layer depends very much on these electrical polarity properties of the
solvent of the electrolyte solution in contact with the electrode metal surface.
C=A8KOld (7.20)
where Ko = 8.85 X 10- 12 F m- I is the permittivity of free space. C for the above
system has a value of about 17 flF cm-2 negative to the pzc. Taking the thickness
The Double Layer at Electrode Interfaces 139
a=(dO/d-l)/Snp=p/Sn (7.21)
(7.22)
include the effects of electrostriction (see Ref. 17), while lateral interaction ef-
fects in the inner layer of oriented adsorbed water molecules are only crudely
treated. For example, the angular dependence of H bonding in water-water in-
teractions 25 .27 ,28 is not considered and cooperative effects in H bonding have re-
ceived little attention in treatments of water in the double layer, except
qualitatively in terms of semiempirical cluster models, and in lattice treatments
by Parsons and Reeves 29 and Guidelli,3o referred to in Section 7.5.6.
Ni
(7.23)
Ni +NJ-
where U is the net energy of the oriented dipole in the field. When lateral inter-
actions are significant, 8 U has the form
Ni
-=e2UlkT
NJ, , (7.25)
Ni -NJ,
9\ = i I =tanh UlkT, (7.26)
N +N-I-
i.e.
(7.28)
fl(9\ - J) - 4naqM
LlV =4nqMd + 4nN .
A
3 (7.29)
1 + aneld
where <5 = tan2012 for a mean angle 0 of preferential orientation of the H20 di-
pole toward the electrode, e.g., due to asymmetric dipole image interactions
and/or to specific chemical affinity of one end of the dipole, such as H 20 for the
electrode metal. fl(9\ - <5) is the mean moment per site on the surface in the array
The Double Layer at Electrode Interfaces 143
of oriented dipoles and a here is the electronic polarizability of the dipoles de-
termining the magnitude of induced moments.
The relation between Ll V, d, and the other quantities shown can be used to
obtain an empirical expression for the effective dielectric constant Be by writing
LlVld =mean field E and E= -4nqM/Be by means of Gauss's law.
Then Be is seen to be given9 by
(7.30)
and its variation with field toward a saturation value depends on the variation
of the dipole orientation function 9\ with field; 9\0 is any residual (specific) ori-
entation when qM = 0 at the potential-of-zero charge referred to earlier; it is in-
dicated experimentally.
The main weakness of the treatments by Watts-Tobin and Mott,6 and by
Levine, Bell, and Smith9 is the neglect ofH-bond structural effects2s.27-30 in the
interphase, i.e., correlated orientation effects. Such effects are not adequately
taken into account by the lateral interaction term wn9t, since this has no general
angular dependence on orientation,2s.27 only extreme orientations being con sid-
ered. 8.9
The limiting two-state situation is undoubtedly a serious oversimplifica-
tion since molecules of the water dielectric in the interphase will be oriented at
e
various angles and some average polarization orientation angle will be a func-
tion of field and Wn e , and will also be determined by the angular dependence of
H-bond energy between neighboring molecules,2s.28 The problem then becomes
a 2-dimensional version of the Kirkwood theory for associated dielectrics so
that the simple, elegant, but perhaps oversimplified features of the Watts-Tobin
and Mott model 7.8 would become lost. The problem of some overestimate32 of
the dipole orientation effect in the two-state modelS was solved by Fawcett33 by
introducing the idea of a three-state orientation distribution, with the "third"
state lying flat along the electrode surface as in Reeve's mode1. 29
surface. This is, of course, a different effect from that associated with specific
interaction of the lone-pair orbitals on 0 in H 20 with the atoms in the Hg sur-
face, but both are connected with the electron charge distribution in the water
molecule and its donor and acceptor properties at metal interfaces. At molecules
containing an S atom (e.g., thiourea), the specific affinity of the S-end of the mo-
lecular dipole for Hg is very much larger.
Frumkin and Damaskin37 assumed that the contribution of the surface di-
pole potential (Xd) to the total surface potential could be written
(7.31)
10
:3
60 4
...
e
I
u 40
lL
--
0
~
30
20
'i",/ ~C·cm-2
From the data required to empirically fit the experimental results, an esti-
mate of the area of the clusters of adsorbed water was given as 0.24 nm2 • The
mean dipole moment of the clusters was found to be ca. 0.75 D. The effective
value of B was also derived asf(HM)'
It should be noted that a capacity hump arises in curves 2 and 3 of Fig. 7.2,
but displaced from the pzc. This is an important feature of most of the experi-
mental capacitance results at the Hg/aqueous solution interface, which has been
the subject of much previous discussion,S,41 including the idea that H 20 dipole
reorientation was involved. The hump is, however, usually sensitive to the type
of anion of the electrolyte, which led Bockris, Devanathan, and MulIerS to offer
an explanation in terms of changing anion adsorption and repulsion in the dou-
ble layer with increasing positive qM' Probably both oriented chemisorbed water
146 Chapter 7
and specifically adsorbed anions 36 playa role since the state of orientation of
chemisorbed water will almost certainly depend on the presence of anions in the
compact layer.
Curve 4 in Fig. 7.2, for K2 = 50 Ji.F cm- 2, corresponds to the experimental
behavior of Ga where the capacity rises sharply at the pzc with no hump.
Stronger chemisorption of water dipoles corresponds to a lowering of K2 (from
200 to 50).
Following Damaskin and Frumkin's paper,37 Parsons 42 presented a more
detailed treatment of the state of a solvent at an electrode interface in terms of a
primitive four-state model. A similar multistate treatment was subsequently
given by Bockris and Habib,43 but apparently without comparison with the pre-
vious 42 work.
Parsons 42 took account more quantitatively of the number of molecules per
square centimeter in the double layer and avoided some of the arbitrary assign-
ments of parameters, discussed earlier, that were involved in the Damaskin-
Frumkin theory.37 Solvent molecules were assumed to exist in two states of
aggregation at the surface of the electrode: free molecules and small clusters.
The free molecules could adopt either of two extreme "up" or "down" orienta-
tions, as in the Watts-Tobin model,6,7 with a dipole moment Ji.. The clusters
could also adopt one of two extreme orientations, depending on the orientation
of their resultant perpendicular dipole moment, Ji.c, with relation to the metal
surface. Ji.c was expressed per molecule of the cluster and a parameter p was de-
fined as the ratio /1cl/1 to characterize the state of polarization of the cluster. The
solvent polarization was expressed in terms of Boltzmann orientation distribu-
tion functions, A+ and A_, for clusters and other terms for free dipoles.
Inner-layer capacities were calculated as a function of a reduced charge pa-
rameter S and are shown in Figs. 7.3(a) and 7.3(b) for the two values of the re-
duced dipole capacity K with A_ taken as 10-8 • A series of curves was given for
various A+ values, varying from 10-2 to 10-6 or 10-7. With A+ taken as 10-2 and
A_ as 10-4, the general features of the experimental capacitance curve for aq.
NaF at 0°C 41 are quite closely reproduced. The calculated capacities C which
are plotted in Figs. 7.3(a) and 7.3(b) are expressed in terms of the ratio
C =C/Ko where Ci is the inner-layer capacitance derivable from analysis of ex-
perimental results and Ko is an inner-layer capacity for a fixed orientation of di-
poles.
The physical significance of A+ must be mentioned because it determines
the general shape of the capacitance vs. S curves [Figs. 7.3(a) and 7 .3(b)], e.g.,
in changing from a form similar to that for Hg [A+ = 10-4 - 10-5 in Fig. 7.3(a)
and 7.3(b)] to that for Ga (A+ = 10- 2). A+ is of course analogous to Damaskin
and Frumkin's parameter K2; here it measures the energy associated (among
other things42) with binding of the dipole to the metal. A large value of Ji.b.+ (0-
end of H 20 dipole adsorbed at the metal) displaces the sharply rising part of the
The Double Layer at Electrode Interfaces 147
.---.-----.-----,--
5
(0 ) ( b)
-2 5
-3
-4
4
-5
-6
-7 4
-6 -4 -3-2
3 C.
C
z
z
10 o -10 o -10
5 5
FIGURE 7.3. Calculated behavior of inner-layer capacitance as a function of reduced charge S
= = =
(after calculations and model of Parsons 42): (a) with K 0.02, P 0.1, A_ 10- 8 ; (b) with K 0.08,
p =0.1, A_ = 10-8 . The values of the log A+ parameter (see text) are indicated on the curves.
capacity curve to more positive S values where the field effect on orientation be-
comes dominant. In this work, the inner-layer capacity behavior is quite well ac-
counted for by H 20 dipole and cluster orientation.
With solvents other than water, different types of inner-layer capacitance
behavior can be distinguished, as shown schematically in Fig. 7.4. It is possible
that type (ii) (Fig. 7.4) would manifest behavior like that of water if a wider
range of positive qM could be explored. Type (iii) is, however, different and cor-
responds to weak association and binding to the surface. The transition from
type (i) to type (iii) is qualitatively reproduced by the theoretical calculations as
larger values of log A+ in Figs. 7.3(a) and 7 .3(b) are taken. In certain solvents,
two humps appear, one on either side of the pzc.
In such cases, it seems that ion interaction in the double layer must be in-
voked 8 to explain at least one of the humps. Also, in water, the development of
the hump depends very much on the nature of the electrolyte anion (Fig. 7.1),
so the capacitance behavior cannot be treated only in terms of water dipole or
cluster orientation without some allowance for specific solvent orientation ef-
fects caused by the adsorbed anions in addition to that caused by excess surface
charge, qM' Indeed, from the known 24 specific influence of ions on the local state
of bulk water, it would be very surprising if similar effects were not of major
importance in the solvent layer in the interphase.
148 Chapter 7
l i) l i il ( iii)
+ 0 -
qM
FIGURE 7.4. Schematic representation of three principal types of inner-layer capacitance pro-
files as a function of qM for aqueous and nonaqueous solvents: (i) water type; (ii) ring-compound
type, e.g., proPllene carbonate, sulfolane; and (iii) humpless type, e.g., CH30H, HCOOH, NH3.
(After Parsons. )
FIGURE 7.5. Laterally associated H20 dipole arrays in the solvent dipole layer at an electrode
surface. (After Parsons and Reeves. 29)
~/~'cy--T~
19 T
If I I fJ
i. ~~~-~ - ~
~"'1--<~~
-------
___ -- ~---d- ___ ~
\ I
~----
electrode-surface Plane
FIGURE 7.6. As in Fig. 7.5, for an element of the W bonded interphasial H20 lattice at an elec-
trode surface. (After Guidelli. 30)
The Double Layer at Electrode Interfaces 151
100
N
IE
u 50
u...
::I..
u
...
......
O~----~-2~0~-----~1~O------~O~----~1~0------J20~--
qM/,.,.C cm- 2
Au 23 8.0
Hg 28 9.8
TJ(Ga)C 34 11.6
Bi 36 12.6
Sn 39 13.7
Pb 40 14.0
Cd 52 18.2
In(Gar 60 21.0
Zn 100 35.0
Ga 135 47.3
Source: Reprinted from S. Trasatti, 1. Electroanal Chern., 123, 121 (1981), with permission from Elsevier
Science.
arnner-Iayer differential capacity at the potential-of-zero charge.
brnner-layer permittivity derived from C; with the inner-layer thickness taken as 0.31 nm.
CLiquid alloys.
A-
n
L7
FIGURE 7.8. Icelike ordertcd H-honded water structure near an electrode surface. The two incli-
nations of the dipoles in the contact layer with respect to the surface normal ~ are distinguished by
the horizontal and vertical shadings. For an uncharged surface they are energetically equivalent.
(From Torrie and Patey.51)
154 Chapter 7
(a)
0.0
FIGURE 7.9. Probability density p(8,r) for molecular orientations as a function of distance rfrom
contact with a neutral surface for a fluid of water molecules with tetrahedral symmetry. All dis-
=
tances are in units of the solvent diameter, ds 2.8 A. (a) 80H, OH-bond orientation; (b) 81" dipolru
orientation. (From Torrie and Patey.51)
The Double Layer at Electrode Interfaces 155
(a)
\0.'>
'\
180
·0
p(e~, r)
~
N
(b)
FIGURE 7.10. As in Fig. 7.9 but for a surface charge density of -13 j1C cm- 2 Note the more
intense orientations. (From Torrie and Patey.51)
156 Chapter 7
metal (approximately one per atom) allow a finite probability of finding elec-
tron density outside the metal to an extent that diminishes exponentially out-
ward from the metal surface. Qualitatively, the electron spillover effect was
recognized a long time ago (e.g., Fig. 2 in Ref. 65) in relation to the intrinsic sur-
face potential, X, of metals.
In the case of an electrode, this spillover effect depends on the electro-
chemical polarization of the metal so that at potentials positive to the pzc, this
spillover electron density is drawn in toward the metal while at negative poten-
tials it is expelled outward to a corresponding extent. The variation may be over
1-2 A (0.1-0.2 nm) or so. This region over which there is an interfacial gradient
of electron density is referred to as the Thomas-Fermi screening distance (see
Fig. 4 in Chapter 6).
Development of this concept of a spillover electron density was initially
due to Lang and Kohn,lO,66 but some earlier treatment is attributed to Rice. 67
More recently, the spillover effect has been examined in more detail by Badiali
and co_workers 12,68,69 and by Schmickler,11,70 especially as it may influence
double-layer properties and the capacitance. The treatments employ the jellium
model for the behavior of the delocalized electron plasma in or near the metal
surface, taking into account the solid atom nuclei array as a diffuse positive
background, a "jellium."
As there is a variation of spillover electron density with electrode potential
around the pzc, a corresponding capacitance contribution, CM , formally arises,
which is referred to as the "metal contribution" to the double-layer capacitance.
It adds as a series contribution to the capacitance, being reciprocally additive to the
other contributions (compact layer, diffuse layer, and solvent polarization). Hence,
only when it is small does it lead to a significant contribution to the overall C.
Insofar as this metal contribution was not included in the classical conven-
tional treatments of the double layer, taking account of it will introduce some
modification to the evaluation of the other components. For example, conven-
tionally, the compact (Helmholtz) layer capacitance contribution, CH , is usually
evaluated from the overall Cd1 value (at a given potential) (actually as l/Cd1 ) by
subtracting a calculated value of the reciprocal diffuse-layer capacitance, since
the diffuse-layer capacitance theory is regarded as reliable at least for dilute so-
lutions up to about 0.1 M. If an additionalllCM term should be included, obvi-
ously then some changes in lICH will result, depending how small CM is. In fact
CM is really part of CH' This complication has been pointed out and emphasized
by Badiali. 69
Double-
Bulk
electron density
- t o zero
METAL SOLUTION
t ~Nominal metal
surface plone
L---
L - ofLOCuS of centers
metal surface
atoms
FIGURE 7.11. Profiles of electron density at the surface of an electrode at three potentials corre-
sponding to: (1) positive surface charge density, (2) zero charge density at the pzc, and (3) negative
charge density. (Schematic; repeated from Chapter 6.)
D Za=o D Z
FIGURE 7.12. Jellium model of charge distribution at a metal interface: left, microscopic view
of the metal interface; right, representation of the metal interface by a charged plane located at Zo.
D is the position of an ideal charged plane. (After Amorkrane and Badiali. 69)
The Double Layer at Electrode Interfaces 159
H 20 dipoles (or quadrupoles). For example, on the negative side, electron spil-
lover can influence shielding of the protons of oriented H 20 molecules at the
metal surface. Both these effects can have an influence on the interphasial ca-
pacitance in a rather complex, interactive way, and can also affect the specific
adsorption of ions, especially for anions, as noted earlier.
In the treatment of the surface region of metals from the point of view of
the electron-density distribution, the so-called "jellium model" is commonly
used. In this model, the discrete nature of the semi-infinite array of ion cores of
the crystal structure of the metal near its interface is ignored and is replaced by
a uniform, structureless background of positive charge, ending abruptly at the
metal's nominal surface (Fig. 7.12). This charge is equal and opposite to that of
the free-electron gas (approximately one valence electron per atom). Owing to
the structureless nature of the jellium, the properties of the electron-jellium sys-
" "
-- -- ..........",
....
a)
...... _--_ ... --- ........\ ..
" '.
\ ".
\
"....
'..
\
\
\
\
\.0.5
-10 5
z/eu
-5
z/eu
FIGURE 7.13. Calculated electron-density profiles n(z)/n for (a) rs = 6 and (b) rs = 2 in the jellium
model. (-) from Smith,?l (---) from Lang and Kohn. lO In (a), the dotted line shows the effect of
second gradient terms. (After Amorkrane and Badiali. 69 )
160 Chapter 7
tern are invariant parallel to the metal interface and vary only normal to it, mak-
ing a substantial mathematical and modeling simplification.
A treatment of this model in an approximate way was first given by
Smith71 in 1969 and a more exact one was published in a now well-known paper
by Lang and Kohn lO in 1970. In Fig. 7.13, we show the electron-density profile
for the jellium model n(z)/n (along the normal coordinate z) for rs = 6 and for
rs = 2 according to the calculations of Smith71 and Lang and Kohn. lO The pa-
rameter rs is defined by rs = (3/4nn)I/3 where n is the bulk free-electron density,
which varies from metal to metal; in fact, rs is the radius of the sphere containing
on the average one electron. The significance of the surface-region variation of
electron density for the structure of the electrode/solution interphase, in particu-
lar that component associated with the surface region of the metal itself, has
been explained in the referenced papers and in works by Amokrane and Badiali,
as reviewed in Ref. 69.
responding to the inner limit of the diffuse layer for the case of finite-sized ions
(Stern-Grahame model 1,5).
The overall result of a rather complex calculation73 is that '1/ as a function
of distance r into the solution and of concentration is given by the complex ex-
pression:
COSh[U'l/I/2] - 1 In cosh[u'l//2] - 1
2Kr=ln--~~~~-- (7.32)
cOSh[U'l/I/2] + 1 cosh[u'l//2] + 1
where u = ze/kT and '1/1 is again the potential of the inner limit of the diffuse
layer at the Helmholtz plane.
The interesting point about this relation is that the final function for 'I/(r),
which appears as the variable '1//2, is equal to the product 2(Kr), i.e., K and r
scale together in determining 'I/(r), so that values of r (proportional to the square
root of concentration) are larger for smaller values of K (nll2) for a given value
of '1/, relative to '1/. The first term on the right-hand side ofEq. (7.32) for 2Kr is
a constant for given electrode polarization and solution conditions.
The above calculation also allows calculation of the zeta potential (~) as-
sociated with the distance over which the diffuse layer is mobile with respect to
the Helmholtz plane in the case of a moving electrode surface or a colloidal par-
ticle subject to electrophoresis. The result is also significant for porous double-
layer capacitor electrodes in relation to electro-osmotic flow of electrolyte upon
discharge or recharge. Several years after Eversole and Lahr's paper, Grahame,
in his review, 1 gave an approximate expression for the '1/ potential as a function
of distance across the double layer, a result that is useful for restricted condi-
tions.
the electrolyte concentration or ionic strength (cf. Ref. 73 and Section 7.7). In
the cases of ions in the electrolyte itself, the ionic atmosphere charge distri-
bution, conjugate to a central reference ion's charge, extends effectively to
a 3-dimensional distance that is reciprocal in the square root of the ionic
strength according to the Debye-Htickel theory.74.75 This relation applies to di-
lute solutions, but for strong solutions (ca. 5 M or more), such as those employed
in capacitors, the concept of an ionic atmosphere breaks down, as it does also
for the diffuse-layer ion distribution at electrode interfaces. Nevertheless, a
rough guide is that the diffuse layer at electrodes effectively extends about 100
nm into the solution, i.e., for the If! potential to fall to within a few millivolts of
the solution potential, ¢Js' for a 0.001 M solution of a uni-univalent electrolyte,
about 10 nm for 0.01 M and 1 nm approximately for a 0.1 M solution. For
stronger solutions (> 1 M), a rather different model consisting of a quasi-lattice
of anions, cations, and solvent molecules near the electrode interface over dis-
tances ~l nm has to be adopted 15 and a diffuse layer, in the original sense, ceases
to exist.
At an electrode interface distributed within a microporous structure, the
configuration of the distribution of electrode potential into the solution phase is
much more complex than at an infinite planar electrode. 72 The problem arises
on account ofthe thickness,76 i.e., the Debye length, (K- i ) of the diffuse part of
the double layer in relation to the width or space available for the ion distribu-
tion to be set up within the pores of the electrode.
In the original Debye-Hiickel theory,74,75 the Poisson-Boltzmann equa-
tion relating the second-derivative operator, V21f!, to the ionic space charge den-
sity became transformed to a second-order differential equation, V21f! = K21f!,
where K2 involves the ionic strength I of the solution,16 i.e., K is square-root in
I. It was also shown that K- i had the dimensions of distance, namely, the effec-
tive radius of the ionic atmosphere distribution around any given ion. A similar
significance applies to the effective thickness of the diffuse-layer ionic atmos-
phere in double-layer theory, which is inversely related to a function of the ionic
strength of the electrolyte.
From this it can be appreciated that in very fine pores of a porous electrode
matrix, say 2-10 nm in extent (diameter), the diffuse region of the double layer
in dilute electrolyte solutions could extend all the way across the pore diameter
and overlap72 with the diffuse layer ion distribution at the other side of the pore
(Fig. 7.14). This situation then becomes similar to that envisaged and mathe-
matically treated by Verwey and Overbeeck in their monograph (see general
reading reference 1) on the theory of the stability oflyophobic colloids, and the
fall of potential with distance in the diffuse layer73 between the inner boundaries
of the double layer is then less than for free, noninterfering interfaces. The ion
distributions then overlap, so that the charge density and potential equations be-
come much more complex 72 than those given in the Gouy-Chapman theory.
The Double Layer at Electrode Interfaces 163
..J
<{
-----/,
to-
Z
w
5a. '-
..... .,- ./
/
--- -'><-
RADIAL
DISTANCE
FIGURE 7.14. Overlap of diffuse double-layer potential profiles (and corresponding ion distri-
butions) in an element of a pore in a porous electrode matrix (schematic).
350r----------------------------,
A-2225
BETl786, 36 (144)F/g
300
PA-1500
BET 1532,31 (124)F/g
250
C'3 A-2200
2::! 150 BET 1556, 37(148)F/g
~
v
......
o
0..
E 100 PF-36
::l BET 551, 58 (232) Fig
U
50
o~~~~~~~~~~~~~~~
o 10 20 30 40 50 60 o 70 80 90 100
Pore Width (A)
FIGURE 7.15. Cumulative pore surface area in a porous electrode matrix as a function of pore
width. Annotations refer to proprietory porous carbon preparations. (After Horovitz. 8l )
depth and detail than is required here to provide the basis for understanding the
origins of double-layer capacitance of supercapacitor devices.
REFERENCES
I. D. C. Grahame, Chern. Rev., 41, 441 (1947).
2. G. Gouy, 1. Phys., 9, 457 (1910).
166 Chapter 7
47. B. E. Conway, Ionic Hydration in Chemistry and Biophysics, Elsevier, Amsterdam (1981).
48. S. Marshall and B. E. Conway, 1. Electroanal. Chem. 1. Chem. Phys., 82, 923 (1984).
49. A. N. Frumkin and 1. Bagtozkaya, Electrochim. Acta, 10,793 (1965).
50. C. Kemball, Proc. Roy. Soc., Lond., A188, 117 (1947).
51. G. M. Torrie and G. N. Patey, Electrochim. Acta, 36, 1677 (1991).
52. C. W. Outhwaite and R. Molero, Electrochim Acta, 36, 1685 (1991).
53. 1. Klafter and 1. M. Drake, Molecular Dynamics in Restricted Geometries, Wiley, New York
(1989).
54. D. Richter, A. J. Dianoux, W. Petry, and J. Teixeira, in Dynamics in Disordered Materials,
Springer Proceedings in Physics, Vol. 38, Springer-Verlag, Berlin (1989).
55. K. L. Ngai and G. B. Wright, Relaxation in Complex Systems, North-Holland, Amsterdam
(1991).
56. 1. M. Drake, 1. Klafter, R. Kopelman, and D. D. Awschalom, eds., Dynamics in Small
Confining Systems I, Mat. Res. Soc. Symp. Proc., p. 290 (1993), publ. Material Res. Soc.,
Warrendale, PA.
57. 1. M. Drake, J. Kiafter, R. Kopelman, and S. M. Troian, eds., Dynamics in Small Confining
Systems II, Mat. Res. Soc. Symp. Proc., p. 366 (1995), publ. Materials Res. Soc., Warrendale, PA.
58. S. Stapf, R. Kimmich, and R. O. Seitter, Phys. Rev. Lett., 75, 2855 (1995).
59. G. Liu, Y. Li, and 1. Jonas, 1. Chem. Phys., 95, 6892 (1991).
60. G. P. Crawford, R. Stannarius, and J. W. Doane, Phys. Rev., A44, 2558 (1991).
61. A. M. Brodsky, M. Watanabe, and W. P. Reinhardt, Electrochim. Acta, 36, 1695 (1991).
62. V. Feldman and M. Partenskii, Electrochim. Acta, 36,1703 (1991).
63. M. F. Holovko, O. O. Pizio, and Z. B. Halytch, Electrochim Acta, 36, 1715 (1991).
64. D. J. Henderson and O. R. Melroy, eds., The Structure of the Electrified Interface,
Electrochim. Acta, special symposium volume, 36, pp. 1657-1889 (1991).
65. B. E. Conway, in Theory and Principles of Electrode Processes, Chapter 2, Ronald Press, New
York (1964).
66. N. D. Lang and W. Kohn, Phys. Rev., B8, 6010 (1973); B7, 3541 (1973).
67. O. K. Rice, Phys. Rev., 31, 1051 (1928).
68. J. P. Badiali, Electrochim. Acta, 31, 149 (1986).
69. A. Amokrane and J. P. Badiali, in Modern Aspects of Electrochemistry, 1. O'M. Bockris, B.
E. Conway, and R. E. White, eds., vol. 22, Chapter 1, Plenum, New York (1992).
70. W. Schmickler, 1. Electroanal. Chem., 100, 533 (1979).
71. J. R. Smith, Phys. Rev., 181, 522 (1969).
72. R. Farina and K. Oldham, 1. Electroanal. Chem., 81, 21 (1977).
73. B. Eversole and G. Lahr,1. Chem. Phys., 9, 798 (1941).
74. P. Debye and E. Hiickel, Phys. Zeit., 24,185 (1923).
75. P. Debye and E. Hiickel, Phys. Zeit., 24, 305 (1923).
76. R. A. Robinson and R. H. Stokes, in Electrolyte Solutions, Chapter 4, Butterwortbs, London
(1955).
77. H. Wendt, private communication (1997).
78. D. H. Everett, Trans. Faraday Soc., 50, 187 (1954).
79. D. H. Everett, Trans. Faraday Soc., 51, 1551 (1955).
80. D. H. Everett and P. Nordon, Proc. Roy. Soc., Lond., A259, 351 (1960).
81. Z. Horovitz, in Proc. Fifth Inti. Symposium on Double-layer Capacitors and Similar
Devices, S. P. Wolsky and N. Marincic, eds., Florida Educational Seminars, Boca Raton,
Fla. (1995).
82. N. K. Adam, The Physics and Chemistry of Surfaces, 3rd ed., Oxford University Press, Oxford
(1941).
168 Chapter 7
83. S. K. Rangarajan, Specialist Periodical Reports (Chemical Society, London), 7,203 (1980);
see also 1. Electroanal. Chern., 82, 93 (1977).
8.1. INTRODUCTION
Some of the nonaqueous electrolyte solution aspects of this field are dealt
with in Chapter 13, which is specifically on that topic.
Usually the solvents favored for electrochemical capacitor applications (as
for lithium batteries) are aprotic ones, i.e., those not containing electrochemi-
cally active H atoms, such as on -NHb -OH, -COOH functionalities in the mo-
lecular structure. This is an obvious requirement for higher voltage operation in
order to avoid discharge ofH2 from active protons in the structure of the solvent,
as with alcohols or carboxylic acids. The most commonly employed and prac-
tically satisfactory nonaqueous solvent for higher voltage electrochemical ca-
pacitors is propylene carbonate, which is sometimes mixed with other solvents
such as dimethoxyethane to improve the electrolytic conductivity of dissolved
R4N+ salts.
In practice, not only is the decomposition voltage of the nonaqueous solu-
tion important for capacitor design and operation, but favorable dissociating
ability for dissolved electrolytes is also required (see Chapter 13). This is also
indirectly related to the solubility of a particular electrolyte in a given solvent.
Both factors determine the conductance of the solutions as a function of concen-
tration, an important matter for optimizing power density. These factors are de-
termined mainly by the Gibbs energy of solvation of the ions of the electrolyte
in the particular solvent under consideration 1,2 (see Chapter 13).
Substantially less work has been reported in the literature on this topic than
on electrode interfaces in aqueous media. 3 Practically speaking, there are usu-
ally experimental problems in purifying and drying solvents, which can add
costs in producing nonaqueous solution capacitors. Various activities have been
carried on commercially in this field at carbon powder and fiber electrodes, but
they often involve proprietary knowledge and techniques. On the fundamental
research side, most work has been directed to studies of the Hg electrode inter-
face in nonaqueous solutions as a basis for comparison with the very extensive
Behavior of the Double Layer 171
results that have been obtained for this metal in an aqueous medium; e.g., see
review Refs. 3,4, and 5.
The types of study include:
Some of these topics, however, have not been worked on in either the depth or
detail that has characterized studies of corresponding aspects of aqueous solu-
tion behavior. 3- s
Whether the solvent is structured or relatively unstructured is of major im-
portance in the capacitance behavior of the interphase. It is also important in de-
termining the state of solvation of ions and especially their partial molar
entropies in solution. 1,6-8 Structure in solvents is usually the result of hydrogen
bonding, although some highly polar aprotic solvents such as nitromethane and
acetonitrile can also exhibit structure due to strong dipole-dipole interactions.
Gases are unstructured, solids are highly structured; over small but signifi-
cant ranges of distance, the extent of structure in liquids is experimentally rec-
ognizable (e.g., by X-ray or neutron diffraction), but only over short ranges of
intermolecular distance, two to three molecules in range. The degree of structure
in a liquid depends on the intermolecular potential energy and its orientational
dependence in the case of dipolar solvents and especially H-bonded solvents.
The extent of structure is usually related to the dielectric constant and viscosity.
Intermolecular structure in liquids can be determined by evaluating the ra-
dial distribution/unction (rdf) and the orientational distribution function around
a given central reference molecule or center. These functions are calculated
from observations of X-ray and neutron diffraction. 9 Some of the earliest work
of the X-ray diffraction type was done on water, 1,10-12 the structure of which is
related to that of ice. The diminution of short-range structure with increasing
temperature was also demonstrated l 1,l3 (Fig. 8.1). Theoretical calculations of
172 ChapterS
(b) 83°C
rdfs have also been made,12-14 with considerable success (Fig. 8.1). However,
most of this work has focused on water and ice, with a little also on methanol. 15
The structural aspects of solvent properties are important in double-layer
capacitance behavior for reasons similar to those for ionic solvation: thus, it is
either the interfacial field at a charged electrode surface or the radial field and
field gradient beyond the periphery of an ion, into solution, that tends to bring
about dipole orientation along the field lines (depending on the dipole-field en-
ergy, ,uE, compared with kD. This orientation is opposed by structural interac-
tions, e.g., intermolecular hydrogen bonding and/or dipole-dipole interactions.
Behavior of the Double Layer 173
Adsorbed ion
co-sphere overlap
FIGURE 8.2. Overlap of regions of solvent in the double layer at an electrode that are influenced
both by the double-layer field and by the field of ions in the Helmholtz layer: (a) overlap between
co-plane and ion-cosphere solvent and (b) overlap between ion solvation cospheres.
well as, in a general way, by their freezing points and viscosities. Structured sol-
vents have high dielectric constants ca. 30 to 115 (HCN)I, and relatively long
relaxation times ca. 1O- 11 S for water. Intermediate solvents have dielectric con-
stants from 10 to ca. 20 and relaxation times of 10- 12 to 5 x 10-13S. Unstructured
solvents have low dielectric constants, 3-8.
The bulk dielectric constants in the above ranges might be expected to be
mirrored in the capacitances and the dielectric constants of double layers con-
taining the respective solvents, but exact values are not directly known. They
can be estimated roughly from measured capacitances and assumptions about
double-layer thicknesses in various solvent media.
However, some of the earliest work on the double layer at electrodes in
nonaqueous electrolytes by Frurnkin 16 showed that the capacitance at Hg did not
correlate with the bulk dielectric constants of the solvents employed. Perhaps
this is not surprising since the behavior of solvent molecules in the field of the
interphase and adjacent to a metal surface depends more on microscopic mo-
lecular properties, such as the dipole moments of individual solvent molecules,
or of their polar functional group(s) (e.g., OH, NHz, CN) and their lone-pair
donicities, rather than the behavior of an interacting bulk assembly, the overall
properties of which determine the dielectric constant.
The origin of this absence of systematic correlation is the lack of a direct
dependence of the dielectric constant of solvents on their individual molecular
dipole moments, especially for associated liquids. In the case of vapors, their di-
pole moments can be derived directly from the temperature dependence of the
Behavior of the Double Layer 175
respective measured dielectric constants, based on the theory of Debye and the
Clausius-Mosotti equation (Chapter 5). However, for liquid-phase dielectrics
and for vapors at relatively elevated pressures, the relationship between dipole
moment and dielectric constant is more complex and its interpretation depends
on models of orientational correlation associated with short and longer range
molecular interaction, especially in the case of the associated solvents.
A further complication arises at charge densities where significant lower-
ing of the dielectric constant values can take place due to dielectric saturation
effects 17- 19 at high interphasial fields resulting from the high surface charges.
Similar dielectric saturation effects occur at solvated ions in the solvation co-
spheres and have been treated theoreticallyp,20,21 In fact, the dielectrically po-
larized layer of solvent next to a charged electrode interface behaves quite
similarly to that existing around and near an ion in its solvation coordination
shell (see Fig. 8.3). Dielectric saturation effects tend to diminish the capacitance
of an electrode interface. There are also compressional effects (electrostric-
tion 22,23) that increase the molecular density of solvent in the double layer,
which tends to change the capacitance in the opposite direction. 23
For the same reasons that protic solvents cannot be used for Li batteries,
because of potential electrochemical discharge of H atoms bound at electro-
negative atom centers, similar restrictions apply to the choice of nonaqueous
solvents and their electrolyte solutes for high operating (cathode) voltage elec-
trochemical capacitors. Also, solvent oxidation on the positive plate of a
charged capacitor can introduce some other limitations. These two effects are
determined by the electrocatalytic properties of carbon surfaces for reduction or
oxidation if potentials adventitiously exceed those for solvent or solute dis-
charge on accidental overcharge of the capacitor device. Therefore, in practice,
there are only a few nonaqueous solvents, or mixtures thereof, that can be reli-
ably used for high-voltage capacitors. Usually the preferred choices are propyl-
-' -- --r-~ , , +
-
/
:---
~\
+
---
I \
I
-+_1
\ +
I'
I
+
\;'
\ I
--
\ + ...-
~
",
---- -
\ /
/ /
+
a) Ion b) Charged electrode
FIGURE 8.3. Models of approach to dielectric saturation at (a) an ion (in its primary solvation
shell) and (b) in the charged double-layer interphase (Helmholtz-layer ions not shown).
176 Chapter 8
1. Waterlike capacity curves: these have a hump near the pzc and minima
either side, that on the positive branch being at higher C than that on the
negative branch. In addition to water, this group includes N-monosub-
stituted formamides and related amide solvents, as well as dimethyl sul-
foxide.
2. Singly humped capacity curves: these are related to the first group since
a hump is observed. The minima are absent, probably because of experi-
mental limitations to the ranges of potential that could be covered. The
solvents representing this case, however, have a common feature in that
they are all cyclic, e.g., ethylene and propylene carbonates, sulfolane,
4-butyrolactone, and 4-valerolactone.
3. Water-unlike capacity curves. These show only a single, parabolalike
minimum, and include ammonia, alcohols, N,N-dimethylformamide
and N,N-dimethylacetamide, acetonitrile, acetone, ethyleneglycol and
pyridine-a series of solvents that show hardly any chemical molecular
similarities!
u
?:' \,
'g 20 'l!
D.
a.
c "."-.
"..,..
u
~
GI
.2 15 ••'•."'0
~
GI
C
.5
.......
·0
+10 0 -10
q1fL C cm- 2
FIGURE 8.4. Inner-layer capacity of an Hg electrode in ethylene carbonate (circles indicate the
results of Fawcett and Macke/o) fitted by a theoretical model based on the treatment by Levine,
Bell, and Smith. 33
34
...
cu
>-
o
CI.I
j5 16
::l
o
Cl
10
FIGURE 8.S. Differential capacity of an Hg electrode for 0.1 M solution of NH4F in methanol
(results of Grahame 35 ). Note difference of shape from aqueous solution curves.
Behavior of the Double Layer 179
CH -CH-CH
3 I 1 2
0,
'c""" °
1\
°
1. Propylenecarbonate II. y-Butyrolactone
N 30
E
~
lI..
::t. ~~................. 30
>. BL ,,-' ....
1\",
E 20 _. . .,J-._ .... \ ..
o EC ' \\.
a. ,/
o \\
...
u VL \ 20
CLI
>- \ ,\
.2 10 \ .
,'.
CLI ' ....~~-.- ........ _ -BL
:0 ,, '-. -'-'-EC-
5 , 10
o ',......... --VL-
of capacitance vs. potential from +0.6 V to -1.5 V, vs. the above calomel refer-
ence potential, follow approximately the same shapes. Toward the more nega-
tive potentials, the capacitance falls to 8 or 13 f1F cm-2, which is not too
different from the values for water at Hg under similar conditions(16 f1F cm-2).
Work on the amide solvents has been more extensive. 25 Capacitance humps
are observed on the negative side of the pzc, but the profile for N,N-dimethyl
formamide is more featureless.
The amide solvents have, however, been little used in preparing electrolyte
solutions for electrochemical capacitors and their stabilities are less than that of
propylene carbonate, which is the favored solvent, sometimes in mixtures with
dimethoxyethane (DME). Such solutions, using R4N+ salts as electrolytes, have
relatively high decomposition potentials in the anhydrous state and thus enable
electrochemical double-layer capacitor devices to be operated up to a plate volt-
age difference of about 3.5 V per cell, or a swing voltage of ±1.75 V.
In conclusion, a useful review on the behavior of non-aqueous solvents at
metal interfaces, by Trasatti,36 should be mentioned.
REFERENCES
9.1. INTRODUCTION
9.1.1 Historical
A substantial fraction of the whole body of electrochemical capacitor de-
velopment has depended, and continues to do so, on an understanding of the
properties of carbon, especially in its more dispersed and conducting forms, in-
cluding materials having fibrous or foamlike morphologies. It has been known
for many years that there are two or really three natural allotropic forms of carb-
on: diamond, graphite, and the fullerenes, as noted in an earlier chapter. The
graphite modification is crystalline and a moderately conducting, anisotropic,
electronic conductor. Diamond is a highly ordered and insulating material. In
addition, amorphous forms of carbon are well known, and transitions between
amorphous and graphitic structures are possible at elevated temperatures, but
are possible for diamond only at extremes of conditions. In more recent years,
other modifications of carbon have been prepared or become known, namely,
the fullerenes (which may exist in interstellar space), glassy carbon, and exotic spe-
cies such as C 2, which was also detected in interstellar space. Carbon "blacks" such
as Shawinigan black or acetylene blacks (soots) are well known and have relatively
high specific surface areas in the range of 30-1000 m2per gram. However, they are
not usually suitable for fabrication of capacitor electrodes.
Carbon has a unique position and electronic structure (ls2, 2s2, 2p2) in the
Periodic Table, being midway along the first eight-element period, so it has in-
183
184 Chapter 9
capacitor development originated directly from the experience gained in the fuel
cell electrode field under the direction of Rightmire, who realized that a 400
m 2g- 1 porous carbon material would give rise to a double-layer capacitance of
80F g-l, assuming a specific surface capacitance of 20 f.1F cm- 2. An energy stor-
age device for electric vehicles, employing large capacitors, was already envis-
aged in the early 1960s.
A brochure published by Sohio Corp., dated April 25, 1969, described a
so-called "electrokinetic capacitor" having the capability of substantial energy
storage. Twenty 100-f.1s discharges at 20 A or 66% of the decline of initial volt-
age could be achieved in 20 f.1s.
Sohio Brochure for Double Layer Capacitor
SOHIO NON-POLAR ELECTROKINETIC CAPACZTOR
Introducti.on
GOHI~
The choice of name, "electrokinetic capacitor," for the device was perhaps
inappropriate however: the charging or discharging processes in a double-layer
electrochemical capacitor involve virtually no electrode kinetics, Faradaic proc-
esses are not usually involved to any substantial extent in such devices except
on overcharge. The actual term "electrokinetic" derives from colloid science
and is connected with the movement of colloidal particles in an electric field-a
very different phenomenon from double-layer charging. The front page of So-
hio's announcement brochure (shown in a publication by Argade from Techno-
chern Corp.) is reproduced above, with permission.
Because of residual surface "valencies," most carbons that have been ex-
posed to air (which is the usual situation) contain adsorbed (mostly chemisor-
bed) oxygen, which can lead to various O-based surface functionalities 3 ,7
(ketonic, peroxyl, hydroxyl, quinonoid). It is these types of surface state that can
be modified by high-temperature treatment.
The Double Layer and Surface Functionalities at Carbon 187
FIGURE 9.1. Crystal structure of the benzenoid layers of graphite and an element of their conju-
gated bonding.
edges of the 2d-structure planes in the case of graphitic materials), their relative
proportion in the material tends to scale with the specific surface areas (cm2 or
m2 g-1) of the material. For such redox reactivity, a significant redox pseudoca-
pacitance, CtfJ (see Chapter 10) arises as well as the desired predominant double-
layer capacity, Cdl • In fact, with some carbon materials, it appears that CtfJ can
amount to some 5-10% of the total realizable capacitance, and scales approxi-
mately with the Cdl value. However, the distinction between the C¢ and Cdl con-
tributions (in principle possible by means of impedance analysis), becomes
difficult when the interfaces are part of a porous matrix system. The extent of
this scaling depends very much on the nature and conditions of high-tempera-
ture pretreatment the carbon material may have undergone prior to fabrication
The Double Layer and Surface Functionalities at Carbon 189
ketone
phenolic
carboxylic
carbinol
o-hydroquinoid
lactone
into a capacitor device and its prehistory of exposure to atmospheric air, leading
to oxygen chemisorption.
In addition to electrochemical (redox) activity, various carbon materials
exhibit titratable acidic and/or basic functionalities related to some of the sur-
face structures 7 illustrated in Table 9.1. Such surface structures influence the
wettability of carbon materials, a matter of considerable importance in maxi-
mizing the access of electrolyte to the surface of carbon modifications in the
preparation of electrochemical capacitor matrices. Note that the requirements
190 Chapter 9
for capacitors in this respect are the opposite of those preferred for gas-diffusion
fuel cell electrodes, in which hydrophobic additives are usually incorporated to
maintain a three-phase gas/liquid/solid interface in the electrode matrix.
Edge quinonoid groups that can exhibit redox C¢ activity are also titratable
as acidic functions in their reduced form (=0 7 -OH ~ -0- + H+). Acidic
phenolic and carbonxylic surface groups probably have only acid or base ac-
tivity.
The presence of various polar surface functionalities on graphitic materials
thus not only affects the potential-of-zero charge (Chapters 6 and 7) but also the
contact angle with the electrolyte under conditions of incomplete wetting of
pores in capacitor-type, high specific-area electrodes. A correlation between the
contact angle of water and carbon, and the quantity of oxygen and hydrogen as-
sociated with carbon blacks was indicated in work by Studebaker and Snow. 9
As might be expected, electrochemical oxidation of carbons increases their wet-
tability due to an increase in 0 content associated with hydrophilic surface
groups. Electrochemical reduction has an opposite effect. These results were
obtained in work by Kinoshita and Bett. lo Related to the wettability is the heat
of immersion of carbon black ll in a slurry, which is substantially larger at low
(2-3) than at neutral pH, indicating the role of basic oxygen groups. An impor-
tant point for electrochemical capacitors is that the accessible porosity, which is
determined by wettability, will influence the double-layer capacitance that can
be obtained, especially in fine-pore, high-area materials.
A voltammogram for the processes occurring on a Union Carbide ZTA
grade of graphite, studied by Blurton,12 is shown in Fig. 9.2. Figure 9.3 shows
comparative behavior at a heat-treated Vulcan carbon. An interesting related se-
ries of results on a carbon fiber electrochemically oxidized to various potentials
in dilute aqueous HN0 3 were given (Fig. 9.4) by Kozlowski and Sherwood,13
who examined the CIs XPS spectra. As potential was increased, component spe-
cies having lower electron binding energies progressively increased; increase in
carbonyl- and quinone-type functionalities with increasing potential (up to 3.0
V) corresponds to the changes observed in the XPS spectra. This interpretation
is not entirely supported, however, since in other XPS work,14 increasing elec-
trochemical oxidation from 0.5 through to 3.0 V in H 2S04 indicates the domi-
nance of )C=O groups at low potentials but an increase in C-O- (ether)
groups at more positive potentials, perhaps a chemically surprising result.
The identification of various surface functionalities on carbon materials
has also been conducted by means of infrared and Raman spectroscopy. These
techniques provide rather detailed information on surface groupings that are
characteristic of various types of carbons (blacks, C fibers, graphitic materials,
activated carbons) and their pretreatments. A detailed account of this work, to-
gether with examples of the characteristic spectra observed, is to be found in
Chapter 3 of ref. 3.
The Double Layer and Surface Functionalities at Carbon 191
250
200
150
100
N
--
E
0 50
«=l
---cQ)
-50
0
~
t)
-100
-150
-200
FIGURE 9.2. Voltammogram for ZTA grade Union Carbide Corp. graphite in 0.5 mol dm- 3
aqueous H2S04 at 303 K. The sweep rate is 10 mV S-I. Reprinted from K. F. Blurton, Electrochim.
Acta, 18, 869 (1973), with permission from Elsevier Science.
1.2r----.-----.----.-----~--~r_--~----~
U
"C
g 0.8
«
0.4
<t
E
..... 0
....Z
w
a:: -0.4
a::
::>
u
.~ -0.8
"C
o
..c
o
U -1.2 :----='::------::-'-:---~L:----_::l::---...L-----.JL---l
o 0.2 0.6 O.S 1.0 1.2 1.4
POTENTIAL/V
FIGURE 9.3. Cyclic voltammograms for the oxidation of heat-treated (2700 DC) Vulcan XC-72
carbon at + 1.2 V in 95% H3P04 at 160 DC. Increasing current responses correspond to increases in
anodic oxidation time: 0,5,60, and 250 min. The sweep rate is 14 mV s-l. Reprinted from K. Ki-
noshita and 1. A. S. Belt., Carbon, 13,403 (1975), with permission from Elsevier Science.
192 Chapter 9
(a) Cd)
0.5 V 2.0 V
l!l
'c
:::l
~ (b)
t
?:
1.0 V
'(jj
c
~
(C) (f)
1.5 V 3.0 V
rather discrepant, varying from 16 to 60 f1F cm- 2 for the basal plane (polished)
of ordinary pyrolytic graphite in 0.9 M aqueous NaF to 60 f1F cm-2 on a similar
surface in 0.5 M aqueous KCl. However, on a cleaved basal plane (which is
likely to be cleaner), a low value of 12 is reported for 0.5 M aqueous KCl. For
stress-annealed pyrolytic graphite, values of C of around 20 are reported! for a
peeled-off basal plane film in aqueous NaF, NaOH, and H 2S04 , while for pol-
ished edge-plane sections, higher values from 50 to 70 f1F cm-2 are found. 2
Carbon blacks have C values from ca. 4.5 to 10,11,18 "active" carbons
around!9 10 to 15 f1F cm- 2, while graphite powders exhibit C values of 20 to 35
f1F cm- 2. On the other hand, "graphite cloth" TGM 285 exhibits!810w values-
between 1 and 3 f1F cm- 2. This is a surprising result and may be a consequence
of uncertain evaluation of true real areas of test samples or of surface contami-
nation by nonpolar organics in the preparation of the cloth. The specific capaci-
tance values for powder materials are given here per real square centimeter, but
this is usually based on some not always reliable "real surface area" measure-
ment per gram. Thus the derived apparent capacitances per "real square centi-
meter" may not be entirely reliable and can depend on pore accessibility and
pretreatmen t.
Another problem is the necessity for specifying the potential range of
measurements (around the pzc). Differences in C by a factor of 2 between po-
tentials that are substantially positive and substantially negative to the pzc can
arise at well-defined surfaces, as is known for Hg.20
Generally, the quality of experimentation and control of conditions in ex-
periments 4 at carbon have not been at all as good or rigorous as work at Hg or
at single crystals of Au, e.g., in work by Hamelin.2! Other problems arise be-
cause carbon surfaces are not as ideally polarizable (see Ref. 20) as Hg or Au
because of surface oxidation reactions and the possibility of intercalation proc-
esses taking place, especially upon cathodic polarization. Thus the electro-
chemical characterization of carbon/solution interfaces is substantially more
complex than that for various metals, especially the noble ones and mercury.
Despite the reservations expressed here, a series of interesting papers was
published by Soffer et a1. 22- 3 ! on porous carbon materials, some of the earliest
in the field, about the time at which Sohio began to develop carbon double-layer
capacitors. Soffer and Folman22 realized that at high-area porous carbon elec-
trodes, the uptake of ions from solution as a carbon interface was being charged
could be directly measured, in their case by determining the changes of conduc-
tivity of the neighboring solution. Thus, using 2 g of a carbon electrode having
500 m2 g-! real area and an integral double-layer capacitance of 10 f1F cm- 2,
they showed that the electrode would adsorb 1 mmol of ions for a I-V change
in potential. (They later developed this phenomenon for selective removal of
ions from bulk solutions.)
The Double Layer and Surface Functionalities at Carbon 195
A very large amount of work has been done on oxidation of carbon includ-
ing of course the ultimate oxidation processes, combustion to CO and CO 2,
Electrochemically, oxidation is much more restricted, especially at ordinary
temperatures, but fuel cells employing a coal slurry have been investigated in a
number of works and applications.
For carbon-based double-layer capacitors, the state of superficial oxidation
especially at edge planes, is of most significance because this can determine the
charge accommodation per gram and the corresponding capacitance. It can also
influence the self-discharge characteristics (Chapter 18) of carbon capacitors
and how carbon materials can be conditioned by heating them to elevated tem-
peratures in a vacuum, nitrogen, or hydrogen, and sometimes in water vapor.
One of the earliest conferences devoted to the state of carbon was the Fara-
day Discussion in 1937 on chemical reactions involving solids, published in the
Transactions of the Faraday Society. This volume included a classic paper by
Meyer34 on surface reactions of graphite with oxygen, carbon dioxide, and
water vapor; and other papers on the characterization of surface groups,? (e.g.,
ketonic, ketenic, and quinonoid) on carbon, including the possibility of forma-
tion of surface peroxide groups due to direct combination with dioxygen mole-
cules, either bridged or end-on.? At elevated temperatures (1450 DC), some
reaction to form surface groups [e.g., a-diketo functions (ortho-quinone)] oc-
curs with release of H 2, though some rupture points at edges lead to decompo-
sition of such groups.
Under conditions of anodic electrolysis, the a-diketo grouping on graphite,
which corresponds to an ortho-quinone structure, is capable of being oxidized. 32
At low current density in H 2S04, the maximum volume of CO generated is
The Double Layer and Surface Functionalities at Carbon 197
equal to that of CO 2, This process occurs at rupture points on the edges of the
graphite planes, with breaking of the outer C-C bonds; a new keto group is
formed in the graphite structure while the outer keto group is oxidized to a car-
boxyl group.
Sihvonen proposed further complex surface-edge chemical reactions?2
Figure 9.5 is a schematic diagram of various reaction product groupings at the
surface of an element of the graphite structure. As indicated earlier, these struc-
tures also determine the electrochemical interfacial state of graphitic carbon ma-
terials and their double-layer properties, including pzc values and specific
adsorption of ions. It must be emphasized, however, that a variety of high spe-
cific-area carbon preparations used in fabricating electrochemical double-layer
capacitors are not graphitic in structure, though some of the surface groupings
referred to here may be present.
In other work, the role played by surface oxides in the oxidation of carbon
was treated by Strickland-Constable,? who emphasized the significance of
:::;C=O groups on the surface, like those in the structure of acetone. He con-
cluded that the oxidized state of carbon surfaces consists of covalently bound
°
surface compound species. This conclusion was in agreement with Schilow,35
who showed that when outgassed charcoal was treated with molecular 2, sur-
face compound species developed that had both acidic and basic properties, but
such species corresponded to only a small fraction of the bound oxygen. In this
work it was indicated that amorphous carbon was still mainly graphitic, but con-
FIGURE 9.5. Surface-edge chemical-oxidation structures and related reaction products devel-
oped at graphite. After Sihvonen;32 in the original paper, Roman numerals identified various reac-
tions and functionalities at the surface that are referred to in that paper.
198 Chapter 9
I I I
4.0f- -
3.0f- -
I I I
+0.5 o -0.5
E/V VS NHE
FIGURE 9.6. Capacitance vs. potential (NHE reference) curves for basal plane of stress-annealed
pyrolytic graphite in NaF + Nal solutions (pH 6) at 298 K and 1000 Hz. x = 0.9 mol dm-3 NaF; /}.
= 0.8 NaF + 0.1 NaI; 0 = 0.9 NaF + 0.01 Nal. (From Yeager, Moller, and Gupta. 6 Reproduced by
permission of The Electrochemical Society, Inc.)
voltammograms taken at 0.1 V s-1 at these surfaces are also shown in the fig-
ures 6 ; they are rather featureless.
On the edge orientation, however, the capacitance curves show much more
structure, as a function of potential; also, there is a major dependence on the type
of electrolyte (aqueous 0.05 M H2S04 and 1.0 M NaOH) and, in addition, the
capacitance values are much higher, being in the range 70 to 100 flF cm-2. The
behavior in 1.0 M NaOH exhibits a maximum around -0.4 V (vs. NHE), which
is reminiscent of behavior at Hg.2o The symmetry of the curves for the basal
plane, the low minimum of the capacitance values, and the non dependence of
the behavior on the presence of adsorbable anions clearly indicate that it is not
a graphite/solution double-layer capacitance that is being probed but rather a
space charge on the inside of the graphite basal plane interface.
The Double Layer and Surface Functionalities at Carbon 201
7.----,-----------,-----------.----------,
BORONATED (0.3 %)
C\I
Ie
u
IJ... 5
:t
......
U ,,
,,
,,
/
/
,
/
4 /
//
' I. //WITHOUT BORON
"
........ _--/ ,/1 M NAOH 10.5 M H2S04
3~----L-----------~----------~--------~
0.5 0 -0.5
E V vs NHE
FIGURE 9.7. Capacitance vs. potential curves (NHE reference) and current vs. potential curves
below, for basal plane of boronated and nonboronated stress-annealed pyrolytic graphite at 298 K
and 1000 Hz. Compare with Fig. 9.6. (From Yeager, Moiler, and Gupta. 6 Reproduced by permission
of The Electrochemical Society, Inc.}
(9.2)
where IfI is the potential at the surface and Ce is the electronic charge carrier con-
centration taken as 6 x 1018 cm- 3 and a dielectric constant, B ::: 3.0.
It is useful to note here that the space charge capacitance Csc behaves like
the ionic diffuse-layer capacitance20 in metal-electrolyte solution behavior at
202 Chapter 9
metals (see Chapter 6); it has rapidly rising values on each side of the minimum
at the potential-of-zero charge. Also, since it is combined in series with a Helm-
holtz layer capacitance, CH, the overall C is determined here by the smaller
Csc (cf. Eq. 9.1):
(9.4)
1'Or----.------.-------r------.------~
1M NoOH
(\/
IE 90
()
l.L.
::l 80
.......
u
O.05M H2SO4
70
FIGURE 9.8. Capacitance vs. potential curves (NHE reference) for edge-oriented pyrolytic
graphite as per conditions for Figs. 9.6 and 9.7. Curves for 1.0 mol dm- 3 NaOH (B) and 0.05 mol
dm- 3 H2S04 (A). (From Yeager, Moller, and Gupta. 6 Reproduced by permission of The Electro-
chemical Society, Inc.)
The Double Layer and Surface Functionalities at Carbon 203
bie centimeter than other types of carbon, depending on the number of basal
plane exposures relative to that of edges. Also to be noted is that high-tempera-
ture pretreatments that enhance graphitic structures will have the effect of in-
creasing the amount of semiconductor behavior of the thermally conditioned
carbon material.
4oor----.----.-----r----.----~--~2.0
1.5
l(1l
--
0~
N .......
E
....... c:
c 1.0 CI.l
~ c:
0
<t U
-u
CI.l c:
CI.l
c
....
;:)
(1l
>-
)(
(/) 0
100
°0~--~----1~0~0~0~~~--2-0~0-0----~--3-0~006°
Temperature / °c
FIGURE 9.9. Surface area modification and bound oxygen change due to heat treatment of a Vul-
can-type XC 72 carbon. (From Chu and Kinoshita. 38 Reproduced by permission of The Electro-
chemical Society. Inc.)
The type of heat treatment and the nature of the precursor of the carbon ma-
terial are major factors in choice and optimization of high-area carbons for dou-
ble-layer capacitors, as they are also for Li-ion host materials for Li battery
anodes. For example, activated carbon fibers (ACFs), having ca. 1600 m 2 g-l,
can be prepared for capacitor devices by carbonization of phenolic resins fol-
lowed by activation in steam at 1000 dc. The relation of types of carbon mate-
rials to their precursors is illustrated in Fig. 9.10 (Chu and Kinoshita38 ).
The graphitization effect of high-temperature treatments is usually greatest
with "soft" carbons, which show the largest changes of microstructure. Hard
The Double Layer and Surface Functionalities at Carbon 205
Carbon Material
Precursor for Double-Layer Capacitors
Petroleum Microbeads
FIGURE 9.10. Relation of types of carbons to their precursors. (From Chu and Kinoshita. 38 Re-
produced by permission of The Electrochemical Society, Inc.)
References
1. I. Tanahashi, A. Yoshida, and A. Nishino, 1. Electrochem. Soc., 137,3052 (1990).
2. A. Soffer and M. Folman, 1. Electroanal. Chem., 38
3.1. Randin and E. Yeager, 1. Electroanal. Chem., 36, 257 (1972).
4.1. Randin and E. Yeager, 1. Electrochem. Soc., 118, 711 (1971).
5. S. Evans, 1. Electrochem. Soc., 113, 165 (1966).
6. K. Kinoshita and J. Belt, Carbon, 11,403 (1973).
7. E. Gagnon, 1. Electrochem. Soc., 122
8. K. Kinoshita, Carbon: Electrochemical and Physicochemical Properties, pp. 294-295, Wiley, New York
(1988).
tial increases in specific capacitance can be obtained using the indicated pre-
treatments.
Sullivan et a1. 39 described another example of an advantageous treatment
of a carbon material for use in an electrochemical capacitor. By means of chemi-
calor electrochemical oxidation of glassy carbon, these authors showed that a
double-layer capacitor material results that is particularly suitable for high
power-density applications due to its low internal resistance. An active surface
region is generated that is porous and permeable to electrolyte. A high specific
capacitance of ca. 250 F cm-3 over a I-V potential step charging and discharging
program was obtained. 39
The Double Layer and Surface Functionalities at Carbon 207
FIGURE 9.11. Effect of heat and gas-phase treatment on carbon fibers as revealed by cyclic vol-
tammetry at 5 mV s-I. (From Chu and Kinoshita. 38 Reproduced by permission of The Electrochem-
cial Society, Inc.)
208 Chapter 9
500r-------------------------------------~
1,4-NophothoQu i none
400
-I
0> 300
Superocid
LL Initiol
.......
Q)
-
(.)
c: 200
o
( .)
o
0-
o 100
U
__ Initial
-
-.........
>- 0.4
' (3
o
0..
o
U
0.2
and surface species was clearly demonstrated in the ESR results of Harbour and
Walzak. 46
A process that can lead to generation of free-radical centers is the forma-
tion of peroxides by reaction of unsaturated organic structures with molecular
oxygen. This can occur at the (edge) double bonds of graphitic structures. The
subsequent dissociation of bridged or linear -O-OH groups can lead to -0' or
-0-0' free radicals on the surface of carbon materials. In the presence of dis-
solved 02> on cathode electrode charging in an electrochemical capacitor,
z
HO or H 20 2 can be formed. In fact, carbon is a well-known electrode surface
for electrochemical generation ofH20 2. H 20 2 can then give rise to free radicals
by well-known surface or bulk reactions, especially in the presence of traces of
Fe species (Haber-Weiss reaction), and is one of the species involved in self-
discharge processes (Chapter 18) at charged capacitors.
A paper by Thrower47 is relevant to the variety ofESR signals arising from
carbon materials. He discusses the great multiplicity of carbons, their physical
properties (Table 9.5) (depending on their source), and preparation and pretreat-
ment procedures. The effects of heating at elevated temperature are discussed,
including X-ray diffraction evidence for modification of crystallite size and
mean spacing between the carbon layer planes. Procedures for preparation and
orientation of carbon fibers from rayon, polyacrylonitrile, and pitch are also
considered in this paper, including characterization methods based on X-ray dif-
fraction, scanning electron microscopy (SEM) and transmission electron mi-
croscopy (TEM). Such carbon-fiber materials are of major technological
interest for fabrication of electrochemical capacitors having good mechanical
integrity and low equivalent series resistance values (see Chapter 17).
Oxygen complex formation at carbon surfaces, which can lead to ESR sig-
nals, follows an initial physisorption at carbons with subsequent chemical func-
The Double Layer and Surface Functionalities at Carbon 213
o
o
I I I
40 60 80
100 150 200
thus the energy state to or from which, on average, electrons are withdrawn or
donated in cathodic or anodic reactions). However, information on the suiface
state of conducting materials is given through lP measurements 50 since lP al-
ways contains a surface dipole contribution, X, often amounting to 20-30% of
lP. This contribution occurs because the experimentally determined lP value al-
ways includes the electrical work of transfer of an electron out from the metal
surface across the metal interface at which a surface potential contribution, ilX,
arises due to any molecular surface dipole structures. Thus changes in X caused
by the presence of such dipoles can be determined and information on the elec-
trical aspects of surface functionalities derived .
•
Differences in lP can be measured by determining differences in surface
potentials using the vibrating capacitor plate method of Volta, later further de-
veloped by Kelvin 5 ! (the Kelvin probe), or by means of contact-potential deter-
minations. Changes in work function are thus related to changes in the surface
dipole potential Xd; Xd is given by
(9.5)
where n is the number of dipoles per square centimeters of surface having a sur-
face dipole moment component, fl, normal to the surface. As n approaches its
The Double Layer and Surface Functionalities at Carbon 215
>Q)
---"'0
0
C'
-e-
I
c
0
...
.0
0
u
"S- 0.1
...........
O~ _ __ L_ _ ~~ __ ~ __ ~
2 4 6 8 10
pH
FIGURE 9.15. Relation of work-function difference between various carbons and a gold plate,
and pH of slurries of the respective carbons. Reprinted from T. J. Fabish and D. E. Schliefer, Carb-
on, 22, 19 (1984), with permission from Elsevier Science.
216 Chapter 9
300~--~----.----.-----r----~--~----~
o
250
C\I
IE 200
u
01
\-
Q)
.......
c
0
'in
\-
Q) 150
E
E
'0
.....
0
Q)
I 100
50~--~----~----~--~----~--~~--~
1 2 3 4 5 6 7 8
pH
FIGURE 9.16. Dependence of heats of immersion of a high-area carbon black on pH in an aque-
ous slurry. Reprinted from T. Murata and Y. Matsuda, Electrochim. Acta, 27, 795 (1982), with per-
mission from Elsevier Science.
ference between the carbons and a gold reference plate is plotted against the
slurry pH. 52 Corresponding data were obtained for seven water-extracted carb-
on blacks subjected to various surface treatments.
The pH relations show characteristic minima at an isoelectric pH around
6.3. The carbon black work function values are assumed to be directly related
to base uptake33 and are therefore determined by acidic polar functional groups
The Double Layer and Surface Functionalities at Carbon 217
A factor that has to be taken into account when using graphitic materials
for capacitor electrodes is the possibility of intercalation of species dissolved in
the electrolyte, especially anions at the anode of a capacitor electrode (on
charge) or possibly also of some cations at the negative electrode. Intercalation
into the layer structure of graphite has been known for many years,32 but more
recently its practical implications have been recognized.
Beck and Krohn 53 studied the reversible intercalation and deintercalation
of anions at highly crystalline graphite electrodes. Interfacial charge transfer
processes coupled with diffusion can be involved. Riidorff and Hofmann 54 were
the first to perform an electrochemically driven intercalative sorption of strong
sulfuric acid (cf. Ref. 19) into graphite. The overall reaction was written 54 as
where n solv. represents the number of solvating solvent (water) molecules as-
sociated with the anion A-in solution. The Gibbs-energy driving force for this
process will be determined by the difference of accommodation energy of the
guest anion in the C~ host and the (change in) energy of solvation of the anion.
In addition, there will be an electrical Gibbs energy component that is deter-
mined by the electrode potential of C x relative to that of the solution in which
A - initially resides. The energy of A-in the lattice will also depend on the ex-
tent, if any, to which the intercalated anion undergoes charge transfer with the
lattice instead of forming the ion pair, C~A-.
Examples (positive and negative) of reversible electrochemical intercala-
tion of anions (which can be significant at positive capacitor electrodes of gra-
phitic powder) into a composite of natural graphite crystal flakes with 20%
polypropylene (CPP) are listed in Table 9.6. The examples cited include acids
commonly employed as electrolytes for aqueous solution electrochemical ca-
218 Chapter 9
pacitors. The intercalation processes were studied by means of slow (mV s-l)
cyclic voltammetry in the cases of 4 M concentrations of H 2S04 , HCI04 and
HBF4 solutions.
Ebert55 reviewed the general electrochemistry of intercalation compounds
of graphite. The general basis of lattice oxidation, forming a delocalized posi-
tive charge on the benzenoid framework of the larger crystal structure with in-
tercalation of anions as counter charges, was emphasized. The sorbed anions
were regarded as being screened by co-sorbed solvent molecules, i.e., the anions
retained some degree of solvation. Thus the mechanism is a phase-transfer of the
solvated anions coupled with electron transfer from the lattice (anodic interca-
lation). The case of sorption of cations (Li+) into carbon host materials now con-
stitutes the major field of lithium ion anodes in the lithium ion battery field.
The whole question of the electronic and lattice-mode structure of graphite
is related to the topic of intercalation. This subject was considered in a review
by Dresselhaus,56 including the 2-dimensional band structure of graphite. 3,22
The Double Layer and Surface Functionalities at Carbon 219
REFERENCES
\. 1. P. Randin and E. Yeager, 1. Electroanal. Chem, 36,257 (1972).
2. J. P. Randin and E. Yeager, J. Electroanal. Chem., 58,313 (1975).
3. K. Kinoshita, Carbon, Wiley, New York (1988).
4. H. E. Becker, U.S. Patent to General Electric Co., No. 2,800,616 (1957).
5. J. C. Currie, in Chemistry and Physics of Composite Media, M. Tomkiewicz and P.N. Sen,
eds., vol. 85-8, p. 174, Electrochemical Society, Pennington, N.J. See also J. C. Currie, U.S.
Patent to Sohio, No. 4,730,239 (1988).
6. E. B. Yeager, 1. A. Molla, and S. Gupta, in Proc. Electrochemical Society Symposium on the
Electrochemistry of Carbon, vol. 84-5, p. 123, S. Sarangapani, 1. R. Akridge, and B. Schumm,
eds., The Electrochemical Society, Pennington, N.J. (1984).
7. R. F. Strickland-Constable, Trans. Faraday Soc., 34, 1074 (1938).
8. H. A. Kozlowska, in Comprehensive Treatise of Electrochemistry, 1. O'M. Bockris, B.E.
Conway, and E. Yeager, eds., vol. 9, Chapter 2, Plenum, New York (1981).
9. M. L. Studebaker and C.w. Snow, J. Phys. Chem., 59, 973 (1955).
10. K. Kinoshita and J. A. S. Belt, Carbon, 13,403 (1975).
11. T. Murata and Y. Matsuda, Electrochim Acta, 27,795 (1982).
12. K. F. Blurton, Electrochim. Acta, 18, 869 (1973).
13. C. Kozlowska and P. M. A. Sherwood, J. Chem. Soc., Faraday Trans., 1,80,2099 (1984).
14. A. Proctor and P. M. A. Sherwood, Carbon, 21,53 (1983).
15. S. Mrozowski and J. F. Andrews, in Proc.IVth Conference on Carbon, p. 207, Pergamon, New
York (1960).
16. L. S. Singer and C. Wagner, in Proc. Vth Conference on Carbon, vol. 2, p. 65, Pergamon, New
York (1963).
17. E. G. Gagnon, J. Electrochem. Soc., 122,521 (1975).
18. Y. Oren, H. Tobias, and A. Soffer, J. Electroanal. Chem., 162,87 (1985).
19. B. Kastening, W. Schiel, and M. Henschel, J. Electroanal. Chem., 191,311 (1985).
20. D. C. Grahame, Chem. Rev., 41,441 (1947).
21. A. Hamelin, in Modern Aspects ofElectrochemistry, vol. 16, Chapter I, B. E. Conway, 1. O'M.
Bockris, and R. White, eds., Plenum, New York (1981).
22. A. Soffer and M. Folman, J. Electroanal. Chem., 38,25 (1972).
23. A. Soffer, J. Electroanal. Chem., 40, 153 (1973).
24. J. Koresh and A. Soffer, J. Electrochem. Soc., 124, 1379 (1977).
25. J. Oren and A. Soffer, J. Electrochem. Soc., 125,869 (1978).
26. 1. Koresh and A. Soffer, 1. Electrochem. Chem., 147,223 (1983).
27. H. Tobias and A. Soffer, 1. Electroanal. Chem., 148,221 (1983).
28. Y. Oren, H. Tobias, and A. Soffer, J. Electroanal. Chem., 162,87 (1984).
29. Y. Oren and A. Soffer, J. Electroanal. Chem., 186,63 (1985).
30. Y. Oren and A. Soffer, J. Electroanal. Chem., 206, 101 (1986).
31. D. Golub, A. Soffer, and Y. Oren, J. Electroanal. Chern., 227, 41 (1987).
32. V. Sihvonen, Trans. Faraday Soc., 34, 1062 (1938).
33. L. Antropov, Theoretical Electrochemistry, Chapter 10.3, p. 277, MIR Publ., Moscow (1972).
34. L. Meyer, Trans. Faraday Soc., 34, 1056 (1938).
35. R. Schilow, Zeit. Phys. Chem., 149,211 (1930).
36. J. D. Lambert, Trans. Faraday Soc., 34, 1080 (1938).
37. The Electrochemistry of Carbon, Electrochemical Society Symposium, vol. 84-5, S.
Sarangapani, 1. K. Akridge, and B. Schumm, eds., The Electrochemical Society, Pennington,
N.J. (1984).
220 Chapter 9
1. K. Kinoshita, Carbon: Electrochemical and Physical Properties, Wiley, New York (1988).
2. R. L. McCreery, in Carbon Electrodes in Electroanalytical Chemistry, A. J. Bard, ed., vol. 17,
p. 221 (1987).
3. R. Barton, Carbon, 10, p. 395 (1972).
4. Faraday Discussion in Trans. Faraday Soc., 34, The Faraday Society, London (1938).
5. Chemistry and Physics of Carbon, P. L. Walker and P. A. Thrower, eds., 16, 119, Marcel
Dekker, New York (1973).
Chapter 10
modynamic reasons between the extent of charge acceptance (IJ.q) and the
change of potential (IJ.V), so that a derivative d(IJ.q)/d(IJ.V) or dq/dV, which is
equivalent to a capacitance, can be formulated and experimentally measured by
dc, ac, or transient techniques (Chapters 16 and 17).
The capacitance exhibited by such systems is referred to as pseudo-capaci-
tance since it originates in a quite different way from that corresponding to clas-
sical electrostatic capacitance of the type exhibited (mainly) by double-layer
capacitors. The term "pseudocapacity" was also used by Grahame in his 1947
review (Chapters 6 and 7), but to refer to the reversible discharge of ions (e.g.,
ofNa+) at high negative potentials at Hg. This usage is, however, different from
that employed here where extents of Faradaically delivered charge are a func-
tion of potential but no continuous currents pass in time.
It is now known that double-layer carbon capacitors exhibit perhaps 1-5%
of their capacitance as pseudocapacitance due to the Faradaic reactivity of sur-
face (edge) oxygen-functionalities (depending on the conditions of preparation
or pretreatment of the carbon material). On the other hand, pseudocapacitor de-
vices, like batteries, always exhibit some electrostatic double-layer capacitance
component proportional to their electrochemically accessible interfacial ar-
eas-probably about 5 to 10%.
At this point, it is useful to compare the potentialities for charge storage in
a double-layer capacitor with that in a pseudocapacitor device and a battery
electrode as shown in Table 10.1. From a thermodynamic point of view, pseudo-
capacitance originates whenever some property, y, proportional to charge
passed, is related to potential by an equation of the form
e
The quantity y can be an extent of fractional coverage of an electrode surface
(generated by the charge required for deposition of adatoms (e.g., H at Pt, or
metal adatoms in "underpotential deposition" reactions), an extent of fractional
absorption, X, into some intercalation host (e.g., TiS 2 or Co02 accommodating
Li), or third, some extent of conversion of an oxidized species to a reduced spe-
cies (or vice versa) in a redox system in solution [e.g., aq. Fe(CN):-lFe(CN)~-]
or one in a hydrous oxide, e.g., Ru02, Ir02' C030 4 (Chapter 11).
Each of the above types of examples corresponds in a formal general way
to an electron transfer process between an oxidized species Ox (e.g., H+ or H 20,
Li+, metal ion redox reagent) and a reduced species, Red (e.g., adsorbed H, Li+
in a host cathode lattice, metal ion in the reduced state in the redox reagent); thus
Ox+ze~Red
amined under ac modulation (Chapters 16 and 17); it varies with the square root
of frequency. This pseudocapacitance has no value for energy storage purposes
and is significant only in the frequency response of electrochemical reactions in-
volving diffusion (Randle's equivalent circuit treatment, Chapter 7).
K
H30+ + M + e ¢ MHads+H20 (I)
fW 1-8 V 8
Electrochemical Capacitors Based on Pseudocapacitance 225
fJ (10.3)
--fJ = KCH+ exp(VFIRT)
1-
taking the argument of the exponent as negative together with negative V for the
cathodic reaction I. This type of process is well known at the catalytic noble
metals such as Pt, Rh, Ru, Ir, and also for some base metal adatom deposition
processes at Au or Ag. For H, it is observed at potentials positive to the revers-
ible hydrogen electrode potential, i.e., before cathodic H2 evolution takes place.
For this reason, the process is referred to as "underpotential deposition" to dis-
tinguish it from the related process of deposition of H during H2 formation at
cathodic overpotentials when continuous net currents for H2 formation pass.
Then process I is formally also the first step of the H2 evolution process, but
takes place under different conditions of H coverage and electrode potential
from those for UPO, in particular on a surface fully covered by UPO H (fJ 2= 1)
in the case of polycrystalline Pt, Rh, Ir, and Ru. At Pd and Ru, H also passes into
the metal lattice by a sorption process after discharge of the H+ ion or from
water.
Processes like that for UPO of H on Pt also occur with electrodeposition
of base metals (e.g., Cu, Bi, Pb) on noble metals such as Au, Ag, or Pt. Thus
monolayers of Cu, Bi, or Pb can be electrosorbed from the corresponding cat-
ions in solution at potentials positive to the respective reversible potentials for
deposition of the regular crystalline bulk metals.
Thermodynamically, the condition required for UPD of 2-dimensional
monolayers prior to bulk phase formation is that the Gibbs energy of the H-to-M
or base metal-to-M bonds be lower than that for H-H or for the intermetallic
bonds in the bulk phase of the deposited base metal. Thus, e.g.
(10.4)
or similarly for base metal to substrate M bonding in the UPO of the base metal
on substrate M in relation to G for bond strength in the lattice of the bulk base
metal. The above relation for the Gs corresponds to the actual numerical value
of the bond energy of H to M being greater than that for H to H in 112 H 2, or
the metal atom substrate bond energy being numerically greater than the metal-
to-metal interatomic bond energy in the bulk metal crystal, taking into account
the coordination number of the metal crystal structure. It is in systems that be-
have thermodynamically in the above way that adsorption pseudocapacitance
can arise if the kinetics of the processes are sufficiently facile, which is usually
the case.
226 Chapter 10
If the charge for formation ofa monolayer ofH on M in process I is ql, then
a pseudocapacitance C~ can be derived from Eq. (10.3) as
(10.5)
(l0.8)
e
which obviously has a maximum of q1F14RT at = 0.5. Similarly, of course,
Eq. (10.6) for C¢ has a corresponding maximum. C¢ initially increases, at low
0, as exp(+VFIRn, while at high 0 when KCH+ exp(VFIRT) » 1, it must de-
crease as exp(- VFIRT), i.e., when I - 0 « e.
With ql taken as ca. 210 pC cm-2, it is found that the maximum in C~ (for
0= 1 - 0 = 0.5) is ca. 2200 pF cm- 2, a large specific capacitance. Note that this
maximum C¢ value is some 100 times the double-layer capacitance per square
centimeter, e.g., for a Pt electrode.
Conway and Gileadi2 also considered an adsorption isotherm more realis-
tic than the Langmuir one for representing adsorption of species that leads to
pseudocapacitance. Chemisorption usually results in polar adsorbate-to-metal
bonds which experience repulsion between their electronic orbitals. Also there
can be some communal electronic effects caused by a change in localized sur-
face electron distribution, referred to as "induced heterogeneity" by Boudart. 8
These effects can be taken into account in a probably oversimplified way by in-
troducing a lateral interaction energy term "gO" into an isotherm having the
*From Eq. (10.2) it is readily seen that B =KCH+ exp[VFIRTJ/{ 1 + KCH+ exp[VFIRTJI and 1 - B =
1/{ 1 + KCH+ exp[VFIRT] I; hence Eq. (l0.8) follows.
Electrochemical Capacitors Based on Pseudocapacitance 227
same "configurational" Gibbs energy term RTln 81( 1 - 8). Then the electrosorp-
tlon isotherm becomes of the Frumkin type, namely,
8 (10.9)
--8 =Kexp(-g8) . cH+exp(VFIR7)
1-
..--...
(g>O)
<pI>
"0 "0
r::T
<l> "
'--'"
w "9-
~ U
<t
a:: w
u
~0.5 z
0 <t
U ~
U
<t
!l.
<t
u
ELECTRODE POTENTIAL
FIGURE 10.1. Coverage, 8, isotherms and Ctp vs. electrode potential profiles for an electrosorp-
tion process involving a zero and a positive g value, i.e., for lateral repulsion (Eq. 10.10) (schematic,
cf. Refs. 5 and 6).
0.8 - Reversible
-'-'-'- Irreversible
0.6
>
..........
o 0.4
+-
c
Q)
+-
o Langmuir
0... 0.2 case ~
I ~.
t .
/.---
..... '
,. I
-4 o 4 8 12 16 20
9
FIGURE 10.2. Widths (AV1I2) at half-height of C,p vs. V profiles as a function of the lateral inter-
action parameter, g. (From Conway and Gileadi 1 and Kozlowska et al? Copyright 1962 and 1977
Royal Society of Chemistry.)
therm equation will contain two exponential terms, exp -[fOIRT] and
exp[VFIRT] (i.e., in combination, exp[(VF - jfJ)IRTJ. This illustrates how VF
must be increased as/is increased positively in order to maintain a given value
of (VF - /O)IRT, which then determines the value of the configurational term9
01(1 - 0) of the isotherm function (Eq. 10.9).
If the g value is negative, up to g = -4, the opposite conclusion applies; the
electrosorption is easier with increasing coverage due to attractive interactions
in the adlayer, so that a relatively lower potential V is required to attain a given
coverage, and the effective potential range required to reach almost full cover-
age (0 --7 1) is then diminished. Because the required charge (ql) is still the same
for monolayer formation, the resulting linear-sweep voltammogram must be
sharper than for the Langmuir case, g or/ =0 (see Fig. 10.3). Note that the in-
tegral under the voltammogram at a sweep rate s = dVldt gives the charge
passed:
V2 V2
0 .0
1.0 b
0.8
9 -8
0.6
e
0.4
0 .2
0.0
-0.2 0.0 0.2 OA 0..6
Potential/Volts
FIGURE 10.3. (a) Ctp vs. electrode potential profiles for an electrosorption process involving
negative g values, i.e., lateral attractions. (b) Related isotherms for coverage, B, as a function of po-
tential for positive and negative g values.
Electrochemical Capacitors Based on Pseudocapacitance 231
for a sweep between potential limits V2 and VI. Then since i(V)/s is a pseudo-
capacitance C¢J' the integral is equivalent to charging the C¢J from potential VI
to V2. The charge passed is then C¢J (V2 - VI) or f~2 C¢J . dV since C¢J is rarely con-
stant with changing potential, especially for elec'trosorption processes. I - 7
Experimentally, the pseudocapacitance behavior represented by the above
equations for C¢J can be directly recorded by means of cyclic voltammetry since
for a sweep rate, dV/dt,
C¢J· dVldt= i
(10.12)
or
C¢J =iI(dVldt)
(10.13)
where i is the recorded response current density for a system exhibiting pseudo-
capacitance, addressed by a potential that varies linearly in time t. Thus linear-
sweep or cyclic voltammetry is the most convenient technique for accurately
recording C¢J behavior, including situations commonly encountered where C¢J is
far from constant and the CV may exhibit more than one current maximum in
the swept potential range. This situation is common on polycrystalline surfaces
where several maxima in C¢J vs. V profiles are observable in UPD studies (Fig.
lOA); it is interesting that even for well-prepared single-crystal surfaces [e.g.,
ofPt(lOO)], more than one peak in the C¢J profile can arise as for H [Fig. 10.4(a)].
Similarly, multiple peaks arise in the UPD ofPb adatoms on single-crystal sur-
faces of Au [Fig. lO.4(b)].
In evaluation of pseudocapacitance by means of cyclic voltammetry, it
must be remembered that there will always arise components of response cur-
rents owing to the ubiquitous presence of the double-layer capacitance. This
will lead to a double-layer charging current, Cdl (dVldt), that is proportional to
the sweep rate; this current is normally 5 to 10% of the (maximum) pseudoca-
pacitance charging currents when C¢J is appreciable. The double-layer charging
component can usually be distinguished from the pseudocapacitance compo-
nent by its different frequency dependence; thus, the double-layer capacitance
response is usually maintained at up to 105_106 Hz in a well-designed measure-
ment system while pseudocapacitances are often dispersed in the range 103-104
Hz due to electrode kinetic rate limitations.
Writing the isotherm function, Eq. (10.9), logarithmically, i.e.
....
I
E
u
ci
:1.
:::::: J 2
100
FIGURE 10.4. (a) Cyclic voltammetry profiles for UPO of H adatoms on clean Pt single-crystal
surfaces: I, (111); 2, (tOO); and 3, (110) surface. (b) Cyclic voltammetry profiles for UPO of Pb
adatorns at indicated single-crystal surfaces of Au. [(a) From Clavilier et aI., 1. Electroanal. Chern.,
295, 333 (1990); (b) from Engelsman et al. 18]
it is seen that differentiation W.r.t. V will give rise l to two reciprocal capacitance
components 2 :
RT (lO.15a)
- . d 1n[8/(1- 8)]
qlF
and
RT (1O.15b)
qlF' g
S~- + 2e ~ 2S 2- (10.16)
10
Cathod ic .. (bl
1.389 9 (0)
.........
..... ..'....,
............. , ."" 8
'
",-
<.>
1.041
'~ / 7', /
u
<; ,/
./ "
... ,
0 ,694
0 .347
N
IE
°
u
<{
E
,,j 0,347
0,694
1.041
'j
<t
1.389
Anodic
0 .5 -0.1
Potential (Volt, E H )
FIGURE 10.5. Almost-reversible cyclic voltammogram for reduction and reoxidation of the
surface region of FeS2 (pyrite). (From Conway and Ku. 15 )
Electrochemical Capacitors Based on Pseudocapacitance 235
The process takes place in the surface region ofFeS2, producing two sulfide ions
that remain in the interface of the lattice. In order to maintain charge balance
with respect to Fe2+ ions, presumably S2- becomes protonated to SH- in the
course of the reduction.
Using cyclic voltammetry, an almost reversible mirror-image cathodic and
anodic cyclic voltammogram is generated, as shown in Fig. 10.5. The system
can be cycled thousands of times with little degradation. For comparison, FeS
(the salt of S2- ions) behaves irreversibly on reduction, as is seen in the cyclic
voltammogram illustrated in Fig. 10.6. This proves indirectly that it is the disul-
fide-sulfide redox reaction that gives rise to the pseudocapacitance exhibited by
4 .40
3 .52
Cathodic ..
u
'0
0
.r::. 2 .64
'0
U
1.76
0 .88
N
IE
u
0 .00
<l:
E
... 0 .88
1.76
.':::' 2 .64
'0
0
c
« Anodic
3 .52
FIGURE 10.6. Irreversible cyclic voltammogram for FeS. (From Conway and Ku 15; contrast Fig.
10.5.)
236 Chapter 10
FeS2' The reversibility arises presumably because there are no phase changes in-
volved and the process is restricted to the surface region. The disulfide system,
FeS2> behaves in a way typical of other disulfides, e.g., the organic molecule
cystine, which is reversibly reducible to cysteine.
500~------------------------------------------'
400
N
IE
u 300
u..
:t.
"-
:>-
r 200
u
~
5'00
FIGURE 10.7. Kinetically calculated pseudocapacitance profiles for a one-electron surface proc-
ess displaced progressively from equilibrium, depending on relative values, KNE, of the rate con-
stants for electrochemical desorption. (From Gileadi and Conway.5 Reprinted with permission from
1. Chern. Phys., 31, 716. Copyright 1964 American Institute of Physics.)
500
400
N
IE 300
u
u..
....:t.
:>- 200
r
U
<1
~ 100
L)
FIGURE 10.8. As in Fig. 10.7 but for a recombination controlled reaction. (From Gileadi and
Conway.5 Reprinted with permission from 1. Chern. Phys., 31, 716. Copyright 1964 American In-
stitute of Physics.)
238 Chapter 10
constants kl and k-l for the forward and reverse directions of the electrosorption
reaction (e.g., process I) was examined in terms of electrochemical kinetic equa-
tions for each direction of the surface process. Analogous equations (but not in-
volving surface coverages) could be written for a Nernstian redox process
similar to those relations for polargraphic behavior of a redox reaction displaced
from equilibrium.
The treatment by these authors 6 is based on introduction of a linearly time-
variant potential into the rate equations for an electrosorption process, corre-
sponding to the conditions of cyclic voltammetry at some constant sweep rate,
s =± dV/dt. The discontinuous change of sign of s arises at the two limits of the
potential span applied to the electrode in cyclic voltammetry. There is a corre-
sponding change of sign (direction) of the response current at those limits if ca-
pacitative behavior is exhibited by the system.
The kinetic treatment of pseudocapacitance given below closely follows
that developed by Srinivasen and Gileadi6 for a process such as reaction I, fol-
lowing the more thermodynamic treatment given by Conway and Gileadi 2 that
is based on adsorption isotherms for electrosorbed species outlined earlier in
this chapter. Using the example of reaction I involving nondiffusion-controlled
electrosorption of H, the Faradaic current density, i, is written in the form of a
Butler-Volmer equation (see Chapter 3 on electrode kinetics)
where kl and k-l are again the rate constants for the forward and reverse direc-
tions of process I for which z = 1, and Pis the barrier symmetry factor for the
charge transfer process (P =0.5). At equilibrium i =0, then a function for O(V)
can be written as
(10.20)
This relation is similar to that derived by Bockris and Kita 17 for the adsorption
pseudocapacitance developed for an electrosorbed species (here H) on account
of the potential dependence of its coverage, Eq. (10.18).
When 0.05 < () < 0.95, i for charging or discharging of the pseudocapaci-
tance is normally substantially larger than the ubiquitously present double-layer
capacitance, Cd], as mentioned earlier, so that the i measured in cyclic voltam-
metry (i = Ct;S) is principally the Faradaic current density for charging or dis-
charging the pseudocapacitance, C¢. However, as discussed in Chapter 17 on
impedance, if the Faradaic resistance for charging C¢ is not negligible, then C¢
and Cdl are not strictly additive since the charging of C¢ is not in phase with that
OfCdl·
Under kinetically reversible conditions, it must be emphasized that at any
potential across a pseudocapacitance curve [as e.g., in Fig. 10.1 or Fig. 10.4
showing experimental behavior for H on three Pt surfaces], the surface proc-
esses remain electrochemically at equilibrium. The same concept applies to a
pseudocapacitance associated with a redox process; thus, at any potential
through a redox titration curve, Ox and Red (Section 10.5), and electrons in the
metal (Eq. 10.35), are at eqUilibrium and it is only the equilibrium ratio of
[Ox]/[Red] that is dependent on potential. The pseudocapacitance for such a
system is simply the differential coefficient of the redox titration curve, ex-
pressed in terms of corresponding redox charge, taken w.r.t. electrode potential.
It is only when the electrosorption or the redox process is driven fast that non-
equilibrium, irreversibility effects arise so that kinetic effects enter into the
pseudocapacitance behavior. Under fully reversible conditions, the maximum
pseudocapacitance is attained and the process behaves exactly like the charging
of a regular capacitor.
(10.23)
(10.24)
Note thatq JFI4RTis the maximum value of C¢, i.e., for {} =1 - (} =0.5 (Eq. 10.9,
g =0).
For the case of irreversible deposition of the electroactive species in a proc-
ess such as I, only one of the two terms of the Butler-Volmer type of equation
(10.17) (cf. Chapter 3) is significant, so that in the deposition direction the
Faradaic current density is simply
i.e., a Tafel-type equation, which after differentiation for linear sweep behavior,
gives
(10.28)
(10.29)
Electrochemical Capacitors Based on Pseudocapacitance 241
The latter relation can be recognized as a Tafel-type equation giving the dis-
placement of Vp as a logarithmic function of sweep rate, s, with a Tafel slope of
RT/PF noted by Gileadi and Srinivasan 6 and treated in some detail by Ko-
zlowska and Conway, 16 corresponding to a logarithmic function of i dependent
onpVF/RT.
The peak current is again found to be proportional to s, but with an appar-
ent maximum pseudocapacitance for the nonreversible behavior of process I,
given by
(l0.30a)
(10.31)
and
k1cH+ exp[[JVFIRT]
B=--------~~~~----~-------
k1cH+ exp[[JVFIRT] + k-l exp -[(1 - [J)VFIRT]
from which also dBldt and dildt for Vet) = V(t = 0) + st can be derived. These
differential equations cannot be solved analytically. but Srinivasan and Gileadi 6
gave a series of numerical solutions plotted as linear-sweep voltammograms in
terms of Ct/J asfiV) for various s values and the Vp values as anfilog s) for various
kl and k-l values (Figs. 10.9 and 10.10).
Kozlowska, Klinger, and Conway7 gave similar plots, but for generalized
kinetic parameters defined as reduced sweep rates slk 1• Then reversible condi-
tions correspond to small slk! values and irreversibility to large slk!. Kozlowska
and Conway16 also demonstrated the transition to Tafel behavior in plots of Vp
vs. log s from quasi-equilibrium behavior for s < So (the limit of increasing
-3 -2
2.0
2
N
'E i
,....
\ :- .'.-..
u . \.
I : ~
i \\. .
(/)
"Cl
o .
~ I .\ .:
...... 1.0
o<"l
Q
/. i
:'\
u" :' \
\
\
\
0.4
0.3
>
"-
Q.
> 0.2
c
:.=
-
c
Q)
0
a..
0.1
0.0
electrochem'lcall electrochemical
reaction reaction
reversible I irreve sible
0.05L---------~--------~0~--------2~------~4
-4 -2
log ( :1)
FIGURE 10.10. Peak potential values for linear-sweep voltammograms for various slkl values
(based on Gileadi and Srinivasan6 and Kozlowska, Klinger, and Conway\
g=10
1- =10
0.6
....
N
0.4
Ie
()
C/I 0.2
ec
""C
u.. 0.0
.., 0.4
g
M
0.2
Potential (Volts)
U
0.4
0.6
0.8
1.0
FIGURE 10.11. Effect of interaction effects on cyclic yoltammograms for a process displaced
from equilibrium. s > so. (From Conway and Klinger, unpublished.)
exceed the exchange current density for the reversible process, i.e., for condi-
tions where either the forward or the reverse terms of Eq. (10.17) become domi-
nant on charge or discharge. Such changes of conditions are exactly the same,
in principle, as those that arise in the polarization of regular, continuous
Faradaic reactions as the overvoltage is progressively increased from zero to ap-
preciable values.
Thus, the behavior of surface processes involving underpotential deposi-
tion is closely analogous to that of regular Faradaic reactions except that the fi-
e e
nite availability of surface sites (1 - ~ 0 as ~ 1) and a corresponding finite
value of ql restricts the possibility of continuously (and exponentially) increas-
ing currents as the potential is raised since the processes take place 2-dimension-
ally on a finitely limited density of surface sites, about 1015 cm- 2•
Note also that a surface (UPD) electrochemical reaction that is proceeding
under equilibrium or quasi-equilibrium conditions has a current that is deter-
mined at all potentials in the sweep, not by an overvoltage, but by a potential
defined by the equilibrium adsorption isotherm, e.g., Eq. (10.7). Thus the latter
is a form of the Nernst equation for relative extents of vacancy (1 - e) and oc-
Electrochemical Capacitors Based on Pseudocapacitance 245
t=)O-3 : =10- 2
1.6
0.8
0 ./. f\'
-0.' 0.2 0.4 -0.1
\ /0.2 0.4
0.8
Ie
N
(,)
f/) 1.6
e
"0
~ (0) (b)
........ 2.4
-
'0. 1.6 t=10-1 .1..-10
k -
l
U
0.8
jJ)
Vp.v'o
L.z
0
-0.'
:r,(00.1 0.'
'Y
0.5
0.8 ,0/I
1.6
(c)
W
I
I (d)
POTENTIALS/V
FIGURE 10.12. Anodic and cathodic CV profiles for various initial cathodic values and for e
various degrees of reversibility of reaction (I). The values of slk are (a) 10-3, (b) 10-2, (c) 10- 1, and
(d) 10; g = 0 for all cases. Reprinted from H. A. Kozlowska, 1. Klinger, and B. E. Conway, 1. Elec-
troanal. Chern., 75, 45 (1977), with permission from Elsevier Science.
~ =10
1.0 g=2
0.5
N
IE 6
u
/
III
"C
...
0
0
I.L.
..........
r<l
0
~
U
0.5
1.0
FIGURE 10.13. As in Fig. 10.12 but with a finite g value. Reprinted from H. A. Kozlowska, J.
Klinger, and B. E. Conway, J. Electroanal. Chern., 75, 45 (1977), with permission from Elsevier
Science.
reaction) can take place according to the kinetics of the surface process or of the
redox reaction will a true overvoltage arise. This occurs when,16 in a linear po-
tential sweep modulation process, the sweep rate s is greater than so, or the
Faradaic current density i is significantly greater than io. The relation between
current responses to linear potential sweep modulation and those to alternating
voltage modulation is discussed in Chapter 16.
then much lower than the maximum C~ when g = O. However, the range is still
usually substantially larger than the double-layer capacity of the same area of
electrode.
When multiple-state adsorption pseudocapacitance arises, as for UPD of
Pb on polycrystalline AU,IS appreciable C~ arises over about 0.7 V, but five
peaks in the C~ vs. V profile arise, several even on single-crystal surfaces of Au.
Only for the redox pseudocapacitance developed at Ru02 in aqueous H 2S04
(Chapter 11) is a wider potential range (ca. 1.4 V) realized, over which C~ is
within 10% constant. At Ir0 2, similar behavior is observed, but only over a
smaller potential range (0.9 V) and with greater dependence of C~ on potential.
The 1.4-V range attainable at Ru02 is near the maximum possible in aqueous
solutions owing to the limitation of the decomposition voltage of water. Simu-
lation analysis of the redox pseudocapacitance by hydrous RU02 indicates that
the broad range of almost constant capacitance can only be accounted for by
several (three) oxide redox processes overlapping in their potential ranges for
charge accommodation, as illustrated in Fig. 11.16 in Chapter 11.
In the case of the electro active conducting polymers such as polyaniline,
polypyrrole, and poly thiophene (Chapter 12), the potential range of appreciable
C~ (depending on the thickness of the electrochemically developed films) is
about 0.7-0.8 V. However, Rudge et al. I9 have developed some derivatized
poly thiophene materials that show two regions of pseudocapacitative activity
corresponding to p and n doping well separated by a substantial voltage differ-
ence of about 3.0 V. These materials are of special current interest; see Chapter
12.
In aqueous solutions, the range of operation of any electrochemical capaci-
tor is determined theoretically by the decomposition voltage of the solvent,
water, i.e., 1.23 V at 298 K and standard pressures ofH2 and O2, In practice, this
range may extend somewhat further, depending on the overvoltages for H2 and
O 2 evolution at the negative and positive electrodes as a function of current den-
sity (the Tafel parameters). However, no significant quantities of H2 and O 2
should be allowed to build up since then serious self-discharge (Chapter 18) can
set in.
In the case of oxide redox capacitor systems, the potential ofthe lowest re-
dox couple should therefore be a little positive to the hydrogen reversible po-
tential and that of the highest should be just below the oxygen potential. This
will achieve the maximum range of redox pseudocapacitance, as found with
RU02' which (as explained elsewhere) must involve several redox processes
overlapping in their potential ranges. If the onset of reversible oxidation and re-
duction behavior is for thermodynamic reasons substantially more positive than
the hydrogen reversible potential, as with Co and Ir thick-film oxides, then the
achievable operating range for the pseudocapacitance-based electrochemical
capacitor will be too short for practical use.
248 Chapter 10
Other oxide-film systems, e.g., the thick films that can be generated at Pt,
Rh, Au, or Ni (in Ni·O·OH), can only be generated anodically at high potentials
in the Oz-evolution potential region and their reduction is highly irreversible.
They hence have no value as pseudocapacitor materials.
It is uncertain if the operating potential range of RU02 could be substan-
tially extended in nonaqueous electrolytes. Protons have to be available, so
some acidic solute in a nonaqueous solvent would be required, e.g., CF3S03H
in a polar nonaqueous medium. Use of an Li salt as electrolyte would in princi-
ple be possible, but then the system would become equivalent to an Li+ ion in-
tercalation battery system with Li+ insertion and deinsertion instead of the
corresponding protonic processes that take place in aqueous acidic solutions at
RU02' Such systems are already well known with cathode materials such as Li-
Co0 2, Mn02, or V60 13 . As explained in the following section, Li+ intercalation
battery systems behave as a transitional class of electrochemical power sources
since they exhibit pseudocapacitance because their state of charge is dependent
on potential for fundamental thermodynamic reasons, but they are commonly
regarded as nonaqueous electrolyte "batteries."
The generality of Eqs. (10.1) and (10.2) was emphasized earlier in this
chapter insofar as they apply equivalently to a 2-dimensional electro sorption
process (UPD), a 3-dimensional sorption process with charge transfer (electro-
chemical intercalation), or a redox reaction at an electrode. The detailed devel-
opment in previous sections was addressed to adsorption pseudocapacitance,
based on Eqs. (10.6), (10.7), (10.9), and (10.10).
Capacitors based on inorganic redox reagents also have a capacitance that
is electrochemical rather than electrostatic in origin. Consider the following ex-
ample:
(10.34)
The Nernst equation for the equilibrium redox potential E for such a 1 e
system is written
BOUND
0.6
,'-,/REDOX
I I
, IE
I \ pc
I \
I
0.4 I
I DIFFUSION
I /REDOX
I
I
0.2
,
I
,,
I
I
c:
.2
U ,- /
--
c: ~~
;
::l
0
c:
.... ,
Q) ;""
.... I
::l
U I
I
I
I
I
I
I
I
I
-0.4 I
, I
I
I
I I
I
I
-0.6 '-' a
Potential IV
FIGURE 10.14. Cyclic voltammograms for the Fe(CN)~-lFe(CN)~- redox couple giving rise to
pseudocapacitance: (a) free in solution (diffusion controlled) compared with surface bound; (b) ex-
perimental example of ferrocyanide bound on poly(vinylpyridine). (From Conway and Duic, un-
published. )
Electrochemical Capacitors Based on Pseudocapacltance 251
-.l
1 mA
T A (lnitiol)
I \
," ,
I ,
,,, , \
\
I \
\
\
\
\ ,
" .... _--
",'----
I
I
, I
,,
I
, I
\ I
" lOOmV
--I I--
b
where X is the 3-dimensional site fraction occupancy by the sorbed guest atom
or ion, e.g., Li.1t is seen that this equation has the same form as Eq. (10.1) (after
conversion to its logarithmic form) and hence will give a capacitance relation
like Eq. (10.2), or the corresponding equations for 2-dimensiona1 electrosorp-
tion or for the redox case. It is because of Eq. (10.41) that Li ion intercalation
batteries can be regarded in some sense as pseudocapacitors since their extents
of charge are a continuous function of their voltage for fundamental reasons.
However, their response times in a capacitative sense are longer than with dou-
ble-layer capacitors owing to the necessity for interlayer diffusion in the solid
host lattice.
The similarity to adsorption pseudocapacitance arises directly because Li+
ion accommodation is really a quasi-2-dimensional phenomenon, occurring at
the layer surfaces of the van der Waals gaps in the layer-lattice structures of
e.g., TiS 2 or MoS 2. It is interesting that the quasi-2-dimensional intercalation
processes involving Li+ ions take place in distinguishable progressive stages, as
revealed by cyclic voltammetry.2o Examples are shown in Figs. 10.15 and
252 Chapter 10
-200
DISCHARGE
200
FIGURE 10.15. Slow cyclic voltammogram (sweep rate 9 /iV S-I) for pseudocapacitance asso-
ciated with U+ intercalation into M002. (From Sacken. 21 )
0.03
0.01
-
<
E 0
-0.01
-0.03
1 1.5 2 2.5 3
FIGURE 10.16. Differential electrochemical sorption and desorption curves showing three-state
accommodation of Li in a fullerene, C60 (compare Fig. 10.15). (From Chabre?2)
Electrochemical Capacitors Based on Pseudocapacitance 253
10.16, where two or three current response peaks are resolved in slow cyclic
voltammetry for Li+ intercalation and deintercalation at Mo0 2 (Fig. 10.15)21
and remarkably at a fullerene (Fig. 10.16).22 It is seen that this behavior is
closely similar to that observed [e.g., as in Figs. 10.4(a) and 1O.4(b)] for 2-di-
mensional electrosorption (Section 10.2.2) of H onto single-crystal Pt surfaces
or of Pb onto gold surfaces. In both types of cases it must be assumed that suc-
cessive lattice array structures are set Up20,23 having distinguishably charac-
teristic Gibbs energies as the lattice occupancy fraction (0 for 2-dimensional
adsorption or X for 3-dimensional intercalation) progressively increases or de-
creases. 20 In both these cases, the asymmetry between the sorption and desorp-
tion peaks is attributable to the slowness of diffusion. The three cases
(2-dimensional underpotential deposition, redox systems, and quasi-2-dimen-
sional Li+ intercalation processes) and their corresponding Nernst-type equa-
tions are summarized in Table 10.3.
Ox+ze~Red
9\ = [Ox]/([Ox] + [Red]) 9\/(1 - 9\) = [Ox]/[Red]
(b) Intercalation system: RT
£=£0+ zF InX/(I-X)
effect occurs when the adsorption is not only electrostatic in origin (i.e., depend-
ent on the charge on the ion and the surface charge density at the electrode) but
also depends on some "specific" electronic interaction between the ion's va-
lence electrons and the electrode's surface orbitals.
Such effects are usually accompanied by a partial transfer of charge, e.g.,
as in the following quasi-chemical equation for adsorption of an anion A-at an
electrode M:
where 0 is some fraction of an electron charge. Process (II) has the nature of a
Lewis acid-base donor-acceptor interaction, the anion being the donor. Ad-
sorption takes place more strongly when M is positively charged (Lewis-acid
character) but at the potential-of-zero charge for many anions. The quantity 0
(or 1 - 0) is a component of the so-called "electrosorption valence" of the anion,
which characterizes its chemisorption behavior at electrodes. 12,13
The charge passed in process (II) can be determined microcoulometrically
in a thin-layer cell or by means of cyclic voltarnmetry: for example, Fig. 10.17
shows the current response for HS0 4ion chemisorption at Au in a single poten-
tial-sweep cycle; the charge under the anodic or cathodic sides of the voltam-
mogram gives the extent of partial charge passed, plus the charge
accommodated in the double layer over the same potential range. These two
charge components are not easily separated except under favorable conditions
by means of ac frequency-response analysis (Chapters 16 and 17). The pseudo-
capacitance associated with processes like II is not normally appropriate for
5
Au (111) 02
-5
FIGURE 10.17. Current-response profile for specific adsorption of sulfate ion at polycrystalline
Au recorded by single-cycle voltarnmetry.
Electrochemical Capacitors Based on Pseudocapacitance 255
In the case of a porous electrode (Chapter 14), however, the distinction be-
tween Cdl and CtP , when the latter is significant, is much more difficult owing to
the distributed nature of both CtP and Cdl throughout the porous matrix, with a
progressively increasing electrolyte resistance down pores (Chapter 17) in a se-
ries-parallel arrangement with the C components. For such reasons, it is usually
difficult to distinguish a CtP component in carbon double-layer capacitors, al-
though it is probably significant owing to reactive surface functional groups
(Chapter 9).
The discussion given here concerning the distinction between double-layer
and pseudocapacitance in experimental measurements has implicitly assumed
that the processes involved in double-layer charging and Faradaic passage of a
charge in charging the pseudocapacitance at the same electrode are independent.
This, however, is not necessarily true and there can in fact be some coupling be-
tween double-layer charging and simultaneous Faradaic processes. Although it
is a somewhat arcane topic, this matter has been thoroughly discussed and
treated in a review by Parsons.z5 It can be a significant factor when quasi-
Faradaic processes such as anion-specific adsorption with partial charge trans-
fer12,13 are involved. However, more detailed examination of this problem is
beyond the scope of this chapter, so readers are referred to Ref. 25 and the lit-
erature cited there.
REFERENCES
1. B. E. Conway and E. Gileadi, Trans. Faraday Soc., 58, 2493 (1962).
2. E. Gileadi and B. E. Conway, in Modem Aspects of Electrochemistry, J. O'M. Bockris and B.
E. Conway, eds., vol. 3, Chapter 2, Butterworths, London (1965).
3. E. Gileadi, Electrosorption, Plenum, New York (1967).
4. A. Eucken and B. Weblus, Zeit. Elektrochem., 55, 114 (1951).
5. E. Gileadi and B. E. Conway, 1. Chem. Phys., 31, 716 (1964).
6. E. Gileadi and S. Srinivasan, Electrochim. Acta, 11, 321 (1966).
7. H. A. Kozlowska, 1. Klinger, and B. E. Conway, 1. Electroanal. Chem., 75, 45 (1977).
8. M. Boudart, 1. Amer. Chem. Soc., 72, 3566 (1952).
9. T. L. Hill, Introduction to Statistical Thermodynamics, Addison-Wesley, Reading, Mass.
(1960).
10. 1. G. N. Thomas, Trans. Faraday Soc., 57, 1603 (1961).
11. S. K. Rangarajan, Specialist Periodical Reports (Chemical Society, London), vol. 7, p. 203
(1980).
12. W. Lorenz and G. Salie, Zeit. Phys. Chem., N.F., 29, 390,408 (1961).
13. 1. W. Schultze and F. D. Koppitz, Electrochim. Acta, 21, 327, 337 (1976).
14. M. I. Temkin, Zhur. Fiz. Khim., 15, 296 (1941).
15. B. E. Conway and J. Ku, 1. Coli. Interfacial Sci., 52, 542 (1973).
16. H. A. Kozlowska and B. E. Conway, 1. Electroanal. Chem., 95,1 (1979).
17. 1. O'M. Bockris and H. Kita, 1. Electrochem. Soc., 108, 676 (1961).
18. K. Engelsman, W. J. Lorenz, and E. Schmidt, 1. Electroanal. Chem., 114, 1 (1980).
19. A. Rudge, 1. Davey, I. Raistrick, and S. Gottesfeld, 1. Power Sources, 47, 89 (1994).
Electrochemical Capacitors Based on Pseudocapacitance 257
1. E. Gileadi, Chapter J in Electrode Kinetics for Chemists, Chemical Engineers and Materials
Scientists, VCH Publishers, New York (1993).
2. D. G. Grahame, Chem Rev., 41, 441 (1947).
Chapter 11
equation with regard to its electrode potential, can give rise to a pseudocapaci-
tance over a range of potentials. This is the main basis of the pseudocapacitance
developed at RU02 in anodic and cathodic cycling; it also originates with a sim-
ple redox couple (e.g., Fe(CN)t-Fe(CN)~-) in a thin-layer cell or anchored on
a polymer as shown in Chapter 10. However, the latter type of system gives ap-
preciable pseudocapacitance only over about a 120-mV potential range,
whereas RU02 gives relatively constant and appreciable capacitance over a 1.4-
V range. 5,6 Later in this chapter we suggest how this important difference may
originate in terms of several overlapping redox processes within the l.4-V po-
tential range.
Ruthenium oxide films can also be formed at Ru metal electrodes by po-
tential cycling over about a 1.4-V range above the hydrogen reversible potential,
e.g., in aqueous sulfuric acid. Initially monolayer oxide formation and reduction
take place (Fig. 11.1), like that at Pt. However, upon continuous cycling, the ox-
ide film progressively grows (Fig. 11.2) since it is not reduced to Ru metal at
the least positive potential of the sweeps (+0.05 V, RHE), as is the initial mono-
layer at Ru or Pt.
Ruthenium dioxide films thus formed give a cyclic voltammogram having
the shape shown in Fig. 11.2 and a corresponding charge and discharge diagram
closely similar to that for a capacitor. 5- 7 It was on this basis that Trasatti and
Buzzanca6 recognized the interesting pseudocapacitative behavior of this Ru02
film material, since an almost rectangular, mirror-image cyclic voltammogram
(Fig. 11.2) is characteristic of a capacitance. A useful but brief review on RU02
as a electrochemical capacitor material for electrical energy storage has recently
been published by Trasatti (see general reading ref. 1). The Ru02 material
formed thermochemically on Ti also gives a voltammogram similar to that in
Fig. 11.2.
Especially with the RU02 films thermally formed on Ti with Ti0 2, or with
Ta205, the cycle life in capacitor charge and discharge between 0.05 and 1.2 V,
or even to 1.40 V (RHE) under some conditions is remarkable, allowing cycling
over 105 times with little degradation. What small degradation may take place
arises due to RuO~- formation at the high potential ends of the anodic voltage
excurSIOns.
By integration ofthe I vs. E voltammogram curves, the charges, q, for sup-
posed oxidation and reduction of Ru atoms in the thermally prepared Ru02
films were related4 to the fraction (%) of Ru atoms involved in solid-phase re-
dox reactions (Table 11.1). This fraction is actually quite small and tended to
decrease with increasing temperature of calcination between 350 and 450°C.
The q values in Table 11.1 cannot be related only to surface redox processes;
some bulk-phase reactions must also take place and some double-layer charging
must of course also be appreciable. This conclusion has been confirmed by
The Electrochemical Behavior of Ruthenium Oxide 261
___- r /
'"
";
..z
0
Irreversible
E region
u Revers ible req ion
I I
<t
~
E
0
c.
~
:; 0
u .5
0
....«I:
u
2.5
J
/
- ---
/'"
/ Reversible profile
FIGURE 11.1. Cyclic voltammograms for Ru metal in aqueous I mol dm-3 H2S04 at 298 K
showing behavior of initial cycles where monolayer oxide formation and reduction, like that at Pt,
arises. Reprinted from S. Hadzi-Jordanov, H. A. Kozlowska, and B. E. Conway, 1. Electroanal.
Chern., 60, 359 (1975), with permission from Elsevier Science.
3.0
-:::::=====:::.
U
'0
o ANODIC-_-_ _ _ _
c:
<{ 2.0
c::t
E 1.0
......
I-
Z
W 0
a::
a::
:>
u -1.0
u
:0 -2.0
-
0
.s::.
0
(j -3.0
FIGURE 11.2. Progressive increase of oxide film growth with potential cycling at Ru, exhibiting
increase of capacitative reversible current response. Reprinted from S. Hadzi-Jordanov, H. A.
Kozlowska, and B. E. Conway, I. Electroanal. Chern., 60, 359 (1975), with permission from
Elsevier Science.
0.5
0.25
<t
E
..... o~--~~~--------------------~
I-
Z
W
c::
~ -0.25
U
-O.5L-________~--------~~------~
o 0.5 1.0 1.5
POTENTIAL, EH IV
FIGURE 11.3. Cyclic voltammograms for (almost) reversibly formed and reduced oxide films of
lr02 on Ir. Annotations indicate distinguishable, almost-reversible, states on the curve. State M is
underlying Ir metal with adsorbed H. (From Mozota and Conway, unpublished.)
264 Chapter 11
11.2. INTRODUCTION
It was explained in Chapter 1 how there are essentially two types of elec-
trochemical capacitors: one based on mainly electrostatic energy storage in the
charged double-layer capacitance associated with the interfaces of solutions and
large specific-area, carbon-based materials (e.g., carbon powders, fibers,
and felts); the other kind originating from the pseudocapacitance associ-
ated with Faradaic adsorption (electrosorption) or redox processes in
which potential-dependent extents of passage of Faradaic charge can
arise; hence a capacitance can be formally measured (Chapter 10).
Two principal types of material in this second category have been discov-
ered and studied: (1) electroactive oxide or hydrous oxide films of transition
metals,I-4 e.g., RuOz and IrOz, and some other oxides such as C0 30 4, Mo0 3 ,
W0 3 , and molybdenum nitride of uncertain composition; and (2) electrogener-
The Electrochemical Behavior of Ruthenium Oxide 265
The device was designed for possible use in a microminature electrical neural
stimulator control module, but the achieved capacitance of 300 flF or a to-cell
series unit much exceeds the 0.7 flF required for this particular application, so
opportunity for further minaturization is available.
The RU02 used was prepared by thermal decomposition of RuCl 3 in an
NaN0 3 flux. Two approaches were employed for forming the Ru02-ionomer
The Electrochemical Behavior of Ruthenium Oxide 267
dc polarization at some appropriate positive potential (e.g., > 1.0 V at Pt), the
rate of oxide film extension is directly dependent on the log of the time of po-
larization (direct log law) for thin-film formation 23 - 25 while for longer times the
inverse log law in the sense of Mott and Cabrera24 applies.
These two principal growth laws for oxide film formation correspond
to different mechanisms of oxide extension and to different ionic and elec-
tronic conductivities of the resulting films. In some cases (e.g., at Pt), the
mechanism changes after some initial reconstructed oxide film is formed,
e.g., to an extent corresponding formally to "pt0 2,,25 which is actually two
layers of PtO in a compact film state. Further growth beyond this film occurs
in a hydrous oxide state that is independently reducible from the compact film
component. However, neither component of the overall film exhibits revers-
ible reduction and reoxidation like Ru02 or Ir0 2. The formation of Ru02 films
upon cycling also appears (like Pt) to take place in two stages, distinguished
in this case by two regions of potential dependence, as shown in work by
Hadzi-lordanov et al. 7 ,12 and illustrated in Fig. 11.4.
E
.,
.24
.
...«;
•
~3
~
.II:.
o
c:
.2
Ci
'02
'j(
o
•
l:
'0
~1
FIGURE 11.4. Two regions of potential dependence of oxidation charge for Ru in aqueous
H2S04 at 298 K. Reprinted from S. Hadzi-Jordanov, H. A. Kozlowska, and B. E. Conway, 1. Elec-
troanal. Chern., 60, 359 (1975), with permission from Elsevier Science.
270 Chapter 11
may be a preferred representation for the singular rest potential. A similar type
of reaction has been proposed for Ni0 2 at low temperatures in aqueous KOH in
the Ni-Cd battery. However, the broad range of oxidation and reduction in the
voltammograms must correspond to several overlapping stages of that process.
The standard potential for the first reaction has been reported as 0.94 V
(RHE) (Pourbaix Atlas of Electrochemical Equilibria). Galizzioli, Tantardini,
and Trasatti5 measured potentiostatically the quasi-stationary potentials set up
at RuOz films at small anodic polarizations, 10-5_10- 3 A cm-2. However, on
open circuit, time-dependent self-discharge and recovery potentials are ob-
served26 ,27 (see later discussion), which eventually approach ca. 0.75 V in acid
solutions. 26
Data for the Gibbs energy of formation of Ru02 enabled a value of 0.43 V
to be derived for the standard potential of the process
but this is not the stationary potential observed in acid media. However, under
cyclic voltammetry conditions, Ru02 is almost certainly, like Ir02, not reduced
The Electrochemical Behavior of Ruthenium Oxide 271
back to the metallic state in the negative-going sweep to 0.05 V (see Ref. 28),
so the process in Eq. (11.3) is not relevant to the experimental situation. (Ellip-
sometry work by Gottesfeld et a1. 22 showed that an iridium oxide film remained
when the underlying surface of Ir became electrodeposited with H.)
In potential-step experiments at Ru02 from ca. 1.4 to 0.05 V, Galizzioli,
Tantardini, and Trasatti5 observed that the electrochemical behavior became
like that of a capacitor. This was one of the early indications of capacitative be-
havior (as a pseudocapacitance) of Ru02, as mentioned earlier. Another indica-
tion was the observation of mirror-image cyclic voltammograms for RU02
reported by Trasatti and Bucanzza6 and by Hadzi-Jordanov et al? However, this
type of observation could be alternatively interpreted as a double-layer current
response at a large distributed surface area of Ru02> as will be seen later (see
Refs. 16 and 17).
Returning to quasi-thermodynamic potentials, Pell, Liu, and Conway26 re-
cently found that either a thermochemically or electrochemically formed (hence
a hydrous film) film of RU02 decayed in potential (on open circuit; see Chapter
18 and Refs. 29 and 30) after anodic polarization to 1.4 V, down to 0.75 V,
while, after discharge to 0.1 V, it recovered in potential to almost that value,
which remained stable for many hours. Thus 0.75 V seems to correspond to a
well-defined redox potential; it happens to correspond (at pH -0) to the line in
the Pourbaix pH potential diagram for Ru for equilibrium between Ru and
RU203, which is an interesting result but one inconsistent with the difficulty of
reducing Ru oxides back to the metallic Ru state, the problem referred to in Eq.
(11.3).
Although superficially (e.g., in the cyclic voltammograms) the thermally
and electrochemically grown Ru02 films behave similarly, Pell, Liu, and Con-
way26 found that the pH dependence of their stationary potentials was reproduc-
ibly quite different, being -30 mV for the former film and -60 m V for the latter.
By contrast, Daghetti, Lodi, and Trasatti31 found also a value of -60 mV for the
thermally formed oxide film. The two values found in the work of Ref. 26 indicate
a qualitative difference between the thermodynamically potential-determining
processes that are involved at the initially anhydrous and the electrochemically
formed hydrous oxide films. Thus the -60-mV slope (corrected for the pH depend-
ence of the RHE) requires a process involving an equal number of electrons and
protons, while the -30-mV slope requires a ratio of elH+ of 2.
A similar recovery behavior (see Ref. 26) at thermally formed RU02 had
been observed earlier by Arikado et aI.,27 but the potential approached was ca.
0.5 V rather than 0.75. In this work, a role for proton diffusion in the recovery
process was proposed.
In the voltammogram for RU02 in 1 M aqueous HCI04 at 60 m V s-l, two
conjugate (anodic and cathodic) pairs of peaks are observed (but not well re-
solved) at ca. 1.14 and 0.6 V (RHE) which were attributed5 to the RU20rRu02
272 Chapter 11
and RU20rRu couples. However, as remarked earlier, Ru02 or other lower ox-
ides are not returned to the Ruo state in the cathodic sweep except when only a
monolayer of Ru surface oxide has been formed 7 as at Pt. 12 In fact, it is precisely
the incomplete reduction of RU02 back to Ru on each sweep that is believed to
be the origin of the phenomenon of electrochemical growth of RU02 films on
potential cycling from 0.05 to 1.4 V. The increase in thickness of the RU02 film
is up to several microns, as is visible under the electron microscope or even un-
der the optical interference microscope. 13
Under potentiodynamic conditions, the initial stages of oxide film forma-
tion are typical of an irreversible, slow anodic process, as also found at pt. 12
Some coverage by surface oxide can be established in an anodic sweep up to a
certain potential, say, 1.0 V. Upon arrest of the sweep, growth continues at con-
stant potential; then when the anodic sweep is restarted, the original i-V vol-
tammogram is only picked up at some 50 to 100 mV higher potentials. This
means that the oxide that is formed at one (higher) potential (V2) in a sweep can
also be formed upon holding in time at a lower potential VI' < V2 .
Galizzioli, Tantardini, and Trasatti5 concluded that not all the Ru atoms in
the Ru02lattice were redox active, giving rise to pseudocapacitance; that is, in
a potential range of 1.35 to 0.3 V, the formal process Ru4+ + e -4 Ru 3+ (in the
oxide) was considered to be restricted to a number of atoms corresponding to
the degree of nonstoichiometry. Coupled with this change of oxidation state
(transfer of electrons) is a corresponding injection or withdrawal of protons to
maintain a charge balance through conversion of 0 2- ions to OH-. Possibly
these coupled redox and proton-exchange processes take place only in the near-
suiface region 26 of RU02, especially when it has been thermochemically pre-
pared. Electrochemically prepared RU02 films are hydrous in nature, so that a
more facile proton penetration, coupled with redox changes of oxidation state,
can take place, as suggested earlier.
The three-dimensional and near-surface (see Refs. 32 and 33) chemical
constitution of thermally formed RU02 was investigated34 using depth profiling
by means of sputtering. Oxygen species are rich in the surface region but de-
crease in concentration toward the bulk, where Ru also decreases (Fig. 11.5).
Cl- ion is adventitiously present and increases somewhat toward the bulk; it
arises from the RuC1 3 used to make the thermochemically generated RU02 film.
A new charge storage mechanism involving protonation ofRu02 (presum-
ably coupled with reduction) was recently claimed by Zheng and Jow. 16 How-
ever, it does not seem any different from the basis of operation of the redox
pseudocapacitance of RU02 recognized in various, much earlier papers 4- 7,27 and
more recently by Sarangapani et al.,9-21 as well as with oxides of Ni. 35 Good
specific capacitance was obtained with an RU02 . xH 20 material made by a sol-
gel precipitation process, followed by heating between 25 and 400°C. Values of
capacitance were up to 350 F g-I while, with the hydrous form, up to 720 F g-I
The Electrochemical Behavior of Ruthenium Oxide 273
1.6
0
...J
W
>=
Z
0 1.2
>-
0: •
\
\
I/)
<l
0 c
Z ::J
'.---.....-.......-.
0 ..: 0.8
u .'..... 16 0- /
W .0
(/) ~ ~
..... 0
U
~ 0.4
U
w
a...
(/)
o 5 10 15 20
Sputtering time / min
FIGURE 11.5. 0 and Ru atom distributions in a thermally formed Ru02 film determined by depth
profiling. Reprinted from T. Arikado, C. Iwakura, and H. Tamura, Electrochim. Acta, 22, 513
(1977), with permission from Elsevier Science.
were obtained. The X-ray diffraction patterns of the materials formed at various
temperatures were recorded as shown in Fig. 11.6. Higher annealing tempera-
tures promoted the formation of more crystalline oxide structures (Fig. 11.6),
which are less active for charge accommodation, presumably owing to their
more anhydrous character.
Further details of the work in Ref. 16 were given in a following extended
paper (Ref. 17) in which, among other things, cyclic voltammograms, which
give the capacitance (C¢ = i/s; see Chapter 10), were comparatively shown for
preparation temperatures of Ru02 varied over the range 25 to 400°C. The ca-
pacitative response currents diminished with increasing temperature of the heat
treatment. The charge and discharge behavior was represented by almost linear
relations between charge and potential, giving almost constant capacitance over
a potential range of 1.0 V, as had been found in other earlier work. 5 ,7,8 The ca-
pacitance as a function of cycle number remained virtually constant after an in-
itial fall by ca. 6% during the first 700 cycles. The specific capacitance (F g-l)
remained constant for various preparations with specific area (m2 g-l) over a
range of 40 to 96 m2 g-l. From this result it was concluded 18 that the capacitative
current response was due, not only to the surface of the oxide, but arose appre-
ciably on account of redox pseudocapacitance (Chapter 10) taking place within
the bulk of the hydrous oxide material, confirming earlier indications.
274 Chapter 11
7000 ,-----:-:--:-:-.---:--------:-::-::-::-:-----,
(110) (101) (211)
6000
(200)
(111 )
O+---~--~--~--_r--_r~~--_,--~
20 30 40 50 60
2 Theta (degrees)
FIGURE 11.6. X-ray diffraction plots for RU02 thermally formed at various temperatures. Indi-
ces identify anhydrous RU02 diffraction peaks. (From Zheng and Jow. 16 Reproduced by permission
of The Electrochemical Society, Inc.)
FIGURE 11.7. Thick, anodically grown RU02 films on Ru metal showing spalling off. (From
Birss, Myers, and Conway.13 Reproduced by permission of The Electrochemical Society, Inc.)
The Electrochemical Behavior of Ruthenium Oxide 275
FIGURE 11.8. Columnar structures of RU02 developed under anodic cycling at Ru metal. (From
Birss, Myers, and Conway. i3 Reproduced by permission of The Electrochemical Society, Inc.)
276 Chapter 11
ration. This determines the microsurface structure and thus the real-to-apparent
surface area ratio.
The macroscopic features of electrochemically prepared RU02 (i.e., films
formed by cycling Ru metal between 0.05 and 1.4 V) were compared with those
of the oxide thermochemically generated on Ti in a paper by Birss, Myers, and
ConwayY Both scanning electron microscopy (SEM) and interference optical
microscopy procedures were used.
Electrochemically grown films were up to several microns in thickness and
spalling off detached sheets of the oxide could be seen (Fig. 11.7) in some pho-
tos. Under the SEM, remarkable columnar structures could be observed (Fig.
11.8), which could account for the large specific capacitance found with this
material. In constrast, the material thermochemically formed on Ti had the mud-
crack appearance well known in the DSA technology field.
We conclude this section by remarking again that capacitative behavior
quite similar to that of RU02 is observed with Ir0 2 in acid solution. However,
reversible charging arises only at potentials positive to ca. 0.6 V. This is due to
the effect of potential, below 0.6 V (RHE), on the electronic conductivity of
Ir0 2 as the result of a change in oxidation state. This behavior is also paralleled
by an electrochromic effect.
(11.4)
(11.5)
or further
(11.6)
The Electrochemical Behavior of Ruthenium Oxide
with
(11.7)
leading to "Ru(OH)2," can take place. Relatively free mobility ofthe protons is
essential, as in the basis of the proton-jumping mobility of protons in aqueous
acid or alkaline solutions. The H+ can be looked upon as an intercalated species,
but unlike Li+ in Mn02 or CoOl> it has localized states (e.g., on 0 2- as OH-) or
in any water molecule, as H30+ at acid pH. A similar proton migration process
may also occur at the thermally formed RU02, but probably only in or near its
surface,5,16,17,37 as studied by Arikado, Iwakura, and Tamura,27 and it depends
on the temperature of the prior heat treatment. 16,17
The above processes may go on more easily in the near-surface region of
RU02 material than in the bulk and will be sensitive to structural and non-
stoichiometric 5 imperfections in the oxide. In parallel with the above re-
dox charge and discharge mechanism, a significant quantity of charge
will also be accommodated through double-layer charging since the
RU02 materials usually have a relatively large specific area of 26 to 90
m 2 g-l, depending on formation temperature, as noted earlier. Further de-
tails of the possible redox steps are given in Section 11.7.
(11.8)
was involved, with the stoichiometry changing from Ir(OHh at 0.6 V (RHE) to
Ir02 at 1.5 V, a process that is associated with a change of color or reflectivity
of the film. A similar redox process was proposed for the electrochemical oxi-
dation of Ru oxide species in hydrated states:
(11.9)
278 Chapter 11
Since the conversion of hydrated RuO to hydrated RU02 requires 2e, J in the Eq.
(11.9) would be about 1. It is important that in their paper, and in J ow's, 16,17 a
hydrated form of RU02 or other oxides is postulated. This is significant for the
mechanism of charging and discharging where facile proton insertion and dein-
sertion37,38, coupled with electron transfer through the electronically conducting
oxide, is supposedly involved. Such a mechanism has precedents in the mecha-
nisms of electrochemical reduction that have been established for Ni·O·OH to
Ni(OHh in the Ni-Cd battery and for the so-called "homogeneous mechanism"
for the first-electron reduction of Mn02.37,38
Based on X-ray emission analysis and SEM examination, Mitchell, Rand,
and WOOdS 14 deduced that ruthenium oxide films formed after 14,000 cycles
were about 200 nm thick (see Ref. 13 on related SEM work). They concluded
that such films were predominantly ofRuO stoichiometry, with a considerable
degree of nonstoichiometry (see Ref. 5), which would account for their good
electronic conductivity. However, a dissolution and redeposition mechanism,
possibly involving RU04, was suggested.
Charge and oxide thickness evaluations by Mitchell, Rand, and Woods 14
gave a value of 96 mC cm- 2passed between 0.06 and 1.5 V for an electrode cov-
ered by a 200-nm film. Taking the density of hydrated RU02 as 25-40% of that
of rutile RU02, ca. 65 wt. % Ru would be calculated. Thus the surface oxide
should contain between 20 and 40 f1g cm-2 of Ru and require a charge of 40-70
mC cm- 2 for oxidation of (supposed) RuO to RU02' These figures are of the
same order of magnitude as the obse:ved charge passed in the cyclic voltammo-
grams. Because there is a high surface area of the cycled material, appreciable
charge is also involved in double-layer charging and discharging, as noted ear-
lier.
A comparison with the charge and discharge behavior of thermochemi-
cally generated RU02 is important and was also considered by Mitchell, Rand,
and WOOdS. 14 The correlations between the experimental and calculated redox
charges led to the conclusion that each Ru atom in the electrochemically formed
oxide film is involved in the one-electron redox reaction, written as Eq. (11.2),
a conclusion also reached by Arikado, Iwakura, and Tamura. 27 However, this is
not the case for the thermally formed film, where the voltammetric charge (for
otherwise similar conditions) is only 3 mC cm- 2 even though the film is visible 13
and appears substantial. The above results 14 support the conclusion by Trasatti
and Buzzanca6 that only 2-7% of the atoms in thermally produced RU02 are
electrochemically involved in a redox electron-transfer process (Table 11.1).
Thus it was supposed that such electron transfers were localized to sites where
water molecules remained trapped in the lattice during its formation. In fact,
Kozawa37 had reported that hydration of RU02 is essential for discharge capac-
ity to be exhibited, which is a reasonable requirement for proton transport to oc-
cur.
The Electrochemical Behavior of Ruthenium Oxide 279
With ruthenium oxide electrodes having real areas of 60-80 times the ap-
parent areas, Arikado, Iwakura, and Tamura27 deduced that approximately one
electron per surface atom of Ru was involved in the electron-transfer redox
process (see Ref. 14 and Eq. 11.2). However, for films prepared at 450 to 550o e,
the charge values were too large for it to be concluded that only surface-atom
reactions were involved, so that some solid-phase, 3-dimensional redox proc-
esses must also be taking place, but not in the whole material. Note that for some
DSA RU02 electrode preparations, the real-to-apparent area ratios are around
400.
Another significant result obtained in work by Mitchell et a1. 14 was proof
of the involvement of proton diffusion (presumably via a jumping process from
OH- to 0 2- etc. in the hydrated oxide). This was found by some clever experi-
ments using Ru02 supported on a Pd membrane from or to which protons could
move. RU02 reacts with an H from the Pd (in an H+ + e process) involving the
reduction step RU02 ~ RuO·OH (Eq. 11.2), as with Ni·O·OH or Mn02?8,39
In addition to cyclic voltammetry work on Ru02, giving highly reversible
cyclic voltammograms, Raistrick 15 has carried out electrochemical quartz mi-
crobalance studies on this material and BET area measurements. The capaci-
tance was found to be proportional to the surface area, and a figure of 380 F g-1
was found for material of 130 m2 g-l. This corresponds (for e.g., a I-V operating
span at a single electrode) to 380 x 106/130 x 104 JiF cm- 2, i.e., ca. 300 JiF cm- 2.
This is of course at least ten times the specific double-layer capacitance ex-
pected at a metal, or oxide film/solution interface and confirms the involvement
of an appreciable Faradaic (redox) pseudocapacitance. However, it has been
suggested by Zheng and JOW 16,17 that this redox capacitance arises principally
at the surface sites on the oxide film. By means of the quartz microbalance tech-
nique, Raistrick et al. I5 ,40-44 showed that the redox process involves only proton
exchange (presumably at vicinal OH--0 2- ions) in the surface.
N
70
2°~
.
IE
u 0
.
o~~·
u
E 60
"cr
50
d .0
01.10)
with more difficulty during the voltammetric evaluation of charge at higher
sweep rates. This becomes a rate-determining step, particularly in hidden, inner-
surface regions. Trasatti wrote the voltammetric charge as the sum of two com-
ponents, the inner and outer charges, for the less and more accessible surface
regions, respectively. He concluded that a kind of proton hopping surface dif-
fusion ofH+ was involved in the outer region, as for nickel-oxide electrodes. 35
In interpreting the self-discharge and recovery behavior of potentials at
charged or discharged RuOz electrodes, Pell, Liu, and ConwayZ6 proposed a
three-layer model, as shown below, between which regions proton and electron
hopping takes place, giving rise to a time-dependent state of surface oxidation
and hence measured potential.
(11.7)
with each of the ions occupying lattice sites coordinating Ru z+ sites. In addition,
intralattice ionization of hydrate water (hence the importance of the ruthenium
oxide being hydrous in its bulk and/or at its surface regions) could provide ad-
ditional OH- (or 0 2-) sites through such steps as
°
solvation as H70; or H 90:t ions into the bulk solution. The binding or the
desorption ofH+ at the sites (as OH- or 0 2-) upon discharge or recharge must
be associated with a corresponding change of oxidation state ofRu atoms as cat-
ions in the surface (or bulk) oxide lattice structure.
The specific capacitance attainable at thermally generated RU02 surfaces
was estimated as 380 F g-l, which corresponds (with a linear charge or voltage
charging curve) to 47.5 kJ kg- 1 calculated for the active material alone. It is sub-
stantially greater40 at in situ electrochemically formed RU02 material owing to
the hydrous structure that is then formed, with corresponding better "bulk" ac-
cessibility for redox reactions.
----
0.5
<t
E 0.1
......
H -0.1
N
J:
......
<I
The figures of Raistrick for the real area per gram (130 m 2) and the capaci-
tance of 380 F g-1 translate to a specific capacitance of 3 x 1061130 X 104 flF
cm- 2, i.e., about 300. This is about 10 times a probable double-layer capacitance
value, confirming the pseudocapacitative nature of the charging process involv-
ing surface redox processes plus a usual 10% double-layer contribution. For a
summary of thermal decomposition processes, see S. Trasatti in Electrodes of
Conductive Metal Oxides (Part B), S. Trasatti, ed. Elsevier North Holland, New
York (1981).
100r-----------------------------------------,
R= 100 Kn (lI)
= 20Kn (0)
= 10 Kft (x)
= 5 Kit (0)
=250 n (0)
• 63 n (+)
>
"-
.....
0::
10
10 100
tiRe
FIGURE 11.11. dc discharge kinetics of an RU02 film capacitance through six values of load re-
sistance, R, as indicated, expressed as a plot of RI vs tiRe. (From Wojtowicz and Conway, unpub-
lished.)
286 Chapter 11
·.~16F
' ..
. .. 3.76 F
0
.-..
.'
.1 •
-1
'.
-2
I..L.
"-
U
-3
..
<.!)
0
....J
-4
.·-11.7p.F
-5
-6
-4 -3 -2 -1 0 1 2 3 4 5
LOG f(Hz)
FIGURE 11.12. Dispersion of capacitance C (as log C) of a small RU02 electrode with frequency
in ac modulation over the range 10-3.4 Hz to 10 kHz. (From Wojtowicz and Conway, unpublished.)
dc conditions. The form of the plot derives from the discharge equation, namely
Vet) =exp[-t(RC)] + constant and V(t) =I(t) R, the time-dependent potential dif-
ference across C as it discharges at current I(t) into R. tlRC is a reduced time,
scaled by the time constant, RC.
The behavior under ac modulation exhibits a major dispersion of capaci-
tance (Fig. 11.12), which is typical of porous electrode behavior. RU02 can also
be dispersed as high-area films, thermally formed on glass, glass particles, or
carbon. Their ac impedance behavior is very similar to that of the anodic (hy-
drous) film on metallic Ru (Fig. 11.2). It is seen that the accessible capacitance
of this particular small RU02 electrode falls from 16 F at 10-3.4 Hz to 11.7 f.1.F
(the double-layer capacitance) at 10 kHz.
0.60
0.30
<{
E
...... QO.2 0.2
.....
-0.30
-0.60
FIGURE 11.13. Cyclic voltammogram for an electrochemically formed and cycled oxide film on
W in aqueous 1 mol dm-3 H2S04. (From Conway and Birss, unpublished.)
288 Chapter 11
1 . 0 0 r - - - - - - - - - - - - - -- - - - - - - - - - ,
0 .50
<l
E
......
I-
Z
w
a::
a:: 0.00
:J
U
-0.50~---~---~------~---~---~
0.5 0 .75 1. 25 1. 5 1.75
POTENTIAL / V
FIGURE 11.14. Cyclic voltammograms for an electrochemically formed C0304 oxide film on Co
in aqueous KOH. (From Simpraga and Conway, unpublished.)
behavior arises on Mo. However, the operating ranges are only about 0.8 V, sub-
stantially less than that for RU02'
Other cheap and easily prepared materials that exhibit large specific
pseudocapacitance values are the family of conducting, electro active polymers
such as polyaniline, polypyrrole, poly thiophene, and their derivatives. Their be-
havior can be regarded as analogous to that of redox-type pseudocapacitors (see
Chapter 12). They represent a special class of materials and will be dealt with
separately in Chapter 12.
This chapter is concluded by reiterating the important and fundamental dif-
ference between pseudocapacitative, reversible discharging and recharging be-
havior [Fig. 11.15(a)] of RU02 and other oxides, and the irreversible behavior
in the cyclic voltammograms for a battery electrode system (e.g., Pb-PbCI 2), as
illustrated in Fig. 11.15(b), where the electrochemical half-cell reaction is
Pb + 2CI- ~ PbCl 2 + 2e. In the first type of system, the anodic and cathodic
voltammograms are almost mirror images of each other; in the second case
of a battery-type material, the anodic and cathodic voltammograms are
widely separated and involve substantial anodic and cathodic overvoltages
around a reversible potential at the crossover potential [Fig. 11.15(b)] for a
change of sign of currents from anodic to cathodic, or vice versa. The irre-
versibility in the case of the battery-type systems such as Pb-PbCI 2, Pb-PbS04 ,
and Mn02-Mn(OHh is due primarily to irreversibility in the phase changes in-
volved and to the widely different Gibbs energies of the oxidized and reduced
forms of the couples involved.
The Electrochemical Behavior of Ruthenium Oxide 289
u 12.5
vB
~ ~ a
v; c:(
~ 6 .25
<1'1
(\J
'E
u 0 ~-+--~~~~--+--+--~--~~--t--+--i--i--;----
c::(
E
......
c 6.25
t::J U
UB
o
J: 12.5
I-
<t
U
0 .2 0 .6 1.0 1.4
Potent ial I V, E RHE
b
Pb/PbCI 2
~ 66"r
:;
v
~H
I
"II POTENTIAL/V, RHE
~ ·or., ,0)" -0.2"
.. 0
FIGURE 11.15, Contrast between cyclic voltammogram for (a) reversible redox processes at an
RU02 film electrode in 1 M H2S04 and (b) the totally irreversible processes of formation and re-
duction of PbCh on Pb where major changes in phase and chemical substance take place. (Diagram
repeated from Chapter 2.)
290 Chapter 11
linear region
I
-- --
---------- Q
.g...
,.--- u
/ "" - - - L Crt/=::: constant ~
o ,/
/
/
Z
~/
Wo ~
(,!)
~
U
c:t C5:
:::c <:{
u u
POTENTIAL ( - +ve)
FIGURE 11.16. Illustrating overlap of three redox capacitance (C¢) responses required to give
almost constant net capacitance over an appreciable potential range, as observed with RU02. Q is
the accumulated charge (schematic). (B. V. Tilak, unpublished).
The mixed metal oxide technology, Ru02 with Ti02 or Ta205, developed
by the Ottawa group for redox pseudocapacitor devices in work with Continen-
tal Group, Inc., was examined in important fundamental ways in an interesting
The Electrochemical Behavior of Ruthenium Oxide 291
paper by Atanasoski. 32 Two topics were addressed: (1) the surface chemistry of
RU02, with emphasis on the oxidation state of Ru species and (2) the distribu-
tion of Ru at the pseudocapacitor material interface. From a combination of
electrochemical, photoelectrochemical, and ultrahigh vacuum (URV) surface-
analysis studies, it was concluded that the electrochemically significant interac-
tion between the oxides of Ru and Ti was confined to the interfacial region.
Ti0 2, as a rutile structure, functions as a support and stabilizing agent for the
RU02, which otherwise tends to disappear from the electrode structure when po-
larized (anodic corrosion) as RU02 and volatile RU04 (cf. OS04). This is the ba-
sis of the high stability of DSA RuOT Ti0 2 composite electrodes.
A significant aspect of this work was that single-crystal Ru02-Ti02 was
examined in comparison with thermally formed (as in the DSA electrode for-
mation process) RUOT Ti0 2 films. The single-crystal work allowed the recon-
structed surface of Ru02 to be compared with the unreconstructed (1 x 1)
°
surface and the hexagonal structure, in relation to surface content of atoms.
°
The surface content and Ti-Ru and O-(Ti + Ru) ratios were determined by
means of Auger spectra taken at the same spot on the surface; the data are shown
in Table 11.2.
Three possibilities have been proposed for the incorporation and distribu-
tion of RU02 thermally generated on an anodic surface oxide film of Ti0 2.32
Further literature on this direction of work on RU02 is found in Refs. 33 and 48
to 53.
The coordination and electronic band structure of RU02 (rutile geometry)
were reviewed and illustrated in Ref. 54 in connection with the use of RU02 as
the DSA anode electrocatalyst material for commercial Cl 2 production. Some
of the same factors (e.g., electronic conductivity) that make this oxide an excel-
lent anode electrocatalyst also make it a very attractive redox pseudocapacitor,
e.g., through participation of several overlapping redox stages which lead to the
electronic conductivity. It is interesting that PbOb which is also an electronic
The use of mixed oxides, that is with additions of Ti0 2, Ta205, and La203,
has formed an important aspect55 of the developing technology of RuOrbased
capacitor devices. In a recent paper by Tilak, Birss, and Chen,56 the electro-
chemical impedance behavior of such mixed oxides was examined over a range
of RU02 contents in RuOr Ti0 2 mixtures. The effects are dramatic, as illustrated
in Fig. 11.17, where the phase angle, q'J, vs. log [frequency] plots are shown for
Ru02 content that increases from 5 to 40%. The experiments were conducted in
5 M aqueous NaCl at 298 K at the open-circuit potential.
90r-----.-----.-----.-----.-----r---~
30 " ~I
II
1\
"",,
o~----~----~----~----~----~--~
10-1 10 2 104
FREQUENCY/Hz
FIGURE 11.17. Frequency dependence of phase angle I/J in impedance spectra of fresh RU02 +
Ti02 composite electrodes having six different Ru contents by indicated percent at 298 K in 5.0 M
NaCI at the open-circuit potential. (From Tilak, Birss, and Chen, in press.)
The Electrochemical Behavior of Ruthenium Oxide 293
At low Ru02 percentages (5, 10, and 15%), the </J vs. log [frequency] be-
havior corresponds substantially to the high-frequency double-layer response.
However, as more Ru02 is present (20 to 40%), the </J curves correspond to a
much lower frequency-response characteristic of the (redox) pseudocapaci-
tance, with the </J dispersion curve rather suddenly moving up toward the pure
capacitance limit of 90° at 0.1 Hz. The complex-plane plots contain related in-
formation but are more complicated to discuss. These results of Tilak et al. show
that the added oxide components do not act just as diluents of the RU02, but in-
timately influence its pseudocapacitative behavior.
+ + ----)
... ....
2.2 ~
.~~------------------------~
FIGURE 11.18. Comparative features of voltammograms for oxide formation, or oxidation, and
reduction for several transition metals with thin or thick oxide films; note cases of reversible vis a
vis irreversible behavior (semischematic).
The Electrochemical Behavior of Ruthenium Oxide 295
+ Nj (thick film)
+ + Ru (thick film)
.~~--------------------~~~ .~~-----------------------4.
V
REFERENCES
1. 1. B. Goodenough, in Progress in Solid-State Chemistry, N. Reiss, ed., vol. 5, Pergamon, New
York (1971).
2. W. D. Ryden, A. W. Lawson, and C. C. Sartain, Phys. Letters, 26A, 209 (1968).
3. H. Schafer, G. Schneidereit, and W. Gerhardt, Zeit. Anorg. AUg. Chemie, 319, 372 (1963).
4. S. Trasatti and G. Lodi, Conductive Metal Oxides, S. Trasatti, ed., vol. A, p. 338, Elsevier,
Amsterdam (1980).
5. D. Galizzioli, F. Tantardini, and S. Trasatti, 1. Appl. Electrochemi., 4, 57 (1974).
6. S. Trasatti and G. Buzzanca, 1. Electroanal. Chem., 29, Appl. 1 (1971).
7. S. Hadzi-lordanov, H. A. Kozlowska, M. Vukovic, and B. E. Conway, 1. Electrochem. Soc.,
125, 1473 (1978).
296 Chapter 11
40. I. D. Raistrick, in Proc. First Inti. Seminar on Double-Layer Capacitors and Similar Energy
Storage Devices, S. P. Wolsky and N. Marincic, eds., Florida Educational Seminars, Boca
Raton, Fla. (1991).
41. C. Ho, I. D. Raistrick, and R. A. Huggins, 1. Electrochem. Soc., 127, 343 (1980).
42. I. D. Raistrick and R. A. Huggins, Solid State Ionics, 7, 213 (1982).
43. I. D. Raistrick, Solid State Ionics, 9/10, 425 (1983).
44. I. D. Raistrick, Rev. Chim. Min., 21, 456 (1984).
45. S. Ardizzone, G. Fregonara, and S. Trasatti, Electrochim. Acta, 35, 263 (1990).
46. B. E. Conway, V. Birss, and J. Wojkowicz, 1. Power Sources, 66, 1 (1997).
47. S. L. Roberson, R. F. Davis, and D. Finello, in Proc. Sixth Inti. Seminar on Double-Layer
Capacitors and Similar Energy Storage Devices, S. P. Wolsky and N. Marincic, eds., Florida
Educational Seminars, Boca Raton, Fla. (1996).
48. L. J. Atanasoska, W. E. O'Grady, R. T. Atanososki, and F. Pollak, Surface Sci., 202, 142
(1988).
49. L. J. Atanasoska, R. T. Atanasoski, F. Pollak, and W. E. O'Grady, Surface Sci., 2309, 95
(1990).
50. M. R. Kozlowski, P. S. Tyler, W. H. Smyrl, and R. T. Atanoasoski, Surface Sci., 194,505
(1988).
51. P. S. Tyler, M. R. Kozlowski, W. H. Smyrl, and R. T. Atanasoski, 1. Electroanal. Chem, 237,
295 (1987).
52. M. R. Kozlowski, P. S. Tyler, W. H. Smyrl, and R. T. Atanasoski, 1. Electrochem. Soc., 136,
442 (1989).
53. F. Hine, M. Yasuda, T. Noda, T. Yoshida, and J. Okuda, 1. Electrochem. Soc., 126, 1439
(1979).
54. B. E. Conway and B. V. Tilak, in Adv. in Catalysis, 38,122-135 (1992).
55. D. Craig, Canadian Pat. No. 1,196,683 (1985).
56. B. V. Tilak, V. Birss, and c.-P. Chen, Proc. Electrochemical Society (Grahame) Symposium,
97-17, 372 (1997), c. Korzeniewski and B. E. Conway, The Electrochemical Society,
Pennington, N.J. (1997).
57. L. S. Roblee, M. J. Mangaudia, E. D. Lapinsky, A. G. Kimball, and S. B. Brummer, Mat. Res.
Soc., Symp. Proc., 55, 287 (1986).
58. R. A-Blageni, A. G. Kimball, L. S. Roblee, G. Kahanda, and M. Tomkiewicz, 1. Electrochem.
Soc., 134, 2637 (1987).
59. X. Beebe and T. L. Rose, IEEE Trans. Biomed. Eng. BMK-35, 494 (1988).
60. X. Beebe, R. D. Raub, and T. L. Rose, Electrochim. Acta, 34, 795 (1988).
61. J. D. Klein, S. L. Clauson, and S. F. Cogan, 1. Vac. Sci. Technol., A7, 3043 (1989).
62. B. A-Blageni, M. M. Boucher, A. G. Kimball, and L. S. Roblee, 1. Mat. Res., 4, 440 (1989).
63. 1. D. Klein, S. L. Clauson, and S. F. Cogan,l. Mat. Res., 4,1505 (1989).
64. F. M. Kalliber and T. L. Rose, 1. Electrochem. Soc., 136, 1765 (1989).
1. S. Trasatti and G. Lodi, Conductive Metal Oxides, vols. A and B, Elsevier, Amsterdam (1980).
2. S. Trasatti and P. Kurzweil, Platinum Metals Rev., 38(2), 46 (1994).
3. B. E. Conway, Electrochemical Oxide Film Formation at Noble Metals as a Surface-Chemical
Process, Progress in Surface Science, S. G. Davison, ed., vol. 49, pp. 331-452, Pergamon,
New York (1995).
4. L. Young, Anodic Oxide Films, Academic Press, New York (1961).
Chapter 12
mers has been likened to that by impurity dopants added to intrinsic semicon-
ductors such as Si or Ge and the terms "p-doping" and "n-doping" are used to
describe the results of electrochemical oxidation or reduction, respectively.
These two terms do not seem, however, altogether appropriate because they do
not correspond to their respective significances in semiconductor science where
the doping arises from the actual addition of chemical electron-donor or elec-
tron-acceptor impurities which give rise to a new conduction band or valence
band of states and a diminished band gap. The electrochemical processes at the
conducting polymers are electrochemical redox reactions associated with se-
quential Lewis acid- or Lewis base-producing steps so that the polymer mole-
cules are converted to multiply charged structures through electrochemical
Lewis-type reactions involving electron withdrawal or electron donation.
It is the possibility of introducing positive or negative charge centers on
electronically conjugated polymer chains by means of electrochemical oxida-
tion or reduction reactions, the extents of which depend on electrode potential,
that has given rise to the substantial current and earlier interest lO- 14 in these ma-
terials for supercapacitor devices. The capacitance developed is substantial and
can be thought of as of the redox pseudocapacitance type (see Chapter 10) that
is associated with Faradaic redox processes. A coupled double-layer capaci-
tance, probably about 2-5% of the specific pseudocapacitance, would be ex-
pected (Chapter 6) also to be observed, a point to be discussed further later. The
utilization of this pseudocapacitance associated with the redox properties of
such polymers in electrochemical capacitor devices is reviewed in more detail
below.
Conducting-polymer systems offer opportunities for storing electrochemi-
cal energy largely through their redox capacitance. Therefore, like Li intercala-
tion systems or RU02, they store energy largely by Faradaic processes that
correspond formally to "battery-type" behavior but exhibit electrical charac-
teristics which are those of a capacitor, i.e., there is a functional relation between
the charge (q) accommodated and the potential (V) of the electrode, giving a de-
rivative dqldVthat corresponds to (pseudo) capacitance (Chapter 10). However,
as explained later in this Chapter, because of the metal-like properties of these
polymers in their conducting states, it can be argued formally that the capaci-
tance developed is ofthe double-layer type. Because the charging and discharg-
ing reactions do not involve any appreciable structural alterations, such as phase
changes, the processes are highly reversible, as for proton intercalation into
RU02 or Li ions into some oxides and sulfides.
Such polymer materials are much cheaper than RU02 or Ir02 and can gen-
erate comparably large specific capacitances, F g-l. Being organic chemicals in
nature and subject to periodic oxidations (on charge) or reductions (on dis-
charge), at least in most cases they do not have the very long-term stabilities or
cycle lives ofthe mixed-oxide type of electrochemical capacitor. However, very
Capacitance Behavior of Polymer Films 301
substantial cycle lives have been achieved with not too much degradation, and
such performance is adequate for many applications. Also, work in recent years
(see later discussion) is revealing new polymer electrode materials that can be
cycled over substantially wider potential ranges than polyaniline or polypyrrole.
The possibility of employing electroactive conducting polymers such as
polypyrrole or polyaniline as electrochemical (pseudo)capacitor materials was
suggested in papers by Gottesfeld 11-14 and by Conway.1O These proposals were
predicated on the excellent reversibility of electrochemical charge and dis-
charge which these materials exhibit over a potential range of 0.8 to 0.9 V, and
the associated mirror-image cyclic voltammograms which they also display and
which are an essential feature for capacitor-type electrical energy storage
(Chapter 10). Such materials are of course much cheaper than RU02, which also
gives mirror-image behavior, but are not as stable over very long-term cycling
(10 5_106 cycle life).
The essential features of the electrochemical behavior of conducting poly-
mers that make them suitable as electrochemical capacitor materials are (1) the
continuous range of states of oxidation that arise with increasing electrode po-
tential and (2) the reversibility of the Faradaic processes corresponding to
charge withdrawal and reinjection. The processes involved thus give rise in cy-
clic voltamrnetry to almost mirror-image voltamrnograms that are characteristic
of capacitor discharge and recharge behavior, and also to response currents that
increase with sweep rate.
The progressive dependence of charge on potential is analogous to that
originating in the titration of a polymeric acid or base [e.g., poly(methacrylic
acid)] as pH is increased (Br~nsted-type ionization due to transfer of protons),
giving rise to poly anions from polyacids or polycations from polybases. How-
ever, such polymers do not become electronically conducting on account of the
Br~nsted ionizations (in that case) induced by pH change. The monomer pKa is
about 4, but as the polyacid is progressively titrated with a base, the pKa con-
tinuously increases to about 10-11 (Fig. 12.1), i.e., the standard Gibbs energy
of the deprotonation of -COOH groups to give -COO- centers progressively
changes owing to interaction effects between the ionic charges on (side groups
of) the polymer chain, namely, -COO- groups. Analogously, with the conduct-
ing polymers, Lewis ionization by oxidation (transfer of electrons) causes a pro-
gressive change of standard redox potential (increase of Gibbs energy) owing
to lateral interactions between the generated positive (and delocalized) charge
centers, which makes further oxidation more difficult (higher electrode poten-
tial required) the more a given degree of oxidation is established.
In the case of polyelectrolytes derived from potential polyelectrolytes
[e.g., poly(methacrylic acid) or poly(vinylpyridine)], the ionization arises by a
Br~nsted deprotonation or protonation, respectively, i.e., by acid/base ioniza-
tion processes involving protons. In strong bases or acids, the degree of ioniza-
302 Chapter 12
14
7
pH Monomer
pK o
0.5
Formal degree of neutralization
FIGURE 12.1. Acid-base titration curve for a monomeric vinylic acid (e.g., methacrylic acid)
and for the corresponding linear polymer having a pKa increasing with degree of neutralization (the
pKa of the monomer is taken as 4).
tion can be up to about one ionic center on the chain per monomer unit. With
the conducting polymers, charges are introduced on the polymer chains by a Le-
wis acid or base type of process formally involving oxidation or reduction with
electron transfer, the electrode surface behaving as the conjugate Lewis base or
acid. In both B[fmsted and Lewis types of ionization at polymer chains, high lin-
ear charge densities can be generated. However, such high charge densities can-
not usually be sustained without some coupled charge-shielding process taking
place. In both cases this is achieved by counterion association with the chain
charges, leading to a Helmholtz type of double-layer configuration, as illus-
trated in Fig. 12.2.
In effect, both with Lewis ionization and Brpnsted protonic ionization, a
quasi-linear, one-dimensional cylindrical Helmholtzlike double layer of
charges becomes developed with the involvement of counterions of the electro-
lyte. In the case of the conducting polymer materials, it becomes somewhat dif-
ficult to distinguish whether the charging process is to be regarded as of the
I-dimensional double-layer (see Fig. 12.2) type or I-dimensional redox pseudo-
capacitance charging, but it is not just a semantic matter. Insofar as the charge
development can be regarded as having some of the characteristics of a Faradaic
reaction, the latter description of polymer capacitance behavior seems formally
preferable. An alternative view is that the distribution of redox potentials is re-
lated to a range of electrochemical Gibbs energies in the polymer for sites that
are candidates for being charged. However, the impedance spectroscopy of such
conducting, electroactive polymer matrices has features similar to those of the
Capacitance Behavior of Polymer Films 303
(a) Polymer
Backbone
ID
P·OOPING
e
..
P·OEOOPING
e
@
Current Current 9
Collector Neutral Solution Collector P·Ooped Solution
Plate Conducting <tl Cations Plate Conducting
Polymer 9 Anions Polymer
FUm Film
(b)
N·OOPING
~
.. N-DEDOPING
e
<tl
Currenl Current
e
Collector Neutral Solution Collector N·Ooped Solution
Plale Conducting @Callons Plate Conducting
Polymer 9Anlons Polymer
Film Film
6
+
+ e
Note that it is the location of the radical (.) site that varies among the resonating
forms of the molecule; the positive charge is located on the aniline N center. The
generation of the free-radical center engenders polymerization.
Following that polymerization, and sometimes coupled with it, various
stages of deprotonation can arise, giving rise (Scheme 1) to recognizable and
characterized intermediates, known in classical organic chemistry; the names
are usually trivial ones, related to the colors of the intermediates. Corresponding
acid or base protonation or deprotonation processes can occur.
In the oxidation and reduction processes, transitions between insulating
and conducting states of the polymers can occur (see the reaction schemes on
following pages). A complex variety of molecular structures can be involved,
as shown in the formulas that follow. Some of the intermediates are highly col-
Capacitance Behavior of Polymer Films 307
LE UCOEMERAl..D1NE
HN~~~ H H H
HNcu.o~ H
EMERAlJ)1NJ!
H
~"U.O~ H
SCHEMEL
ored, golden, green, etc., and the colors change during the progression ofpolym-
erization and oxidation. The electropolymerizations can be effected most con-
veniently in situ on an inert substrate electrode subjected to cyclic polarization
(cyclic voltammetry) over an appropriate potential range. The resulting polymer
films adhere to metal or carbon substrates and are reasonably stable.
It is outside the scope of this chapter to discuss in any detail the organic
chemistry of aniline polymerization and the associated series of complex oxi-
dation (and reduction) steps that can take place. Also, the redox behavior is de-
pendent on the protonation or deprotonation associated both with pH variation
and with oxidation or reduction, respectively. Anion binding (association) is
usually an important concomitant process accompanying oxidative polymeriza-
tion and the oxidative half-cycle associated with charging, and leads to the for-
mation of double layers.
However, we give in a few reaction schemes and chemical formulas some
of the essential changes that occur in aniline upon its polymerization and oxi-
dation since they are important for understanding the processes of charge ac-
commodation and the development of metallic conductivity. These are
308 Chapter 12
aqueous medium H H
strong acid
X=H
0
I:-@-@-IN+-H
-N+ 0
I I
H H
NH2
$
aqueous medium neutral H H
X-@-~-@-~
or weak acid
X=H, CI, OCH3
OCH:zCH3, COOH H
CN,N02
X
aqueous medium
strong base
X-@-N .. N-@-X
~CNlpyrldine
SCHEME 3.
Capacitance Behavior of Polymer Films 309
-@-~-@-~- NH-NH
-@-~-@-a- +
NH-~H
-@-~+-@-~- +
NH2 -NH
-@-E+-@-~t- ++
NH-~H
-@-N==O=~- +
.
N=N
==O=N==O=N- N=N
SCHEME 4.
(.)
AmiDe form: A
t-O-t·:=o-i·A-l
Salt Corm : S
(b)
(cj
SCHEMES.
310 Chapter 12
illustrated in the accompanying schematic formulas above and below. These re-
action schemes have been discussed in much more detail in the original litera-
ture (see review Refs. 9 and 38).
It can be seen how a linear structure, capable of being successively oxi-
dized (or reduced) down a polymer chain in one dimension, is analogous to the
2-, or 3-dimensional situation where successive oxidation or reduction stages
can occur in conducting hydrous oxides of transition metals (Ru02, Co02) or
progressively in quasi-2-dimensional intercalation processes involving Li, e.g.,
in TiS 2 , MoS 2, and Co02. In all these cases, large capacitances can arise as
pseudocapacitance, offering the potential for using such materials as superca-
pacitor electrodes.
The main points of interest, for the purposes of a supercapacitor material,
are (1) the possibility of a linear structure being developed with a sequence of
oxidation and re-reduction sites that could give rise to a redox process for which
charge accepted or delivered is a function of potential; and (2) the development
of a semimetallic conductivity along electronically conjugated double-bond
structures in a linear array in the oxidized state of the molecule (cf. Schemes 2
and 5).
Notwithstanding the complex series of states that the poly aniline structure
can exist in (see above), it is unclear at the moment why poly aniline gives
clearly three current-response peaks in cyclic voltammetry (Fig. 12.3) (formally
reminiscent of underpotential deposition of base metals on a noble metal where
appreciable pseudocapacitance arises but originates for different reasons) in the
oxidation and reduction cyclic voltammogram while o-anisidine (the o-OMe-
substituted aniline) gives only one main peak (Fig. 12.4).
In practice, the electrochemical response of polyaniline is also quite de-
pendent on the co-anion of the electrolyte, the behavior in HCI, H 2S04 , or
HCI0 4 being appreciably, indeed almost qualitatively, different. This can be
atttributed to different anion binding to the polymer system in its various oxi-
dation states, which is analogous to the specificity of anion adsorption at elec-
trodes of Au or Hg and their effects on H UPD at Pt, and also to counterion
binding at polyelectrolyte chains. Such anion binding at elementary units of the
poly aniline chain is illustrated in Scheme 6 and Fig. 12.2.
Scheme 1 shows five states of progressive oxidation (dehydrogenation at
the -NH- centers) of the so-called "leucoemeraldine" polymer (reduced form;
"leuco" = relatively uncolored). The completely dehydrogenated polymer (at
the Ns except for the end groups) is called "pernigraniline." Corresponding
changes in conductivity occur in the course of progressive oxidation. 39
A reaction mechanism for radical cation coupling of aniline, leading to the
formation of a linear polymer, is shown in Scheme 2 which indicates (cf. Refs.
16 and 39) the steps that are believed to occur by radical coupling, leading to
the formation of linear polymer structures. Other aromatic coupling steps are
Capacitance Behavior of Polymer Films 311
'::fF NG
1 S INSULATING
OX!t RED H
(TYPE I) H+
{N=O=N-aH+X- ~ tN=O-~--c».
(TYPE II)
-'--N=O=N~)( ~ 1 N = O = N -~ \ +e-
"\ - ~n \: - )(~n
'=O=N-o-'N
\ - -
)
X
... ACID.
BASE ((==O=N-o-~=)\-t
2 A INSULATING 2 S CONDUCTING
((=O=N-o-N
3 A INSULATING
H~: ((=er-O-ry::"'l 3 S CONDUCTING
SCHEME 6.
H H
a) (-o-J-o-t ~2ne-2nH+ .. (-o-~-Q=N-t
Insulatlng-deprotonated Insulating-deprotonated
reduced tonn oxidized tonn
H
nHw H+ solv Hsolv
n w
Hsolv
b) (-o-J-o-J-t~ (-o-~+==O=~+-)n
protonated tonn protonated oxidized tonn
InsUaior c:onctx:tor
first oxidation level
H H+solv H
conductor I protonated
Hsolv Hsolv -2)( -2T"
e) (-o-~+==O=~'-)n~ (-o-~-o-~-t
2)( .2T"
first oxidation level protonated reduced tonn
conductor I protonated Insulator
SCHEME 7.
Various chemical structures of poly aniline can occur (Scheme 4), includ-
ing salt forms, as shown in Scheme 5 and 6.
The relationship between insulating and conducting stages of electroactive
conducting polymers is of great importance in redox supercapacitor devices.
Some examples for the polyaniline structural units were shown in Scheme 3 and
4. The role of pH (protonation, deprotonation) involvement and anion (A -) as-
sociation in the transition between conducting and insulating states is shown in
Scheme 7.
The general behavior of the conducting polymers that have potential use
as capacitor materials is formally that of a redox pseudocapacitor (Chapter 10).
Capacitance Behavior of Polymer Films 313
They exhibit the typical mirror-image type of cyclic voltammogram (Fig. 12.3)
that is a required aspect of reversible charging behavior over a range of poten-
tials as exhibited by Ru02 and by regular double-layer-type capacitors.
At each potential along the voltammetric scan, a new equilibrium potential
is established that corresponds to some fraction (y) of the polymer chains having
been oxidized, leaving some remaining fraction (1 - y) unoxidized or in the re-
duced state (see Chapter 10). y represents a I-dimensional fractional extent of
oxidation of the polymer chain (or of full linear charge density) analogous
to '9\, the 3-dimensional state of oxidation in a bulk redox system, or to e,
the 2-dimensional state of occupancy of sites in an electrosorption process,
e.g., UPD of H on a metal surface lattice.
The electro-oxidation isotherm for charge accommodation as a function of
potential will, in the first analysis, be like a Langmuir isotherm or the exponen-
tial form of a Nernst equation. However, the substantial range of charge accep-
tance on the voltage polarization scale that arises (ca. 0.8-0.9 V or more)
indicates the strong role of intercharge repulsion or corresponding electronic in-
teraction effects, so that potentials for charge formation on the polymer chains
depend on the charge density already resident on the chain, a behavior also char-
acteristic of double-layer capacitance.
Most of the electroactive polymers can be generated in the conducting state
by chemical or electrochemical oxidation, which introduces positive charges
(so-called "p-doping") on the repeating units of the polymer chains. Conjugate
reduction returns the structures back to a less or nonconducting condition. Some
polymers, however (e.g., poly acetylenes, poly-o-phenylene, and polythio-
phenes), can also be rendered conducting by reduction, corresponding to so-
called "n-doping."
In contact with a solution, the polymer matrix is perfused by the electrolyte
so that charge neutrality during charging or discharging is achieved by ion as-
sociation with the charged chains, as with polyelectrolytes. Hence ions (anions
or cations) have to move in and out of the matrix upon charge or discharge. Cor-
respondingly, changes of solvation and electrostriction around the polymer
chains must take place in concert with the charging or discharging processes, as
also occurs in polyelectrolyte ionization. Conformational changes of the poly-
mer chain also take place to minimize its Gibbs energy, as with polyelectrolytes.
The ion distribution (ion association or ion binding), corresponding to the
requirement of electroneutrality was illustrated schematically in Fig. 12.2 in re-
lation to polymer chain oxidation or reduction.
As with adsorption pseudocapacitance and other pseudocapacitance be-
havior, the key factors with the electroactive, conducting polymers are (1) that
the material itself has or acquires intrinsic electronic conductivity and (2) more
significantly, that the cyclic voltammograms for oxidation and re-reduction are
314 Chapter 12
(almost) mirror images of each other over an appreciable range of electrode po-
tentials, e.g., 0.8 V for PANI (polyaniline) in aqueous solutions.
In Chapter 10 it was explained that at each and any potential in the scanned
range, a reversible electron transfer (redox) process is established so that cycling
between the oxidized and the reduced states is facile and reversible. The capaci-
tance charging current vs. potential profiles are differentials of the redox titra-
tion curve for the material and virtually no kinetic polarization (Chapter 3) is
involved except at high sweep rates (s > so; see Chapter 10) or at overcharge po-
tentials.
As emphasized earlier, mirror-image cyclic voltammetry behavior is es-
sential for a pseudocapacitor system to behave electrically like a regular capaci-
tor or, more particularly, like a double-layer capacitance. This kind of
requirement is well demonstrated by the behavior of a variety of electroactive
conductive polymers, hence their potential value as cheap electrochemical ca-
pacitor materials, as recognized in the recent literature.l0.ll.13.14.36.40
ANILINE
I-
Z
w
a::
0: POTENTIAL
:::>
u
FIGURE 12.3. Sequence of voltammograms for polyaniline oxidation and re-reduction in suc-
cessive cycles as the film builds up on a gold electrode in aqueous H2S04. (From the author's labo-
ratory with Gu Ping; cf. Gholamian. 6)
o-ANISIDINE
I-
Z
w
0: ~~----------------~~---------/~-------
0: POTENTIAL
:::>
u
FIGURE 12.4. Voltammogram for a poly-o-anisidine film grown on a gold electrode in aqueous
H2S04. (From the author's laboratory, with Gu Ping.)
316 Chapter 12
Interesting results related to this question were found by D' Aprano and Le-
clerc,39 who showed voltammograms for poly(2-methylaniline) (PMA), poly(2-
methoxyaniline) (PMOA), poly(2-methoxy-5-methylaniline) (PMOMA), and
poly(2,5-dimethoxyaniline) (PDMOA) in 1 M aqueous ReI. These authors also
recorded the conductivity of films ofthese materials (Fig. 12.5) and found max-
ima at 0.42 V (vs. SeE) for PANI, PMA, and PABA; 0.35 V for PMOA and
PMOMA; and 0.28 V for PDMOA, the films being virtually nonconductive in
the fully reduced (leucoemeraldine) or fully oxidized (pernigraniline) states in
the case of PANI. They also examined the optical (electronic) spectra of these
PMOMA with the change in the oxidation state (Fig. 12.6).
In this work some attempt was made to explain the multiplicity of peaks
observed in the voltammetry of PANI; it was suggested that they may arise as
a result of some degradation products formed during the electrochemical po-
lymerization and/or side-couplings (branching defects in the linear polymeriza-
tion). The selectivity of head-to-tail (isosteric) couplings was diminished by
methoxy substitution on the ring. The range of appreciable anodic and cathodic
electroactivity ofthese polymers was about 0.5 to 0.7 V, which is similar to that
for PANI itself.
A different basis for explanation of the multiple current peaks observed
with PANI films was offered by Jiang, Zhang, and Xiang. 16 Peaks these authors
designated a and d at 0.13 V and -0.04 V (vs. SeE) may relate to protonation
and deprotonation processes (I, II) while they thought that peaks designated as
band cat 0.42 and 0.35 V may be associated with electron transfer coupled with
anion ion pairing with the charged chain (II, III). Some of the anodic and
cathodic separation between the respective peaks may be due to an iR drop in
the film and/or to some kinetic irreversibility.
Another and possibly more correct explanation is that the multiplicity of
the peaks for PANI arises simply from a stepwise oxidation to the first radical
cation and thence to the dication (bipolaron), based on electron-proton or on
electron-counterion coupling, depending on the acidity or the counterion' s mo-
bility, i.e., its Stokes's law diameter. Alternatively, another probable reason is
that some component of artha coupling could lead to the minor peak(s) ob-
served between the two main ones, as suggested by Genies et aI.9
An interesting and original variant was prepared and investigated by Got-
tesfeld et al. 14,42: poly-3-(4-fluorophenyl)-thiophene (PFPT) in an electrolyte of
tetramethylammonium trifluoromethanesulfonate (TMATFMS) in acetonitrile.
Structures of the PFPT (formula 3) and related nonfluorinated repeating (y)
groups (formulas 1 and 2) are shown below.
The cyclic voltammogram of PFPT (Fig. 12.7) is strikingly different from
that for PANI in that it exhibits two widely separated regions of almost revers-
ible electroactivity that correspond to both positive and negative charge injec-
tion (coupled with ion association). The voltage range within each
Capacitance Behavior of Polymer Films 317
0.006r-----------------~~----------_,
PMOMA
'E 0.004
u
If)
"-
~
0.002
0.3 PDMOA
IE
u 0.2
If)
"-
~
0.1
0.0
-0.2 0.6
FIGURE 12.5. Conductivities of PMOMA and PDOMA conducting polymer films as a function
of electrode potential. (From d' Aprano and Leclerc. 39 Reproduced by permission of The Electro-
chemical Society, Inc.)
1.0.-------...,-----.-----,------,------,
PMOMA
::J
d
...... ................
w .....
u
Z
<t
m
a::
o
(/)
m
<t
electro activity region is about 0.4 V, but the two regions (peak-to-peak) are
separated by 2.6 V. In a two-electrode system, this allows one region to be
worked against the other with a wide redox pseudocapacitance charge ex-
change, i.e., with a capacitor operating over half of the 2.6-V range given above.
The current response behavior in cyclic voltarnmetry is better than that for
poly thiophene itself (formula 1) which also, however, exhibits two separate re-
gions of positive or negative charge accommodation.
~ s y
The forms of the voltammograms are reminiscent of those for the polycy-
clic hydrocarbon, rubrene, in acetonitrile, oxidized and reduced at a Pt elec-
trode. However, no polymer film is formed in that case, but the neutral molecule
can be either reduced to a carbanion radical (-) or to a carbonium ion radical (+)
in a diffusion-controlled process. The anion and cation radicals recombine in the
diffusion layer with the emission of red light43 (electrochemiluminesence).
The behavior of the poly thiophene system is different from that of PAN!.
The latter can be oxidized to a p-type polycation (with associated co-anions) but
on re-reduction reverts to a relatively less conducting neutral state which limits
the power achievable with this material as a (pseudo )capacitor electrode. fn the
case especially of the fluorophenyl derivative, 3, of thiophene, the polymer ex-
hibits both oxidizability and reducibility (n-doping) so there are two potential
ranges of electroactivity (Fig. 12.7). Thus in the fully charged state of a two-
electrode capacitor made with this material, a total voltage drop of about 3.0 V
across the cell can be achieved. This corresponds to maximum positive charge
injection into the positive electrode and maximum negative charge into the
negative plate. Corresponding co-anion and co-cation insertion adjustments into
the polymer interphases take place to achieve local charge balance as in the
charging of the double layer at a metal/electrolyte interface. Thus a
quasi-I-dimensional double layer tends to be set up locally along the
polymer chains, though the latter are not linear for en tropic reasons, as
with any polymer in solution except stretched rubber.
It should be mentioned that the discharge of such a capacitor device based
on polythiophenes means that the excess electron (and counterion) charge on
each plate is brought down to zero, but in this case a potential difference of about
2.0 V remains between the plates (Fig. 12.7) rather than zero V, as would be the
Capacitance Behavior of Polymer Films 319
-'-' -,- -
60
- - - Me4 NCF3 SO"3
- -- - - BU 4 NPF6
40
zo
<l:
E
'- 0
r-
z
w
0: -20
0:
::>
U -40
25 mV/s
-6.0
case with a PANI Type I capacitor (Fig. 12.8 and section 12.5). This is because,
with the poly thiophene material, high charge capacity with reversible charge in-
jection is associated with only about 0.5 V at each of the extreme ends of the
negative and positive potentials of the overall 3.0-V range (Fig. 12.7) of the vol-
tammogram of the active material. This is an advantage in that all of the charge
(a) (b)
~Vl-:
, i i
v
FIGURE 12.8. (a) Schematic representation of half-cycle charge and discharge operation of a
Type I combination of polymer electrodes making an electrochemical capacitor, (b) The decline of
potential, V, with time or charge, Q, on discharge. Reprinted from Rudge et aI., 1. Power Sources,
47, 89 (1994), with permission from Elsevier Science.
320 Chapter 12
(a) (b)
""'-I----V2- ---:
I
v
--'""'----::-t-+----;-.. V &t
,.I Q 2 ,,~-):
L.----~--7-- 0 &t
• I 01
\ I
,,'
FIGURE 12.9. As in Fig. 12.8 but for the Type II capacitor electrodes. Reprinted from Rudge et
a!., 1. Power Sources, 47, 89 (1994), with permission from Elsevier Science.
Capacitance Behavior of Polymer Films 321
(a) (b)
:--VO~ V
i I ! Va
\ I
'''I .. ' Oa
FIGURE 12.10. As in Figs, 12,8 and 12,9, but for the two-region, Type III electroactivity shown
in Fig, 12.7. Reprinted from Rudge et aI., 1. Power Sources, 47,89 (1994), with permission from
Elsevier Science.
TABLE 12.1. Charge and Energy Density Obtained in Experiments on the Three
Schemes for the Application of Conducting Polymers to Electrochemical Capacitors
Source: Reprinted from Rudge et aI., J. Power Sources, 47, 89 (1994), with permission from Elsevier Science.
"Type I: polypyrrole; Type II: polypyrrole end poly thiophene; Type III: functionalized poly thiophene:
poly-3.(4-f1uorophenyl) thiophene.
bCharge and energy densities calculated per geometric square centimeter of the carbon paper electrodes,
<Charge and energy densities calculated per gram of active material on both electrodes in the capacitor
configuration. This does not therefore include the mass of the carbon paper support material.
322 Chapter 12
terials-design viewpoint and from the stored energy density that is achievable
with the higher operating voltage that is obtained. Some performance data ob-
tained in this work for the three types of polymer capacitor systems are shown
in Table 12.1.
Most of the electroactive polymer systems exhibit a nonconstant pseudo-
capacitance, namely, a current-response curve in cyclic voltarnmetry that exhib-
its a maximum or several maxima. This behavior is in contrast to that of Ru02'
the voltammogram for which approaches the ideal rectangular shape expected
for a regular capacitor, i.e., it exhibits almost constant pseudocapacitance over
a 1.4-V range, as illustrated earlier (Chapter 11).
FIGURE 12.11. Scanning electron micrograph of fibrous carbon paper matrix for growth of con-
ducting polymer films. Reprinted from Rudge et ai., 1. Power Sources. 47.89 (1994). with permis-
sion from Elsevier Science.
Capacitance Behavior of Polymer Films 323
~~ O.52V
_ _----~OV
-4~--~----~----~--------~--~
4
FIGURE 12.13. Simulated (upper curves) and experimental (lower curves) relations between the
ellipsometric parameters ".!l "'I'
and for conversion of a polyaniline film on Pt in 2 M Hel at a 50-
mV s-I scan rate at 500 nm and a 60° incidence angle, between 0 and 0.52 V. The simulated curves
correspond to three conversion modes A, B. and C. (From Gottesfeld. Redondo. and Feldburg. 12
Reproduced by permission of The Electrochemical Society. Inc.)
Capacitance Behavior of Polymer Films 325
tive index (n) and optical absorption coefficient (K) of the film, usually by
means of computer fitting or simulation procedures. Since the electrochemi-
cally formed polymer films are usually nonuniform, theoretical difficulties arise
in making a rigorous analysis of the optical data. However, the progressive con-
version of the films on potential cycling can be easily followed, as was shown
in the detailed work by Bard et al.,47,48 represented in the plots of Fig. 12.14.
This investigation of propagation directions (during film conversion) by means
of ellipsometry was first described for conducting polymers in Ref. 12 (Fig.
12.13).
In the EQCM method, the resonant frequency of an electrically driven, lon-
gitudinally vibrating, piezoelectric quartz crystal (covered by a thin, conducting
metal film of Pt or Au) is measured, and the changes in frequency (lowering)
due to development of a film, or to adsorption of ions or molecules, are re-
corded. This system detects the nanogram sensitivities at weight changes caused
by film formation, so that growth of very thin films can be followed 14,25 in situ
by means of cyclic voltammetry.
The SEM pictures of the polymer films (Fig. 12.12) showed growth of the
polymer around individual fibers of a carbon fiber substrate, and microscopic
inspection at increasing levels of magnification revealed self-similar structures
of the film down to very small dimensions, i.e., the film growth was essentially
fractal, at least in a qualitative way. Because of this nonuniformity of the poly-
mer deposits, theoretical difficulties can arise in interpreting the ellipsometric
parameters experimentally evaluated, as Dignam49 has shown for the effects of
roughness of surfaces.
In the case where the polymer films are of interest for electrochemical ca-
pacitor development, the use of EQCM and ellipsometry techniques by Rudge
et al. 14 provides an important in situ way of following the growth of the films
·-OXIDIZED
v-REDUCEDINEUTRAL)
40 100
30
1Jt0 - - -'00-- --- " 0 . _ ... ,
........... ,
20
0
,
____ ______________ L - - - . l'
10
0
60 80 100 120 140 160 180
f:j,0
FIGURE 12.14. Overlying ellipsometry plots for continuing growth of polyvinylferrocene films.
(From Carlin, Kepley, and Bard. 47 Reproduced by permission of The Electrochemical Society, Inc.)
326 Chapter 12
significantly over the potential range for which polypyrrole is highly conduct-
ing (0.44 to 0.84 V, RHE). The space charge capacity was constant from 0.74
to 0.54 V but became reduced as potential was lowered to 0.34 V. It appears that
as the potential is reduced toward the supposed redox potential (0.34 V, RHE)
of the film, the structure of the interphase begins to change from that of a mixed
metal semiconductor to that of a semiconductor.
Using the results for polypyrrole perchlorate, it was shown that a Mott-
Schottky relation could be constructed by plotting the inverse square of the
space charge capacitance against the potential; this gave a flat-band potential of
-0.23 V (RHE). The slope of the plot was negative, as expected for a p-type
semiconductor.
The best fit of the impedance behavior to various equivalent circuits re-
quired a constant-phase element corresponding to a value of the a-exponent
[a = (D - It' where D is the fractal dimension of the roughness] equal to
0.53, which gave D = 2.89 for the fractal-represented surface. This corre-
sponds to a material having an interface with a significantly 3-dimensionally
distributed surface, as concluded by Gottesfeld" from his SEM images (Fig.
12.12) of poly thiophene films on carbon fibers.
propagation of the conversion process will be uniform within the film volume.
Taking r as a typical duration of electrochemical perturbation, d as a film thick-
ness, and P as the dominant resistivity, the above conditions correspond to r >
pdC where C is the electrical capacitance per unit cross-sectional area of the
film associated with the charging process.
Mode B: This arises when p for electronic resistivity is much less than the
ionic resistivity. Then the film conversion process propagates as a front moving
from the film/electrolyte interface toward the substrate/film interface. The con-
dition r < Pion dC then applies.
Mode C: This is for the condition when the ionic resistivity is negligible
compared with the electronic resistivity, i.e., for the condition r < Pelect de. Then
the propagation front moves in a direction opposite to that in mode B.
Mode D: A fourth mode arises for directional propagation of film conver-
sion as in modes B or C, but with graded film oxidation or reduction along the
thickness direction as determined by diffusion from the leading interface into
the volume of the film.
Ib in'·'" tJ
U film thickness
arlier
part of
conversion
tsr
t
Bth ..
iddle
port of
conversion
D
1
FIGURE 12.15. Schematic representation of modes 1, 2, and 4 for conducting polymer propaga-
tion (as defined by Lee, Kwok, and Bard48 ) during film growth.
36
-200 31
-
N
::r: ~r \fir
'-
<J -400 110 26
21
tis
FIGURE 12.16. Simultaneously obtained optical (ellipsometric) and gravimetric (EQCM) results
for growth of poly aniline film. Reprinted from Rishpon et aI., J. Electroanal. Chern., 294, 73 (1990),
with permission from Elsevier Science.
47
SOLID CURVE:
~_ _ _'4..;;i,",,·7o...- A. 1.51 - 0.01 i
44
41
If
38
35
FIGURE 12.17. Experimental (points) and simulated (solid line) li vs. IjI plots for galvanostatic
film growth of poly aniline at a current-density of 77 flA cm-2 (potential = 0.50 V vs. SCE). Re-
printed from Rishpon et aI., J. Electroanal. Chern., 294, 73 (1990), with permission from Elsevier
Science.
Capacitance Behavior of Polymer Films 331
1Zoor------.-------r------,-------.---__~
960
720
./
Af/Hz
"0/
480
0·~----~~~-----7.60~----~9~0------~12~O----~1~
OPTICAL THICKNESS; nm
FIGURE 12.18. EQCM results for polyaniline film growth scaling linearly with the ellipsomet-
ricall y determined film thickness values. Reprinted from Rishpon et aI., J. Electroanal. Chern., 294,
73 (1990), with permission from Elsevier Science.
REFERENCES
1. R. B. Kaner and A. G. MacDiarmid, 1. Chem. Soc., Faraday Trans., 1,80,2109 (1984).
2. R. B. Kaner and A. G. MacDiarmid, Synth. Metals, 14, 3 (1986).
3. A. G. MacDiarmid, R. B. Kaner, R. 1. Mammone, and A. 1. Heeger, 1. Electrochem. Soc., 128,
1651 (1981).
4. K. Kaneto, M. Maxfield, D. P. Nairns, and A. G. MacDiarmid, 1. Chem Soc., Faraday Trans.,
1,78,3417 (1982).
5. T. Kobayashi, H. Yoneyama, and H. Tamura,l. Electroanal. Chem., 177,281 (1984); 177,
281 (1984) and 161, 419 (1984).
6. M. Ghoiamian, J. Sundaram, and A. Q. Contractor, Langmuir, 3, 741 (1987).
7. H. Letheby, 1. Chem. Soc .• London, 15, 161 (1862).
8. J. Schmidt, Organic Chemistry, trans. by H. Gordon Rule, p. 782. Gurney and Jackson,
London (1943).
9. E. M. Genies, A. Boyle, M. Lapkowski, and C. Tsintavis, Synth. Metals, 36, 139 (1990); see
also 1. Electroanal. Chem., 195, 109 (1985).
10. B. E. Conway in Proc. 34th Intl. Power Sources Symposium, p. 319, Catalog no. 90CH 2863-9,
Institute of Electrical and Electronics Engineers. New York (1990).
11. S. Gottesfeld, in Proc. First Int!. Seminar on Double-Layer Capacitors and Similar Energy
Storage Devices, S. P. Wolsky and N. Marincic, eds. Florida Educational Seminars, Boca
Raton, Fla. (1991).
12. S. Gottesfeld. A. Redondo. and S. W. Feldberg. 1. Electrochem. Soc., 134, 271 (1987).
13. A. Rudge, I. Raistrick. S. Gottesfeld, and 1. P. Ferraris, Electrochem. Soc., 39, 273 (1994); and
Electrochim. Acta, 39, 273 (1994).
14. A. Rudge, J. Davey, I. Raistrick. and S. Gottesfeld, 1. Power Sources. 47,89 (1994).
15. J. O'M. Bockris and D. Miller, in Conducting Polymers: Special Applications, Proc.
Workshop, L. Alcacer, ed., D. Reidel, Boston, Mass. (1987).
16. Z. Jiang, X. Zhang, and Y. Xiang, 1. Electroanal. Chem., 351, 321 (1993).
17. Z. Jiang, Y. Xiang, and J. Wang, 1. Electroanal. Chem., 316,199 (1991).
18. D. E. Stilwell and S.-M. Park, 1. Electrochem. Soc., 135, 2491, 2497 (1988).
Capacitance Behavior of Polymer Films 333
19. Y.-B. Shim, M.-S. Won, and S.-M. Park, 1. Electrochem. Soc., 137, 538 (1990).
20. C. D. Batich, H. A. Laitinen, and H. C. Zhou, 1. Electrochem. Soc., 137, 883 (1990).
21. H. Weiss, O. Pfefferkorn, G. Kotora, andB. D. Humphrey,!. Electrochem. Soc., 136,3711 (1989).
22. T. Ohsaka, Y. Ohnuki, N. Oyama, G. Katagiri, and K. Karnisako, 1. Electroanal. Chem., 161,
399 (1984).
23. M. A. Habib and S. P. Maheswari, 1. Electrochem. Soc., 136, 1050 (1989).
24. N. S. Sariciftci, H. Kuzmany, H. Neugebauer, and A. Neckel, 1. Chem. Phys., 92,4530
(1990).
25. J. Rishpon, A. Redondo, C. Derouin, and S. Gottesfeld, 1. Electroanal. Chem., 294, 73
(1990).
26. H. Mao and P. G. Pickup, 1. Am. Chem. Soc., 112,1776 (1990).
27. X. Ren and P. G. Pickup, 1. Phys. Chem., 97, 5356 (1993).
28. H. Mao and P. G. Pickup, 1. Chem. Soc., 1. Phys. Chem., 96, 5604 (1992).
29. Z. S. Zhao and P. G. Pickup, 1. Chem. Soc., Faraday Trans., 90, 3097 (1994).
30. X. Ren, S. K. Mandai, and P. G. Pickup, 1. Electroanal. Chem., 389, 115 (1995).
31. I. H. Jenkins and P. G. Pickup, Macromolecules, 26, 4450 (1993).
32. X. Ren and P. G. Pickup, 1. Electroanal. Chem., 396, 359 (1995).
33. A. R. Hillman and E. F. Mallen, 1. Electroanai. Chem., 220, 351 (1987).
34. F. B. Li and W. J. Albery, Langmuir, 8, 1645 (1992).
35. F. B. Li and W. 1. Albery, Electrochim. Acta, 37, 393, (1992).
36. B. E. Conway, in Proc. Third IntI. Seminar on Double-Layer Capacitors and Similar Energy
Storage Devices, S. P. Wolsky and N. Marincic, eds., paper no. I, Florida Educational
Seminars, Boca Raton, Fla. (1993).
37. B. E. Conway and L. Duic, Report to Continental Group Inc., on supercapacitor research and
development, July (1978).
38. A. A. Syed and M. Dimesan, Talanta, 38, 815 (1991).
39. G. D' Aprano and M. Leclerc, 1. Electroanal. Chem., 351, 145 (1993).
40. B. E. Conway in Proc. Symposium on Electrochemical Capacitors, F. M. Delnick and
Tomkiewicz, eds., 95-29, 15, Electrochemical Society, Pennington, N.J. (1996).
41. Gu Ping and B. E. Conway, (in press) 1999.
42. X. Ren, J. Davey, A. Rudge, 1. Ferraris, and S. Gottesfeld, in Proc. Fourth IntI. Seminar on
Double-Layer Capacitors and Similar Energy Storage Devices, S. P. Wolsky and N. Marincic,
eds., Florida Educational Seminars, Boca Raton, Fla. (1994).
43. B. E. Conway and A. Pighin, 1. Electrochem. Soc., 122, 5 (1975).
44. B. E. Conway, in Techniques oj Electrochemistry, E. Yeager and A. 1. Salkind, eds., Chapter
5, Wiley, New York (1972).
45. M. Born and E. Wolf, Principles ojOptics, Macmillan, New York (1964).
46. S. Gottesfeld, Y-T. Kim, and A. Redondo, in Physical Electrochemistry, I. Rubinstein, ed.,
Chapter 9, Marcel Dekker, New York (1995).
47. C. M. Carlin, L. J. Kepley, and A. 1. Bard, 1. Electrochem. Soc., 132, 353 (1985).
48. C. Lee, 1. Kwok, and A. 1. Bard, 1. Electrochem. Soc., 136, 3720 (1989).
49. M. 1. Dignam, 1. Chem. Soc., Faraday Trans., 69, 65 (1973).
50. D. L. Miller and 1. O'M. Bockris, 1. Electrochem. Soc., 139, 967 (1992).
51. E. Buhks and I. M. Hodge, 1. Chem. Phys., 83, 5976 (1985).
52. 1. C. Clayton and D. J. DeSmet, 1. Electrochem. Soc., 123,174 (1976); see also Electrochim.
Acta, 21, 1137 (1976).
53. A. Rudge, J. Davey, F. Uribe, 1. Landeros, and S. Gottesfeld, in Proc. Third IntI. Seminar on
Double-Layer Capacitors and Similar Energy Storage Devices, S. P. Wolsky and N. Marincic,
eds., Florida Educational Seminars, Boca Raton, Fla. (1993).
334 Chapter 12
54. D. Finello, D. Harrison, and R. K. Bunting, in Proc. Second Inti. Seminar on Double-Layer
Capacitors and Similar Energy Storage Devices, S. P. Wolsky and N. Matincic, eds., Florida
Educational Seminars, Boca Raton, Fla. (1992).
55. K. Sugimoto, as in Ref. 57.
1. P. Novak, K. Muller, K. S. V. Santhanam, and O. Haas, Chern. Rev., 97, 207 (1997).
2. W. J. Albery and R. Hillman, Reports of the Chemical Society, London, C (1980).
Chapter 13
13.1. INTRODUCTION
For regular electrical capacitors, high power densities are achievable ow-
ing to the usually low equivalent series resistance and corresponding phase an-
gles near 90 0 • This is one of the reasons for the interest and practical
development of high-capacity capacitors in recent years,l,2 including those for
so-called "star wars" applications and for hybrid power supplies for electric ve-
hicles.
The properties of the electrolyte-solution system, solvent plus solute salt,
required for electrochemical capacitors determine their electrical behavior in
three ways: The first is in a primary manner by determining the conductance of
the electrolyte of the device and its equivalent series resistance (esr), and thus
335
336 Chapter 13
its power output capability. The second is through anion adsorption from the
electrolyte, determining in part the specific double-layer capacitance, especially
at potentials positive to the potential-of-zero charge of the carbon electrode ma-
terial employed. The third is through the dielectric properties of the solvent,
which also determine the specific double-layer capacitance value and its de-
pendence on electrode potential, as well as the extent of ionization or ion pairing
of the solute salt, which influences the conductance.
In Chapters 1 and 2 it was shown how two types of supercapacitors have
been developed in recent years: one based on the large double-layer capacitance
developed at high-area porous or powdered carbon matrices! invaded by a suit-
able electrolyte and the other based on utilization of the large pseudocapaci-
tance2 ,3 associated with underpotential deposition, electrosorption processes
(e.g., H on Pt, Pb on Au), or with redox processes at high-area, porous conduct-
ing oxide materials [e.g., RuOz, Ir02 (in acid), or Co0 2 (in alkali)], as treated in
Chapter 10. Both types require high conductivity of their respective electrolytes
to deliver optimum power (see Chapter 15).
In order for highly reversible charge and discharge processes to take place
at high rates (giving rise to higher power operation), the internal electrolyte and
structural resistance of such porous, high-area materials must be minimized;
otherwise the principal desirable feature [expectation (2)] of capacitative fast
charging or discharging would be lost or seriously attenuated. Put in other terms
of impedance response, the phase angle of the impedance behavior should be as
near as possible to 90 0 at all frequencies-a rather idealized requirement in
practice, especially for porous electrode structures (see Chapter 14).
One of the principal factors determining the power spectrum (i.e., the
availability of power withdrawn over various time domains or in various fre-
quency ranges) of porous electrode supercapacitors is therefore the resistivity of
the electrolyte, R e , in the pores and the extent of its physical contact with the
maximum accessible area of the pores of the matrix. In addition, minimum con-
tact resistance, Reo between particles of the electrode structure is desirable. The
latter is a function of the materials used in the electrode. Diminution of contact
resistance can be achieved with compression of the matrix, but this usually di-
minishes the volume fraction of electrolyte, resulting in a relative increase of
Re. An optimized combination must be achieved.
In this chapter, the properties of solutions of electrolytes and their role in
the equivalent circuit of porous electrode supercapacitor systems is examined,
In addition to aqueous acid and alkaline solutions for low-voltage aqueous su-
percapacitors, some nonaqueous electrolyte systems that are available for ca-
pacitors operating at rather higher voltages (e.g., 3.5 to 4.0 V) will be
considered. For the latter purposes, some of the electrolyte solutions or solvents
available for Li battery technology are applicable, with substitution of Li salts
by tetraalkylarnmonium ones. We examine first some fundamental factors that
The Electrolyte Factor In Supercapacitor Design 337
determine the conductance of electrolytes because this determines the esr of po-
rous electrode systems used for capacitor devices.
The two principal factors involved in conductance are (1) the concentra-
tion of free charge carriers, cations, and anions of a gi ven salt or acid solute; and
(2) the ionic mobilities, or conductance contributions per ion, of the dissociated
ions of the electrolyte solute.
The factors that in turn determine (1) and (2) are (3) the solubility of the
salt in the solvent of choice; and (4) the degree of dissociation, a, of the dis-
solved salt "molecules" into free ions, or conversely, the extent of cation-anion
association or pairing of the ions of the dissolved salt or acid. Three stages of
ion pairing, depending on the extent of retention of solvation, are illustrated in
Figs. 13.l(a), 13.1(b), and 13.1(c).
FIGURE 13.1. Types of ion pairs in an electrolyte solution: (a) solvated-ion pairs, (b) solvent-
shared ion pairs, and (c) contact ion pairs.
338 Chapter 13
MA (13.1)
(1 - a)c ac ac
The Electrolyte Factor in Supercapacitor Design 339
(13.2)
where 0 < a < 1 and activity coefficients have been taken as unity. For many
salts and acids in water, a ~ 1 (strong electrolytes) except toward the limit of
solubility of very soluble salts. However, it is important (in a negative way) that
for nonaqueous, high operating voltage (3.5-4.0 V) supercapacitors, the extents
of dissociation of many salts are substantially less than lowing to ion associa-
tion (weak electrolytes). The association is often between partially solvated
ions, leading to a species referred to as "solvent-shared ion pairs" (see Fig.
13. 1(b»).
where m and n can be less than the respective solvation numbers for the free in-
dividual solvated ions. 4 The total concentration of salt and dissociated ions de-
pends on the solubility (see later discussion). When the species in Eq. (13.3) are
extensively formed, especially in low dielectric constant solvents, free ions are
withdrawn from their charge-conducting role, so both K and A decrease.
For weakly dissociated salts or acids in poor solvents, the A value is mainly
determined by K and a in Eq. (13.2) for process (13.1) or related equilibria. In
fact (according to Arrhenius), Ac is then determined almost entirely by the dis-
sociation, and A/Ao = a where Ao (or A~) (> Ac) is the equivalent conductivity
at infinite dilution, lim(Klzc) as c ~ 0 (see Table 13.1 for aqueous Hel and ace-
tic acids as examples).
Substitution of a in Eq. (13.2) by A/Ao leads to Ostwald's dilution law by
which the applicability of the Arrhenius relation for a in Eq. (13.2) can be tested
in various ways for weak electrolytes. Such plots give distinguishable relations
for weak and strong electrolytes (Fig. 13.2) where, for the latter, the Arrhenius
equation, a = A/Ao, does not apply.
For the solutions employed as electrolytes for nonaqueous solvent double-
layer capacitors, there is significant weak electrolyte behavior so that a is ap-
preciably less than its value, which is near 1 in aqueous solutions. This usually
leads to larger esr values for nonaqueous solution devices than for aqueous ones
using the same electrode materials and cell geometries. Also the Ao values are
usually different.
In strongly dissociating solvents such as water, Kc is relatively large
and a ~ 1, so that the concentration of species (13.3) is small. However,
Ac is still found to progressively decrease with c in relation to Ao for infinite
dilution. This is due to the long-range electrostatic attractions between the
340 Chapter 13
free,dissociated ions (it also occurs with the ions arising from weakly dissoci-
ated salts, but the effect on A is much less than that due to small K or Iowa),
which also depends on the dielectric constant, e, of the solvent. Up to moderate
concentrations, Ac decreases with the square root of c, an effect treated in the
well-known theory of Debye and Huckel (1923), and later by Onsager (1926).
The different effects of an increasing concentration of a dissolved salt or
acid on equivalent conductivity in the case of weakly dissociated (or ion paired)
electrolytes compared with strongly dissociated salts for which long-range in-
teractions are more important are illustrated in Fig. 13.2 and are usually easily
distinguishable experimentally. Intermediate cases, of course, arise.
___ A
~""
, CD
, \,
,, '
,,
,
FIGURE 13.2. Comparative conductivity behavior of a strongly and a weakly dissociated (or ion-
paired) electrolyte as a function of concentration (schematic).
The Electrolyte Factor in Supercapacitor Design 341
and/or associated poor wettability, i.e., unsuitable contact angles between the
molten electrolytes and elements of the carbon surface.
(13.5)
where Zl and Z2 are the charge numbers for the ions. U is an attractive energy,
tending to diminish interionic free motion when Zl and Z2 are opposite in sign.
Equation (13.5) applies especially to long-range interactions as treated in the
theory of Debye and Huckel (1923).
When x becomes comparable or equal to the sum of the ionic radii or
solvated-ion radii ri,s (Eq. 13.4), an ion-paired situation, (Eq. 13.3), arises and
the energy U is then
The Electrolyte Factor in Supercapacitor Design 345
(13.6)
When the (negative) energy U in the above equation is > or > > kT, the ex-
tent of ion pairing is substantial (a« 1). Similarly, a usually increases with a
rise in temperature, leading to improved conductance. This of course is a com-
mon problem with supercapacitors and batteries, i.e., their internal resistance in-
creases at lower temperatures and their power delivery capability (Chapter 15)
becomes substantially diminished.
In some cases (Fig. 13.1), when solvated ions are paired their solvation
shells become shared (a case of solvent-shared ion pairs), so that x <
r;,s,+ + r;,s,_. In poorly solvating solvents, the plus and minus ions come into a
contact situation [Fig. 13.1(c)] (contact ion pairs, Fuoss). Then, the maximum
plus/minus interaction arises electrostatically but is counterbalanced by a sub-
stantialloss of solvation energy of the two ions.
In these close-encounter situations, which lead to diminution of the con-
ductance of an electrolyte, the normal value of B for the solvent becomes inap-
plicable and a lower local value due to dielectric saturation should be used for
the region between and near the ions. Thus ion-pairing equilibrium constants for
an electrolyte in various solvents do not follow simply a liB relation although
there is often a general qualitative trend. For example, three solvents having the
same nominal B (=20) (e.g., acetic anhydride, n-butyronitrile, and trimethyl-
phosphate) can exhibit quite different ion-pairing effects for a given electrolyte
solute, with consequent substantial differences between the Ac vs. cor c I12 rela-
tions, the latter corresponding to the behavior of fully dissociated electrolytes
(Debye-Hiickel effect).
However, for the short-range interaction effects involved in ion pairing, it
is often the lone-pair electron donicity that is more significant than the B (Table
13.5). In the cases of the three solvents above, the respective donicity numbers
are quite different, namely, 10.5, 16.6, and 23 in a range of 0 (reference) to 38.8
for a variety of solvents (Table 13.5).
The ion pairing in various solvents can be quantitatively characterized by
infrared, Raman, and NMR spectroscopies, often in a specific way.4,II,I2 A sum-
mary of factors determining electrolyte conductance is given in Table 13.6.
Solvent DN e
1,2-Dichloroethane (ref. solvent) 10.1
Sulfuryl chloride 0.1 10.0
Thionyl chloride 0.4 9.2
Acetyl chloride 0.7 15.8
Tetrachloroethylene carbonate 0.8 9.2
Benzyl chloride 2.3 23.0
Nitromethane (NM) 2.7 35.9
Dichloroethylene carbonate (DEC) 3.2 31.6
Nitrobenzene (NB) 4.4 34.8
Aceticanhydride (AA) 10.5 20.7
Phosphorus oxychloride 11.7 14.0
Benzonitrile (BN) 11.9 25.2
Selenium oxychloride 12.2 46.0
Acetonitrile (AN) 14.1 38.0
Sulfolane (TMS) 14.8 42.0
Propanediol-l,2-carbonate (PDe or PC) 15.1 69.0
Benzylcyanide (nitrile) 15.1 18.4
Ethylene sulfite (ES) 15.3 41.0
iso-Butyronitrile 15.4 20.4
Propionitrile 16.1 27.7
Ethylene carbonate (EC) 16.4 89.1
Phenylphosphonic difluoride 16.4 27.9
Methylacetate 16.5 6.7
y-Butryronitrile 16.6 20.3
Acetone 17.0 20.7
Ethyl acetate (ETAC) 17.1 6.0
Water 18.0 81.0
Phenylphosphonic dichloride 18.5 26.0
Diethyl ether 19.2 4.3
Tetrahydrofuran (THF) 20.0 7.6
Diphenylphosphonic chloride 22.4
Trimethylphosphate (TMP) 23.0 20.6
Tributylphosphate (TMP) 23.7 6.8
Dimethylformamide (DMF) 26.6 36.1
N,N-Dimethylacetamide (DMA) 27.8 38.9
Dimethylsulfoxide (DMSO) 29.8 45.0
N,N-Diethylformamide 30.9
N,N-Diethylacetamide 32.2
Pyridine (PY) 33.1 12.3
Hexamethylphosphoramide (HMPA) 38.8 30.0
Hydrazine 44
Ethylenediamine 55
Ethylamine 55.5
t-Butylamine 57.0
Ammonia 59.0
Trithylamine 61.0
(a)
liquid
pore Cdl
electrolyte
(b)
FIGURE 13.3. (a) Transmission-line model (Chapter 14) for a single pore. Re and Rs are the oh-
Z,
mic resistance of the electrolyte and the solid electrode material, respectively, is the electrode
Faradaic impedance and Cdl is the double-layer capacitance. (b) When RI = Rs = 0, the equivalent
circuit in (a) becomes simplified to that shown as (b). (See Chapters 14 and 16).
From various works it appears that the best nonaqueous electrolyte for
higher voltage electrochemical capacitors is Et4NBF4, 1 M, in propylene car-
bonate, possibly mixed with dimethoxyethane to improve (lower) its viscosity
and thus raise ionic mobilities. The above solution has a specific conductance
of 13 mS em-I.
1
-,
°
+3 +2 +' -2 -3
Aqueous
\------111.11 H,SO,(Pt)
p, { I - - - - - - - l i pH 7 Buffer IPII
! - - - - - - - ; I ' .II N.OHIP'I
\-_ _ _---;1' .II H,SO,lHgl
~{ rl- - - - - - - ( 1 1 . 1 1 KCllHgi
I r - - - - - - - - I I ' .II NaOHIHgl
) - - - - - - - - - ; 1 0 , ' .II Et,NOHIHgl
)--------lI'.M
1 HCIO,ICI
C{
) - - - - - - - - - - 1 1 0,' .II KCIICI
Nonaqueous MoeN
p, 1 - - - - - - - - - - - - - - - - - - - ; 1 0,' .II TBABF.
I - - - - - - - - - - - - - - - - - l i ~,~~l TBAP
\----------------11 Senzonitrile
O".If TBABF. THF
\ -_ _\---------------...,1
_ _ _ _ _ _ _ _ _ _ _ _---;1 PC 0,' AI TBAP
CH,CI, O.lA.TEAP
\--------------;1 0,',01 TBAP
1------------11 ~~'M TBAP
)-------------ll ~,~'.w KI
u +3 +2 ., -, -2 -3
1
....----- ,
W V- i.(dl)- V+ , / POTENTIAL
~
~ ~------
::) 1 I
U
U : 1 ..
"C
o
.c
I I FARADAIC
c; : : DECOMPOSITION
3 ~I·------------~·I
: IDEAL POLARIZABILITY RANGEl
-FA-R-A-O--i.
....
·I-C-- 1 :
OECOMPOSITION:
FIGURE 13.4. Estimated potential ranges (decomposition limits) for aqueous and nonaqueous
electrolyte solutions. (From A. 1. Bard and L. R. Faulkner, Electrochemical Methods, Wiley, New
York (1980). Reprinted by permission of John Wiley & Sons.) The lower curves illustrate decom-
position limits, V+ and V-, in a cyclic yoltammetry experiment; i(dl) = double-layer charging cur-
rents and iF-Faradaic decomposition currents.
Other factors are the ionic radii of the solute salt ions and the magnitudes
of their charges, often ± Ie, which the determine strengths of solvation and of
ion pairing or degrees of dissociation of the solute salt. A summary of the vari-
ous properties involved is given in Table 13.9.
All these factors are involved in determining the two leading quantities that
determine specific conductance at a given concentration, namely, (1) the mobil-
ity of the dissociated ions and (2) the concentrations of free charge carriers, the
cations and anions, at the experimental salt concentration. A further factor that
determines optimization of solution properties for electrochemical capacitors is
the temperature coefficient of specific conductance, which is determined by the
temperature coefficients of factors (2) to (5) in a complex, interactive way.
A number of relevant properties of nonaqueous solutions have recently
been considered in a comparative way, with tabulations of data, by Barthel and
Gores 18 in their useful article on solution chemistry. Various improvements to
the properties of a nonaqueous solvent for electrolyte solutions can be achieved
by mixing it with one or more other polar aprotic solvents (e.g., di-
methoxyethane) since the mixture properties of binary or ternary mixed-solvent
systems are rarely additive in proportion to the mole fractions of the compo-
nents, nor are they usually predictable. 4 Overall, the two main factors for opti-
mization of the electrochemical performance of double-layer-type capacitors
are good electrolytic conductance and the widest voltage range of electrochemi-
cal stability.
Some tabulations of selected data taken from the articles by Barthel and
Gores 13 ,18 are reproduced, with permission, in the appendix to this chapter.
Readers are also referred to the very large computer-accessible databank
(ELDAR) on electrolyte solution properties that has been assembled by Barthel
and his associates at the University of Regensburg, Germany. The description
of this databank has recently been published. 19
354 Chapter 13
li K Zn Cd AgCI Cu Ag
- -+ +- - - - - - - - - - -1- -I -'It- - "t ~ - 1" -
_~i~ ___________~~.sj~A~~ __ ~g_
-~~---------- - ~x~--~-~----
_ ~i~___________ -~-~_)t-A9SJ.f~ -f!-
_.!:+~ __________ ~,n_~~u__~ ___ _
Li K
--t- -t- - -------------t--
MCI Ag
--+
AgCI Ag
----------------~-~--+- DMSQ
-3 -2 -1 6
POTENTIAL I V vs H2 /H+
SCHEME 1. Potential scales for several solvents, using the hydrogen electrode in the given sol-
vent as the conventional reference electrode. The point of zero charge of mercury in the absence of
specific adsorption is marked as a cross. Reprinted from R. Parsons, Electrochim. Acta, 21, 681
(1976), with permission from Elsevier Science.
whatever solute ions are within it) is a quantity of prime importance because it
determines the theoretical and often practical voltage range over which the de-
vice can be operated. The practical operating range can usually exceed the ther-
modynamic decomposition limit if substantial overvoltages at the cathode (e.g.,
Hg) or anode (e.g., Pb0 2) arise in aqueous solutions, or for processes in
nonaqueous media.
Reduction potentials
I I
SCHEME 2. Reduction potentials of redox systems in water versus nhe(aqueous) and in acetoni-
trile vs. normal H2 electrode (acetonitrile). Reprinted from A. 1. Parker, Electrochim. Acta, 21, 671
(1976), with permission from Elsevier Science.
356 Chapter 13
CI Rb K Ag Li
--+++ - - - ---t--+ - H20
CI Rb K Ag Li
-;----+ +------+-+- - CH 30H
CI RbK AgLi
- -+ - -t;- - - - - - - f t - - -HCOOH
CI Rb K
--+--t+ -? HCONH 2
CI Rb K Li Ag
-t----++ - - - - --++- - CH 3CN
CI
-1--- DMF
CI Ag
-r- - - - - - - - - - - -1- ? DMSO
CI Rb K Ag Li
-+ ----1-1- - - - - - I - -1-- -(CH 3 )ZCO
I I
2 3 6
--+----
H _ -Sd____ _Zt_1~_
H Cd Zn Cu
---f- - --+---+-+
H Cd Zn
-1----- ---I----f--
H Cd Zn Cu
- --1-- --I- -----I-I-
H Cd Zn Cu
--1---- --+----1----1-
H
------1- DMSO
H
----+--
I I
1\ 12 18 20 22
a~ leV al/eV
SCHEME 3. Real solvation energies of some common ions in various solvents. The lengths of
the arrows indicate schematically the probable contribution of the oriented solvent dipole at the sur-
face to the real solvation energy of a monovalent cation ex potential effect). Reprinted from R.
Parsons, Electrochim. Acta, 21, 681 (1976), with permission from Elsevier Science.
tetraalkylammonium salts, often with PF6 or BF4 anions, are the preferred sol-
utes for capacitors, while Li+ salts are often involved in high-energy recharge-
able battery systems where deposited Li is the anode material, as metal or an
intercalate in carbon.
The donor properties of solvents as classified by Gutmann 10 (Table 13.5)
provide a basis for ordering of solvation energies, mainly of cations, among
nonaqueous solvents. The donicity scale also provides a measure of the strength
of interaction of various solvents with polar molecular solutes, e.g., CF3I where
the 19F NMR chemical shift is linearly related24 to the donicity number (DN)
(Fig. 13.5). An opposite trend is observed when the chemical shifts of 23Na+
(CI04") in various solvents are plotted against the DN (Fig. 13.6).
From an electrochemical direction, there are trends of polarographic half-
wave potentials, E 1I2 , for Zn2+, Cd2+, and T1+ with solvent donicity as shown in Fig.
13.7. This plot reflects the dependence of the Gibbs energy of solvation of the cation
MZ+ in the solvents on the DN in the redox reaction MZ+ + ze + Hg ~ HgIM. Gen-
erally, the E1/2 values shown tend to increase with solvent donicity number. How-
ever, in this plot from the literature, it is unclear on what scale the E1I2 values have
been referenced. If a reference electrode had been used internally in the respective
solvents, then a solvent effect on the reference electrode potential would have been
15
12 DMF. DMA
0°
TMPO °OMSO
E
a.
a.
"- 6
u..
a>
(,()
8 16
FIGURE 13.5. Relation of Gutmann donor numbers lO to 19 F NMR chemical shifts in interaction
of solvents with CF3I. (From Erlich, Roach, and Popov?4)
358 Chapter 13
12
9
E
8:
...... 6
0
Z
If) 3
N
flO
0
-3
FIGURE 13.6. Relation of Gutmann donor numbers lO to 23 Na+ (CI04) chemical shifts in various
solvents.
DMSO
DMF
-0.3 AC
5
SF
> -0.1
......
~
W
0+ 0- 0- 0+
C =OandC=O,
360 Chapter 13
)N )N
) N-P 0 ++ )N-P-O HMPA
)N )N 5.20
+
) S 0 ++ )S-O: OMSO
3.90
+
-c N: ++ -c N: AN
3.40
)~ 0 ++ )N C 0 OMF
3.90
+
)~ S ++ )N C-S SOMF
4.40
are comparably significant in the resonance hybrid, so a very low dipole mo-
ment results. In the diagram, the dipole moments are in Debyes, i.e., units of 10-
!8 esu (see Chapter 4), which is approximately the electronic charge, 4.80 x
10- 10 esu, multiplied by an effective charge separation distance of about 0.0205
nm (or 0.205 A).
Similarly, DN and AN values depend on resonance aspects of the elec-
tronic structure of the solvent molecule except in simple cases. Examples 23 are
illustrated below.
Here we return to the key practical matter; that is, the complex equivalent
circuit by which it is necessary to represent29•30 the electrical response of porous
electrode supercapacitors and the associated distribution of Rand C elements.
Here the main concern is the distributed electrolytic resistance Re in the liquid
electrolyte, as shown in Fig. 13.3, which illustrates the equivalent circuit of a
lengthy pore (see Chapter 14) filled with a resistive electrolyte in contact with
an electronically conducting surface at which a double-layer capacitance Cdl or
a C¢ + Cdl is exhibited. 3 ! As explained in Chapter 14, such a circuit has no single
or unique relaxation frequency w" or values of the time constant "ReC;" there
is a widely distributed range of Wr values or ReCs which corresponds to a power
spectrum on discharge or recharge.
The Electrolyte Factor in Supercapacitor Design 361
This situation occurs because the inner regions of the pore (i.e., its surface
elements) are electrically accessed only through a progressively increasing Re
down the pore (ERe), i.e., there are progressively increasing IR drops. The dou-
ble-layer capacitance is completely chargeable, or dischargeable, only under dc
or low-frequency time scales. Hence a dispersion of capacitance occurs. A de-
tailed treatment of the electrical behavior of porous electrodes is given in Chap-
ter 14.
M; + Ai
~sub II
(SUblimatio~t
With acids, HA, there is a chemical proton transfer reaction with the sol-
vent (here H 20):
Ways are available for separating the derived salt (M+, A -) values into in-
dividual ionic components,4,33 but they can have no fundamental thermody-
namic basis. However, various empirical procedures are quite successful. 33
Calculations based on ion-solvent dipole electrostatic energies give values
in moderate agreement with the data derived from experiment. Approximately,
the ion-dipole energies gained when an ion enters a polar solvent balance the
energy that must be provided to break up the crystal lattice of strongly interact-
ing ions in the solid phase and transfer them as free but solvated ions into the
solution bulk.
The equilibrium solubility of a salt is detennined by the standard Gibbs en-
ergy (~GO) of solution of the ions from the salt crystal. Negative ~GO values cor-
respond to good solubility of a salt (i.e., to provision of a high concentration of
plus and minus ion charge carriers) and good conductance.
Thus the conductance of a salt, among other things, depends greatly on the
polarity or dielectric properties of the solvent. The latter also detennine what
fraction of the dissolved ions at a given concentration (below the solubility
limit) are plus or minus paired (factor 3), usually partially retaining their solva-
tion shells of coordinated solvent molecules [Fig. 13.I(b)].
Table 13.11 gives some idea of ionic hydration energies for some simple
monovalent ions relative to the value for the proton. They are all large (negative)
values on the absolute scale. Di- or trivalent ions have much larger solvation en-
ergies, which are related to the square of the charge number. There have been
various attempts to make a priori calculations of individual ionic hydration (or
solvation) energies. The first procedure was carried out by Born in 192034 and
was based on the difference between the self-energy of charging (see Chapter
4) the ion in a solvent of dielectric constant s and that in a vacuum (B = 1). This
difference is a Gibbs energy given by
(13.7)
for an ion of charge Zie and radius rio Equation (13.7) gives the correct magni-
tude for I1G s for ions in water. Better estimates are obtained if calculations 35 ,36
are based on the electrostatic energy of coordination and orientation of solvent
dipoles around the ion, with some allowance for solvent structure modification4
in the region around the solvated ion. A critical examination of the various types
of ab initio calculations and corresponding models used is found in Ref. 14 and
in the relevant original papers.
Equation (13.7) relates the I1G s to the dielectric constant of the solvent, B,
in the term liB. From the nature of this relation it will be seen that it will not give
a good account of the specificity of ion-solvent interaction energies since for B
values above about 15-20 (i.e., for a variety of common solvents that are good
364 Chapter 13
media for dissolving salts), lie is a small quantity compared with 1, so that tl.G s
remains a relatively large negative quantity. In fact, it can be seen from Eq.
(13.7) that except for quite small values of e for nonpolar solvents, the magni-
tude of tl.G s is determined mainly by the loss of the ion's charging energy in a
vacuum (the Zie212ri term with e = 1) as the ion is transferred into the solvent
medium. The ion-dipole interaction mode1 34•35 gives a better account of speci-
ficity for ion-solvent interactions through the individuality of solvent dipole
moments and donicities,1O as well as coordination numbers for solvent mole-
cules around ions.
Since the solubility equilibrium constant (the solubility product Ksp) is
logarithmically related to AGO (AGo = -RTln Ksp ), relatively small differences
of AGO, associated with differences oflattice and solvation energies, make large
differences of Ksp; these can vary from 10- 13 to Wi for a variety of salts, and
also from one solvent to another. Hence, large differences of conductance can
arise, so that for battery or supercapacitor electrolytes either well-dissociated
acids or extensively soluble electrolytes must be used.
For nonaqueous solvents, solvation energies are usually smaller than for
water so solubilities and conductances are often less. Tetraalkylammonium salts
or salts of large anions such as Ph4B-, Ph4As-, PF6, AsF6, and BEl are often
reasonably soluble in nonaqueous solvents, although they are somewhat ion
The Electrolyte Factor in Supercapacitor Design 365
The following are sources of published data on electrolyte solution and sol-
vent properties relevant to capacitor development and testing.
Cl.
....
u
f:"
..
I
a
e
Ne
u
en
.....
<;
-
I
"0
E 6
N
E
u
(/) 5 DOL-THF
.....
-<
A3
3~--~----~----~--~
o 25 50 75 100
DOL concentration/mol %
FIGURE 13.A3. Molar conductivity of 1 M LiBF4 in DOL-DME and DOL-THF mixtures at
30°C. (Data from Matsuda et aI. 7,8)
N
E
u
CJ)
....
-<
2
'0 25 50 75 100
DOL concentration Imol %
FIGURE 13.A4. As for LiBF4 but with 1 M LiCI04. (Data from Matsuda et al.7.8)
The Electrolyte Factor in Supercapacitor Design 369
.(/)
.
5~-------------------'
DOL-DME
o 4 ~• _ _ ._. .....
E •
:l
E
~
.JfI:.
(/)
b
t
o 25
A5
50 75 100
DOL concentration /mol 0/0
FIGURE 13.AS. Walden product (AI}) for DOL-DME and DOL-THF mixtures with 1 M LiBF4.
(Data from Matsuda et aI. 7,8)
15V\
.-
I to
•
(5
E
Ne
0
(/)
......
5
<:
A6
0 25 50 75 100
DME or THF conelmol %
FIGURE 13.A6. Variation of A (1 M LiCI04) with solvent composition: 0 DMSO-DME; •
DMSO·-THF. (Data from Matsuda et alY)
370 Chapter 13
to~--------------~
/.~.
"J
; "j
'0
e
"'eu
VI
'- 5
<:
A7
80~--------------------'
o 100
15
10
'j
(5
E
t\I
E
u
5
(/)
.......
<:
A9
o- 20 40 60
€r
FIGURE 13.A9. Correlation between A (LiCl04 I M) and Br of solvent: 0 PC-DME; t:, S-DME;
• DMSO-DME. (Data from Matsuda et al.7,8)
1/1
0 6
Cl.
I
'0
E
N 4
b
.......
~
<: 2
A10
0 20 40 60
€r
FIGURE 13.AIO. Correlation of Walden product AI} (l M LiCI04) with solvent er: 0 PC-DME;
• DMSO-DME; t:, S-DME. (Data from Matsuda et aI. 7 ,8)
372 Chapter 13
0-
u
'-
All
OL----2~0~--~~--~----~--~1=OO
Moss % PC
FIGURE 13All. Viscosity of PC-DMM mixture at 298 K.
GO AsFs
CIO"..,
~.
Ace
~
BU4N+, BPh; -x___..
30 Li+ xe~ • CI04'
o AsF.-
x
• BPh.-
Bu4~
o Lt
10
A1:2. ...
0 50 100
Pure PC
"lope
FIGURE 13.A12. Variation of mobility at infinite dilution, A~, S cm2 mol-I, for some cations
and anions plotted against % PC in PC-DMM mixtures.
The Electrolyte Factor in Supercapacitor Design 373
13.12.4 Conductivities
The conductivities of various tetraalkylphosphonium fluoroborates and
one trifluoromethylsulfonate at 0.5 M concentration in propylene carbonate so-
lution were compared by Morimot0 37 and the effect of temperature (-25.0 and
+2SOC) was determined. Phosphonium salts were found to be preferable with
REFERENCES
1. 1. Raistrick (review) in Electrochemistry of Semiconductors and Electronics, 1. McHardy and
F. Ludwig, eds., p. 297, Noyes Publ., N.1. (1993); see also 1. Currie in The Chemistry and
Physics of Composite Media, Electrochemical Society Proc., vol. 85-8, M. Tomkiewicz and
P. N. Sen, eds., Electrochemical Society, Pennington, N.J. (1985).
2. B. E. Conway, 1. Electrochem. Soc., 138, 1539 (1991).
3. B. E. Conway and E. Gileadi, Trans. Faraday Soc., 58, 2493 (1962).
4. B. E. Conway, Ionic Hydration in Chemistry and Biophysics, Elsevier, Amsterdam, (1981).
5. V. R. Koch, C. Nanjundiah, and 1. L. Godlman, in Proc. Fifth Inti. Seminar on Double-Layer
Capacitors and Similar Energy Storage Devices, S. Wolsky and N. Marincic, eds., Florida
Educational Seminars, Boca Raton, Fla. (19995).
6. V. N. Plakhotnik et al., Elektrokhimiya, 24, 964 (1988).
7. M. Morita, T. Fukumasa, M. Motoda and Y. Matsuda, J. Electrochem. Soc., 137, 3401 (1990).
8. M. Morita, M. Goto, and Y. Matsuda, Bull. Chem. Soc., Japan, 59,1967 (1986).
9. L. Werblan and A. Balkowska, J. Electroanal. Chem., 354, 25 (1993).
10. V. Gutmann, Chemistry in Britain, 7, (3), 102 (1971).
11. A. I. Popov, Pure Appl. Chem., (IUPAC), 41, 275 (1975).
12. B. W. Maxey and A. 1. Popov, J. Am. Chem. Soc., 89, 2230 (1967); 91, 20 (1969).
13. J. Barthel and H.-J. Gores, Pure Appl. Chem., (lUPAC), 67, 919 (1995).
14. A. 1. Bard and L. R. Faulkner, Electrochemical Methods, Wiley, New York (1980).
15. V. R. Koch and C. Nandjundiah, in Proc. Fourth Inti. Seminar on Double-Layer Capacitors
and Similar Energy Storage Devices, S. Wolsky and N. Marincic, eds., Florida Educational
Seminars, Boca Raton, Fla. (1994).
16. T.1. Melton and R. 1. Simpson, J. Electrochem. Soc., 137, 3865 (1990).
17. J. Robinson and R. Osteryoung, J. Am. Chem. Soc., 101, 323 (1979).
18. 1. Barthel and H.-I. Gores, in Chemistry of Nonaqueous Solutions: Current Progress, G.
Mamentov and A. 1. Popov, eds., Chapter 1, VCH Publ., New York (1994).
19. J. Barthel and H. Popp, J. Chem. Information Compo Sci., 31, 107 (1991).
20. B. E. Conway, in Ionic Hydration in Chemistry and Biophysics, Chapter 11, Elsevier,
Amsterdam (1981).
21. L. Benjamin and V. Gold, Trans. Faraday Soc., 50, 797 (1954).
22. R. Parsons, Electrochim. Acta, 21, 681 (1976).
23. A. 1. Parker, Electrochim. Acta, 21, 671 (1976).
24. R. H. Erlich, R. Roach, and A. 1. Popov, J. Am. Chem. Soc., 92, 4989 (1970).
25. D. P. Wilkinson and B. E. Conway, Electrochim. Acta, 38, 997 (1993).
26. U. Mayer, V. Gutmann, and W. Gerger, Mh. Chem., 103, 1360 (1972).
27. E. M. Kosower and E. P. Kleindinst, J. Am. Chem. Soc., 78, 3483; 5700 (1956) and 80,3253;
3267 (1958).
28. K. Dirnroth, C. Reichardt, T. Siepmann, and F. Bohlmann, Ann. Chem., 53, 661 (1963).
29. Third IntI. Seminar on Double-Layer Capacitors and Similar Energy Storage Devices, S.
Wolsky and N. Marincic, eds., Florida, Educational Seminars, Boca Raton, Fla (1993).
The Electrolyte Factor in Supercapacitor Design 375
30. Second Inti. Seminar on Double-Layer Capacitors and Similar Energy Storage Devices, S.
Wolsky and N. Marincic, eds., Horida Educational Seminars, Boca Raton, Ha.
31. L. Bai, L. Gao, and B. E. Conway, 1. Chem. Soc., Faraday Trans., 89, 235, 243 (1993).
32. N. K. Adam, The Physics and Chemistry of Surfaces, Oxford University Press, Oxford (1941).
33. B. E. Conway, 1. Soln. Chem., 7, 721 (1978).
34. M. Born, Zeit. Physik, I. 45 (1920)
35. 1. D. Bernal and R. H. Fowler, 1. Chem. Phys., I, 515 (1933).
36. D. D. Eley and M. G. Evans, Trans. Faraday Soc., 34, 1093 (1938).
37. T. Morimoto, in Proc. First Inti. Seminar on Double-Layer Capacitors and Similar Energy
Storage Devices, eds. S. Wolsky and N. Marincic, Horida Educational Seminars, Boca Raton,
Ha. (1991).
14.1. INTRODUCTION
The point has often been made that electrochemistry is a two-dimensional sci-
ence since its processes, including charging or discharging of double layers,
proceed on surfaces rather than in bulk. When the condition of2-dimensionality
is imposed on an electrode reaction (e.g., at a plane electrode interface), then a
coupled condition arises, namely, reagents must diffuse to and products diffuse
away from the electrode surface. Mechanical or hydrodynamic assistance to this
mass-transfer condition is often provided, (e.g., in electrode-synthetic proc-
esses), but the requirement of diffusion or migration to or from the electrode still
obtains. Even in charging the capacitance of the double layers at high-area elec-
trodes, there is some reorganization of the distribution of cations and anions of
the solution, especially in a two-electrode double-layer capacitor where ions of
opposite charge must be differentially accumulated at the two respective elec-
trode interfaces of each cell of the device. Hence there must be electrolytic and
diffusional migration of ions during charging or discharging.
The limitations of planar electrodes exhibiting 2-dimensional electro-
chemistry are largely attenuated if high-area, porous, or particulate electrodes
having a quasi-3-dimensional nature, are employed. Then diffusion limitations
are eliminated or largely attenuated since path lengths for transport of ions or
molecules in the solution are very much diminished relative to the situation at
plane electrodes (semi-infinite diffusion). The transport situation is then locally
like that in a thin-layer cell.I
377
378 Chapter 14
important are (1) the pore-size distribution and (2) the accessibility of electro-
lyte to the distributed pore area of the material. Coupled with the last factor is
wetting by the electrolyte and capillary action within the pore matrix. The latter
can be assisted by the addition of surfactants. The requirements for optimum
utilization of a high-area electrode material for a double-layer capacitor are the
opposite of those for a fuel cell, where a broadly distributed gasfsolid/liquid
"three-phase" interface is necessary to achieve maximum power. For a capacitor
electrode, zero residual gas occupancy of pores is the desideratum, but is not al-
ways achievable. While pore-size distributions can be determined on high-area
porous carbon materials (e.g., by employing the mercury penetration method up
to high injection pressures), such data usually do not reflect the actual distribu-
tion of electrolyte-occupied pores, which is a much more difficult factor to
evaluate reliably.
High-resolution scanning electron microscopy can provide visualization of
pore structures in the dry state, down to ca. lO-nm scales, while on very thin-
sectioned preparations, transmission electron microscopy provides information
almost down to atomic resolution, 0.5 - 1 nm. However, few detailed studies of
this kind are available.
From another direction, heats of wetting by an invading electrolyte can be
useful, but more for comparative purposes between two or more preparations
rather than for the absolute evaluation of the heat of wetting. Some results of this
kind are shown for carbon materials in Chapter 9.
The wetting of, and capillary action within, pores are determined by (1) the
local interfacial tension and (2) the contact angle, two not-unrelated quantities.
However, in very fine pores, the significance of the contact angle becomes
nebulous since a macroscopic meniscus is not formed in the regular way. Of
course, in addition, the occupancy of pores by the device's electrolyte is of
prime importance in determining the ohmic resistance of capacitor electrodes
and their equivalent series resistance.
In the following pages of this chapter a brief account is given of the nature
of porous electrodes and the models that have been proposed to represent them,
together with some analysis of their ac and dc behavior. The problems that occur
in the case of electrochemical capacitors originate from nonuniform primary
current distribution,2 (i.e., that determined by inhomogeneities of ohmic solu-
tion resistance along conducting pore channels and/or of the electrode matrix)
or finite resistance of the matrix structure itself. This leads to a continuous vari-
ation of electrical relaxation rates (reciprocals of RC time constants and conse-
quent frequency response) throughout the matrix, inward from the outer
geometrical interface of the electrode structure in contact with bulk solution, to-
ward the inside distribution of pore channels and pore surfaces, the latter pro-
viding the large-area interfaces for double-layer charging. Some model
diagrams of electrode pores will be seen later in this chapter.
380 Chapter 14
(14.1)
LlV=IR+ ~f J.dt=constant
or
Differentiating
LlV.C) dl (14.3)
d [- - =O=RC-+I
dt dt
then
(14.4)
or
(14.5)
so that
t (14.6)
-lnl=-+r
RC
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 381
The integration constant r is found from the condition that at t =0, all of
the potential drop LlV is falling across R (/ is at its maximum value), i.e., 1=
LlVIR. Then
LlV (14.7)
-In-=r
R
or
Alternatively
That is, the charging current through R into C declines exponentially on a time
scale characterized by a reduced time, tIRC, where RC is the time constant of
the series RC combination. I~O as t~oo; then Ll V = the potential across C and
that across R is zero since I has become zero.
The above elementary example was worked through in order to illustrate
the situation with more complex equivalent circuits. (The equivalent circuit to
a real system is that arrangement of R, C and possibly inductive L components
in series and/or parallel connections that reproduces the observed frequency re-
sponse of the experimental system, including the phase angle as a function of
frequency w or log wand the correct relations between the real and imaginary
impedance components Z' and Z' in the complex plane over a range of experi-
mental frequencies. In more complex cases, the equivalent circuit may not ac-
tually represent the physical basis of the process occurring at the electrode
although for an interfacial electrode reaction, a real double-layer capacitance
component, Cdt> must always form a component of the equivalent circuit with
which often R, other C, or L components may be in series and/or parallel.
From the above, it can be seen how a complex network of parallel RC cir-
cuits (each a series RC combination) such as that illustrated in Fig. 14.1 will
have a distribution of characteristic RC time constants and therefore different
charging or discharging relaxation times, depending on the values of Rand C
for each circuit element in the network. A network such as that as shown in Fig.
382 Chapter 14
LR;----------------- -z"
f I I
I I
electrolyte
resistance R
/ within pore
electrolyte impedance Z
(double-layer capacitance
and faradaic impedance)
FIGURE 14.1. The equivalent circuit of a pore invaded by a conducting electrolyte and having a
distributed RC network (transmission-line model). Typical-Z' vs. Z response asf(w) also shown.
14.1 represents in a crude way the equivalent circuit of a porous high-area ca-
pacitor device. The overall frequency-response behavior approximates that of a
transmission line that exhibits a -45 0 phase angle over a wide range offrequen-
cies, such as the Warburg impedance (see later discussion and Chapter 10) in-
volved in a diffusion-controlled Faradaic reaction. In fact, as shown in the paper
by de Levie,3 the differential equations for the charging behavior of the capaci-
tance in a transmission-line network have some formal mathematical similarity
to the equations for diffusion or heat transfer. 4 In addition to the series RC ele-
ments, there may be potential-dependent Faradaic or ohmic leakage resistance
elements locally in parallel across the double-layer capacitance elements which
determine the self-discharge behavior (Chapter 18) of the network.
It will be noted that the time scale for charging any RC series elements becomes
normalized in the ratio tiRe, a reduced time scale, i.e., common charging behavior oc-
curs for that scale. The time-constant, Re, appears here as it does in other cases,
e.g., discharge through a resistor or the critical frequency, Wr = liT = liRe, for
the top point of the Z" vs. Z' semicircle in the complex-plane plot for a parallel
RC circuit or the admittance plot for a series RC circuit (see Chapters 16 and
17).
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 383
t~~~~<
z+dz ./
FIGURE 14.2. Element of the equivalent circuit of a pore identifying the quantities involved in
the treatment of its impedance. (After de Levieh
av
dy=-dz =-zRdz so
. aV
-+iR=O
(14.11)
az az
ai
di=-dz=-C-dz
av (14.12)
az at
Here V is used for V(z,t) for brevity.
If we now differentiate Eq. (14.11) dldt and Eq. (14.12) dldz and combine
the results, we obtain
*In order to keep consistency with the mathematical development in Ref. 3, the symbol i is used
here for current and the letter I is defined in Eg. (I4.20b).
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 385
(14.14)
Equations (14.13) and (14.14) were identified3 as the basic differential equa-
tions describing the system under investigation in terms of i and V, respectively.
In the following sections Eq. (14.14) will be solved with
and
The solutions of these equations were obtained with the aid of a Laplace trans-
formation.
For the case of potentiostatic conditions:
. 1
I(Z,t)="R dV
dZ E'rr-RC~
="R-Y lm J exp[-rlt] (14.15)
from which the current i(O,t) at the orifice of t e pore can be obtained as
and
386 Chapter 14
and
(14.19)
i(O,t)=~-V(1I2WRC) {sinwt+ cos wt}
°
From the above equation for V(O,t) and Eq. (14.19), it can be concluded that the
phase angle between the potential imposed on a pore at its orifice z = and the
resulting charging current is 45°, so the charging current of a pore behaves for-
mally like the Warburg diffusion impedance of a flat electrode. The 45° phase
angle, independent of frequency w, is a characteristic feature of transmission-
°
line behavior.
Finally, the condition V(oo,t) = will virtually be fulfilled if
t> 8
- -V(wRC)
with
and
i(O,t) =I (14.20b)
reads
V(z,t) =R f i·dz
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 387
so
V(Ot) ~ ~(n:cJ
IR 04.23)
and
General conclusions from this model can be represented 3 in two diagrams, Figs.
14.3 and 14.4, in which the potential scaled as VIE or current scaled as ill is plot-
ted as a function of reduced time tlr, or the current is plotted as a function of
time for different depths down the pore.
As concluded by de Levie,3 upon the imposition of potentiostatic or gal-
vanostatic conditions (e.g., through a potential or current pulse) at the orifice of
1..0..---------------------,
t
..........
0.8
...
o
w
......
>
5 10 15 20
tIT
FIGURE 14.3. The potential (current) response, VIE or il/, of the pore as a function of reduced
time tlr, when a potential (current) step function with amplitude E(l) is applied at the orifice of the
pore. The characteristic time T depends on the coordinate z along the axis of the pore, on the solution
resistance R, and on the double-layer capacitance C, both per unit pore length, according to T =
iRc/4 (see p. 384). Reprinted from R. de Levie, Electrochim. Acta, 8, 751 (1963), with permission
from Elsevier Science.
388 Chapter 14
1.0
t
.....
"I-
0
0
W
">
-1.0
t: ....
z
0 2 3 4 =(wRC 12)1/2
FIGURE 14.4. The potential (current) response VIE or ill, at different distances z from the orifice
of the pore as a function of time t, when a sinusoidal potential (current) with amplitude E(I) and
angular frequency w is maintained at Z =0; R is the solution resistance per unit pore length and C
the double-layer capacitance per unit pore length. Numbers below curves are values of the quantity
7J(wRCI2)!I2. Reprinted from R. de Levie, Electrochim. Acta, 8, 751 (1963), with permission from
Elsevier Science.
the pore in contact with an electrolytic solution that penetrates the pore(s), the
potential or the current within the pore changes more sluggishly the greater the
depth within the pore. In the potentioharrnonic case, however-which as a con-
sequence of the neglect of transient terms, is in the Levie treatment equivalent
to the galvanoharrnonic case-the frequency maintained at the orifice is left un-
changed throughout the pore, whereas its amplitude decreases with increasing
z down the pore.
Finally, it is very useful to define a quantity characteristic of the fraction
of the pore effectively playing a part in the charging process. The foregoing
equations suggest the use of z ..J(tlr) = ..J4tIRC or zl..J(1l2wRC) for such a
penetration depth in the dc pulse or ac cases, respectively. This penetration
depth increases with time in potentiostatic or galvanostatic measurements, and
decreases with frequency in the alternating voltage or alternating current tech-
niques. Hence, after a very short time or at high frequencies, what is virtually
measured is the capacitance response of the more or less flat external electrode
surface, the pores being unable to follow the variations in potential or current
sufficiently quickly. Thus there is a major dispersion of capacitance. After a cer-
tain lapse of time or at lower frequencies, the influence of the pores, however,
becomes relatively more important because the inner electrode surface is usu-
ally very large in comparison with the outer or projected one. Consequently, if
the pores are adequately described as circular cyclindrical, but of nonuniform
diameter, the narrow pores, as it were, tune in after a longer time or at lower fre-
quencies than the wide ones.
These conclusions are very important for recognition of the power limita-
tions associated with porous electrode capacitor devices, especially those based
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 389
90~--~~---------------------------,
75
0
.....
-e-
50 rZw
-ir--
40 2
10- 1 10 104
LOG [r~w/D]
FIGURE 14.5. The phase angle I/J, in degrees, between the applied alternating voltage and the re-
sulting alternating current in cyc1indrical diffusion, plotted as a function of mean diffusion coeffi-
cient D, radius ro of the cylinder and angular frequency w. Reprinted from R. de Levie, Electrochim.
Acta, 8, 751 (1963), with permission from Elsevier Science.
390 Chapter 14
0.8
.... 0.6
....""'-
Q.
~ 0.4
>-
....u
0.2
0
10 5 10
FIGURE 14.6. The ratio of the current icyl in cylindrical diffusion to the current ipl in plane dif-
fusion, ceteris paribus, in potentiostatic measurements, plotted as a function of mean diffusion co-
efficient, D, radius, ro, of the cylinder, and time t. Reprinted from R. de Levie, Electrochim. Acta,
8,751 (1963), with permission from Elsevier Science.
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 391
V+dV V
L l.:9.!
FIGURE 14.7. A small section dz of the equivalent circuit of a pore with uniformly distributed
electrolyte resistance, R, double-layer capacitance, C, and Faradaic impedance, ZF, all taken per unit
pore length. z is the distance from the orifice of the pore measured along the axis of the pore; V and
i are the potential and the current respectively. The electrode itself has no resistance (lower hori-
zontalline).
unit length of pore. Diffusion, coupled to the Faradaic impedance, was consid-
ered only in the radial directions, not along the direction of the pore. This is jus-
tifiable as long as the penetration depth is much larger than the pore radius.
The general differential equations, analogous to those for the non-Faradaic
case are, for the infinitesimally small section, dz, of the pore, are
dV dV . (14.26)
dV=-dz=-Rdz so -+lR=O
dZ dZ
. ~ d' (14.27)
dl =- dz
dZ
=- -ZV dz so
V
-....!.... + -
dZ Z
=0
Equation (14.27) is now differentiated w.r.t. z and combined with Eq. (14.26),
giving
(14.28)
and likewise differentiating Eq. (14.26) and W.r.t. z combining with Eq. (14.27),
giving
(Fe R (14.29)
---e=O
dZ 2 Z
The solution of this latter equation is
in which the reciprocal of the real part of ..J(R/Z) can be recognized as a pene-
tration depth like that for the non-Faradaic case.
Further analysis yielded
eX1J -Z~
(14.31)
.( ) 1 de
z Z =- R dZ
E
= ..J(ZR) 'lZ )J sm. wt
and
(14.32)
i(O) = _bsinwt
"'/(ZR)
The phase angle ¢J between potential and current at Z =0 is given by the ratio of
the imaginary to the real component of lI..J(ZR) and since the argument of the
root of a complex quantity is half the argument of the complex quantity itself,
it is found that
b (14.33)
2¢J =arctan-
a
in which we denote the complex quantity lIZR by a + bj, a and b being real co-
efficients, j ==."J-l and the minus sign for ¢J being omitted.
Other cases involving the radial diffusion effect were also treated by de
Levie but are outside the scope of this discussion of the behavior of porous elec-
trodes. They are treated in some detail in Ref. 3.
In a second paper9 containing the fourth part of his seminal work on the
electrochemical behavior of porous electrodes,9 de Levie showed that the theo-
retical treatment of the first three (contiguous) parts of that work could fully ac-
count for the behavior of a model brush electrode designed to simulate the
behavior of a porous electrode. The brush electrode, made from parallel Pt wires
with the wire tightly wound around the brush arrangement, is shown in Fig.
14.8. The experimentally determined impedance behavior, plotted in the com-
plex plane (Z" vs. Z') for this model electrode system, is shown in Fig. 14.9 for
three concentrations of KCI electrolyte at 25°C: 0.1 M, 0.3 M, and 1.0 M. The
experimental data plot out exactly as 45° lines corresponding to the 45° phase
angle expected for a cyc1indrically porous electrode. The brush electrode was
comprosed of 2000 Pt wires 50 J1 in diameter, each about 10 mm long <f dz = 1
cm).
Geometrically such an electrode matrix does not provide strictly cylindri-
cal pores; in fact, it has a conjugate space between the circular metal cylinders
in contact, having hexagonal symmetry. However, the simulation provides an
excellent match to the behavior of a cylindrically porous electrode. A sintered
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 393
Pt wire,
O.5mm cp
Jeno gloss
platinum brush
electrode
FIGURE 14.8. Platinum wire brush electrode as model of porous electrode having parallel pores.
(After de Levie. 3)
silver powder electrode, made from spherical silver particles, also gave imped-
ance behavior exhibiting a 45° phase angle independent of frequency.
A useful summary relation of the qualitative variation of phase angle on
log (frequency) can be given as shown in Fig. 14.10, which illustrates how the
160 20
30
120
40
~
....... 80
-N
40
0 50 150 250
tIn
FIGURE 14.9. Measured cell impedance of the model platinum brush electrode (Fig. 14.8) in 0.1
to 1.0 M aqueous KCl at 298 K plotted in the complex plane for a frequency range of 20 Hz to 1
kHz. Lines are drawn with a slope of 45°, corresponding to transmission-line behavior. Reprinted
from R. de Levie, Electrochim. Acta, 8, 751 (1963), with permission from Elsevier Science.
394 Chapter 14
50r-------------------------------------------~
pore double-layer
exhaustion capacity
o 30
...... diffusion (capaci10r)
.g...
10
Log tJJ
FIGURE 14.10. Schematic representation of the dependence of the phase angle ¢ of the apparent
electrode impedance of a pore on the angular frequency w. In each horizontal part of the graph, the
dominating response effect in that frequency region is indicated. (After de Levie. 3)
and
(14.35)
di=-¥dZ so dildz+¥=O
d2i _ Ri = 0 (14.36)
dz 2 Z
and
d2V_RV=O (14.37)
dz 2 Z
These are the basic differential equations for the model under the above condi-
tions. Then, for the semi-infinite pore:
and
and also
.
l(Z) =-1 . -dV =- E exp( -z'lRIZ)
_~ (14.39)
R dz -YZR
with
i(O)=~ (14.40)
ill
Thus the pore behaves as an impedance, .,izR, which can be called the ap-
parent pore impedance, Za, since Z, and correspondingly ZR, is a complex quan-
tity that can be represented by real and imaginary components in the complex
plane. In this plane, Z is represented by a vector of length IZI and a phase angle
¢. The correspondin~ctor {Z has the length ..yjzJ and phase angle ¢/2. Since
R is scalar, rz and -vZR differ only in their vector magnitude. The calculations3
lead to the following conclusions under the assumption that the curvature of the
pore has no influence on Z:
From the mathematical equations developed, it turns out that the reciprocal
of the real part of-VRIZ can be identified as a quantity characteristic of the frac-
396 Chapter 14
tion of the pore length that is effectively involved in the ac response measure-
ments. It is thus a penetration depth, A, which is defined as
Table 14.1 shows calculated (Ref. 3) maximum values of A for various values
of the radius (ro) and electrolyte specific resistance (P).
The behavior of a simple redox reaction in a semi-infinite pore was treated
in Bockris and Srinivasan's monograph6 on fuel cells, based on analyses pub-
lished by Newman and Tobias lO and by Micka and Rousar. II - 13 Expressions for
the current and overvoltage distribution in the pore were derived, based on el-
liptic integral calculations.
These treatments are relevant more to Faradaic processes at fuel cell e1ec-
trodes l4 than to capacitors although, as stated earlier, significant relevance
arises when self-discharge Faradaic leakage currents are involved. We give be-
low some of the principal equations leading to relative current distribution and
total current, It, and for the overvoltage distribution down a pore.
Two cases were considered6 : (1) for an overvoltage <100 mV and a trans-
fer coefficient (Chapter 3) value a = 0.5, for which both backward and forward
currents of the Faradaic reaction near equilibrium (based on the Butler-Volmer
equation; see Chapter 3) have to be taken into account; and (2) for the simpler
case where overvoltages are> 100mV and then only the forward direction of the
reaction need be treated.
The differential rate dIz of the Faradaic reaction in the element dz along the
pore of radius ro is given in terms of the overvoltage, t7, at Z =z; the transfer co-
efficient, a; and the exchange c;:urrent density, i o, by
Source: Reprinted from R. de Levie, Electrochim. Acta, 8, 751 (1963), with permission from Elsevier Science.
Notes: ro = Radius of the pore (j1); p = specific electrolyte resistance (ohm cm); C = double-layer capacitance,
taken to be 20 J1. cm- 2; w = angular frequency, taken to be 500 rad S-I (approx. 80 Hz).
(If other components of Z are present besides the double-layer capacitance, A will be smaller than indicated
above.)
The penetration depth deduced for the earlier general case was d ..J2WT or II ~wRC 12 for ac modulation.
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 397
dz (14.43)
dlJ =Iz - ,
Knlo
where I z is the current generated in one pore from z = 0 to z = z and K is the spe-
cific conductivity of the electrolyte. Differentiating Eq. (14.43) and combining
the resulting equation with (14.42) leads to
d2lJ
dz2 (2). { l(al]RTF) -
= Kr2 10 exp [ I]
exp -(1 - a) RT FJ } (14.44)
and
.. -;(dl])
Iz=t= It =Knro l dz z=O
(14.47)
iz tan( If/)x=x
(14.48)
it tan( If/)x=l
398 Chapter 14
and
. =Kn~aT
2RT (4a)112 . h Yo (14.49)
It sm "2 tan ()
If! =1
where:
sinh(yol2) (14.50)
cos(lfI) =
sinh(yl2)
'II (14.52)
f(k,lfI) =fo (1 - k2 d.1f!2
sm IfI
)112
2iof2F (14.53)
a=--
KRTro
z (14.54)
x=l'
'IF (14.55)
y= 2RT
k= = sin () (14.56)
cosh(Yol2)
f(k,lfI) is the elliptic integral of the first kind and tables of this integral are avail-
able as a function of () and 1fI.
Case 2 for 'I » 100 mY.
For this case, the relative current-density distribution, the total current den-
sity, and the overpotential distribution were given 6 as follows:
and
4RT
11z-11o=Flnsec [(a2 12) exp("2
1
(1'0)]x (14.59)
The latter equation is the expression for the ohmic potential drop in the solution
fromz = 0 to z = z. According to this equation and Eqs. (14.53) to (14.55), it fol-
lows that the ohmic potential drop in the solution depends on the parameters
i o, 11 0, ro, and t-
In the general case, for which Eqs. (14.57) to (14.59) must be used, IzlIt is
initially linear with x (= zit), having a slope of 45° with the x axis, but as 110 in-
creases, it varies rapidly with x (Fig. 14.11). The overpotential vs. current den-
sity plot in Fig. 14.12 shows two sections depending on the current density-at
lower current densities the normal Tafel slope is observed, whereas at higher
1.0r------------------lP
0.8
+,0.6
.......
"-N
.......
0.4
0.2
1.0
> 0.8
c
:;: 0.6
c
CD
15
e- OA
CD
>
0 0 .2
O~------~~-----J--------~ ______~
10 -2 10-1 1 101
current densities the Tafel slope is double the normal value. On the other hand,
for very low io «10-9 A cm-2) or large specific conductivity (K) values >10
ohm- 1 cm- 1, the current distribution is linear with distance down the pore (solid
lines, no points, in figure 14.11) and the predicted Tafel slope retains its normal
value.
The pioneering theoretical work by de Levie3,9 was taken further by
Keiser, Beccu and Gutjar, 15 who derived relations for the impedance as a func-
tion of frequency for various geometries of a single pore and applied the results
to the case of a porous electrode. By means of comparisons calculated for vari-
ous electrical models in relation to the overall impedance curve, they showed
that the average pore structure of a porous electrode could be estimated. Again,
the mathematics are complex and laborious. Essentially, the transmission-line
equivalent circuit was used but various pore shapes, as illustrated in Fig. 14.13,
were investigated. They gave rise to a characteristic series of complex-plane
curves of Z' vs. Z' for selected parameters (Fig. 14.13) representing different
form-factors for the pores.
First, a cylindrical pore was considered oflength t and radius r, with a uni-
formly distributed double-layer capacitance at a smooth surface. The electrical
properties of the pore were regarded as made up of RC elements in a transmis-
sion-line arrangement along a length variable, x as in Ref. 3.
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 401
0.4
0.3
=
N
I
0.2
o. ,
For the impedance change, dZ, along the pore length x (z in de Levie's no-
tation), the complex resistance was written
defined asf(I1); for a cylindrical poref(l1) == 1 but has other values for differently
shaped pores (see Fig. 14.13). Then an integration of the differential equations
above gives an explicit result:
For other pore form factor values, only numerical integration can be performed.
The general curve for -Z'IRo vs. Z"fRo, i.e., a complex-plane plot, is shown in
Fig. 14.14 for a series of ifA values.
For a series of R, C combinations (R" C,; Rb C2 ••• RN, CN) in a transmis-
sion-line network, Zb the impedance of N-k elements gives the recursion for-
mula
(14.64)
(14.65)
0.6
2
0.5
0
0.4
(t)
_0::
...... 0.3
N
I 0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5
Z'IR o
FIGURE 14.14. Master complex-plane impedance curve for form-factor values, ttl., and
Ro = IJ7rKr2. l. = 0.5 (rKlwC)ll2; notation of Ref. 15. Reprinted from Keiser et aI., Electro-
chim. Acta, 21, 539 (1976), with permission from Elsevier Science.
Note that for pore-form numbers 3 and 4, there is a tendency for an initial
(high tf).. values) semicircle to become developed. It is interesting that this has
been observed experimentally with a compressed porous Ni electrode. 7
CIC
0~-~8~~~-~4~~~0~~~4~~~8~
X
FIGURE 14.15. Average relative ionic concentration across the cell for various values of the y
parameter. The dashed line represents the ionic concentration profile before charging; Yl = 1.155,
Y2 = 10.40, Y3 = 22.49, Y4 = 46.20, and Y5 = 104. Reprinted from C. J. E. Farina and K. B. Oldham,
1. Electroanal. Chern., 81, 21 (1977), with permission from Elsevier Science.
12
10
>< 6
"0
~"
"0
4
0
-8 -4 0 4 8
X
FIGURE 14.16. Plots of the undimensionalized electric field d~/dX vs. x. y values as in Fig. 14.15.
Reprinted from C. 1. E. Farina and K. B. Oldham, J. Electroanal. Chern., 81, 21 (1977), with per-
mission from Elsevier Science.
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 405
Various interfaces (e.g., coastlines and crystals) have in recent years been
modeled in terms of so-called fractal geometries, i.e., structures that are self-
similar on various scales. Similar applications have been made to porous elec-
trodes. Mulder et al. 8 have examined Tafel currents and related admittance
spectra at fractal interface electrodes, e.g., those having a typical self-similar
406 Chapter 14
o
00 0
o
b) eoeDeoe
a a
oDe a
a
FIGURE 14.17. (a) Elements of an electrode/solution interface having a fractal structure based
on hexagonal (60°/120°) elementary geometry. (b) Cross-section geometry of a square fractal pore
structure. (Sapoval, ref. 23).
ns =6n 2 - 12n + 8
Note that for sufficiently large n, nslnv ~ 61n. For a sufficiently large spherical
particle (e.g., one having a diameter of 50 atomic diameters, that is about 15
nm), the number in the bulk compared with the number in the surface would
scale approximately as 4/3 n?/4n?, i.e., with rl3. In practice, some particles of
powder materials (e.g., soots) are probably fractal and so have greater surface-
to-volume atom ratios than in the case of regular cubic clusters. For those inter-
ested in mathematics, the differences between sequential ns values given above
for cubes of atoms with n > 2 form an arithmetic progression of numbers ad-
vancing by 12.
The electrochemical accommodated charge is proportional to ns and thus
the stored energy would be (qns) x V for a potential V where q is the excess
charge of the interface calculated per atom of the substrate based on ca. 1.5 x
10 15 atoms (real cm2rl. The weight of material required to accommodate this
charge is proportional to nv x A, so the energy density of the accommodated
charge will be
where A is the atomic weight of the substrate material, q the charge accommo-
dated per atom, as above (e.g., 0.18 to about 0.3 e atom-I), and Vis the voltage
(relative to that of another electrode).
As an example take a carbon sample having 100 m2 g-1 (a low figure), i.e.,
106 cm2 g-l. This is 1.2 X 107 cm2 per mole (A = 12) of carbon; but 1 mol == 6 X
1023 atoms and 1 cm2 accommodates on the order of 1015 atoms; therefore
nslnv for such a sample of Cis (1.2 X 107 X 10 15 )/(6 X 1023 ) = 0.02, or 2%. From
the formula deduced above for n,lnv> 2, we find n =:: 300 for such carbon
particles. This illustrates the commonly perceived importance of utilizing
carbon materials that have the highest possible real area per gram but that
have materials properties (e.g., wettability and pore distribution) of such a
kind that maximum access of electrolyte to the particle surface (the ns factor)
is still maintained, allowing the best achievement of stored charge and hence
energy density. Working out a compromise between these two factors in
double-layer capacitor devices is usually a materials-science art in this field,
depending very much on the pretreatments of the carbon materials and their
biological or fossil origins (see Chapter 9). In fact, for various carbon mate-
rials having a range of particle sizes and corresponding specific areas per
gram, the materials giving maximum storable energy (energy density) may
not coincide with the specifications of another material that delivers maxi-
mum power density (see Chapter 15). This factor has to be taken into ac-
count in optimizing materials specifications in designing an electrochemical
capacitor for particular purposes.
The question of the role of pore size and size distribution in porous carbon
materials for electrochemical capacitors was usefully considered by Shpz who
made comparative double-layer capacitance and BET (N z) surface area deter-
minations on various high-area carbon materials.
Various methods have been employed for real surface area measurements,
the best known one being due to Brunauer, Emmett, and Teller (BET) and vari-
ants based on Kr desorption into a chromatograph detector. The BET method
is, however, less satisfactory for microporous materials. Other procedures are
due to Dubinin and to Joyner, Barrett, and Halenda; and another is based on up-
take of Zn 2+ ions by adsorption from liquid (aqueous) solution. The latter pro-
cedure may probably be assumed to give real areas relevant to electrolyte
solution/carbon interfaces since the samples are actually wetted by the electro-
lyte.
According to IUPAC classification, pore sizes can be grouped in three
classes: micropores, <2 nm; mesopores, 2 to 50 nm; and macropores, >50 nm.
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 409
These figures may be compared with the diameter of a hydrated sodium ion (ca.
0.65 nm) or of a water molecule (0.286 nm).
With Spectracorp microbeads of activated carbon, measured double-layer
capacitance values (200 to 2600 J1F cm2 external area) are very high, so much
of the microporous structure must apparently contribute to the capacitance. Sur-
face-area distributions with respect to pore width determined on two Spectra-
corp carbon samples (M20 and M30) are shown in Fig. 14.18. A large
proportion of the real surface area arises from pores in the 0.5- to 5-nm range of
diameters. It was the conclusion of Soffer et aL 23 that it is these smallest pores
that give rise to most of the BET area that are wetted, consequently contributing
to the measured double-layer capacitance.
The dc capacitance distribution as a function of total surface area (m 2g- 1)
is shown in Fig. 14.19. The dc capacitance divided by external surface area,
plotted against micropore surface area and divided by external surface area, is
shown in Figs. 14.20 and 14.21 for activated microbe ads and activated carbon
fibers. These results illustrate the relative importance of the microstructure area
in obtaining the desired large double-layer capacitance values per gram. The
slopes of the lines in these two graphs are significantly different, being 0.07 for
the microbeads and 0.20 for the activated fibers.
4.5
'0>
•
M20B
ll...
......
W 4.0 I- -
•
U M20A
Z
•
M20C
~
U 3.5 l- -
<t
0.. MISA
<t
•
U
3.0 I- • M200 -
""',
"
•
M20E M30
Q
•
•
MISC
2.5 l-
M,,,
-
MIO
2.0
• • •MISB
I I I
1000 1250 1500 1750
TOTAL SURFACE AREA 1m2 g-1
FIGURE 14.19. Relation of dc capacitance to real surface area of designated carbon preparations.
(Ashurst Technology Center Inc., from Shi.22)
,.-,
N
E 30
~
'--'
0
. 25
<I>
'-
<t
-
<I>
U
0
\ ..
20
~
en
"0
c ...
<I>
15
-;;:
UJ
......
QJ
u
10
c
.E
'u0
0. 5
8
u
0
0 30 60 90 120
Micropore Surface Area I External Surface Area
FIGURE 14.20. dc capacitance (C) divided by external surface area (S) plotted against a micro-
pore surface area divided by the external surface area for activated carbon microbeads. (Ashurst
Technology Center Inc., from Shi?2)
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 411
1
,....,
~ 3.0
~ 2.5,
(1)
u
.E 2.0
5
(/)
g
1ii 1.5
";(
w
......
~ 1.0
c:
E
·0 •
8. 0.5 /-
(3 ,....
g 0.0 _ _ _ _ .~ _ _ _ _ _ _L _ _ _ __ 1 . _
o 5 10 15 20
Micropore Surface Areo / External Surface Area
FIGURE 14.21. As in Fig. 14.20, but for activated carbon fibers (same source).
It must be stated, however, that although the very small micropores con-
tribute substantially to the real area per gram, this fraction of real area is not nec-
essarily the most useful or electrochemically accessible since it is accessed only
through an appreciable cumulative solution resistance (transmission-line
model). Also, whether such pores are wetted by the electrolyte and hence elec-
trochemically chargeable is questionable. Certainly they will contribute only in
a small degree to the charge storage capacity under high-rate or short-duration
power-pulse discharge or recharge, contrary to the implications of the conclu-
sions in Ref. 22. These matters have been the subject of controversial discus-
SIOn.
Other high-area porous carbon materials for electrochemical capacitors
that are attracting current attention are glassy carbon structures,24 new carbon-
fiber preparations,25 and carbon-polymer tubes (related to fullerene struc-
tures).26 The latter have excellent properties for access by electrolytes and
consequently very high specific capacitances are attained.
"E -1 .5
I
"E -1.5
0 0
C C
C -1 .0
-- --
:? -1.0
'0. 0>
~ I :1
~
.§ E
i\l --0.5 ~ --0.5
0.0 0.0
1.0 1.5 2.0 2 .5 3.0 3.5 4.0 0 .0 0.5 1.0 1.5 2.0 2.5 3 .0
Z(real)/O em' Z(reall/O em'
-80.0 -80.0
(b) I (b)
'"<D ~
~ 0>
~
g' -40.0 :!?. -40.0 I" 4
"l:l ~
4 VI
CD <0
III
-- J:::.
~
•
. 3. 0-
~ -20.0 ~ -20.0
0.0 . _I v.v
0
"0 10° 10' 102 103 104 lOS 10- ' 10° 10 ' 10 2 10 3 104 10 5 ':s'
1\1
log (w/rad 5-') log(w/rad s-') "C
CD
-......
~
(iii) m
-1 .2
(a)
()
I ~
:r
'"E -0.9 CD
u 3
C
-...
C -0.6
~
III
01 CD
:r
D)
'"E <
~ -0.3 o'
...
~
0.0 "8
0 .0 0.3 0.6 0.9 1.2 1.5 1.8 ac:
1/1
Z(reall/O cm 1 m
(b)
~
Co
; 4 ~
0»
0,
::~ >
"0
~ -40.0 "2-
-...
0»
0'
III
.c
'" o·~
:::I
Q. -20.0 1/1
6'
o
D)
0.0 -1
10 10° 10 ' 10 2 103 104 105 l
log(w/rad s - ') 5
iil
FIGURE 14.22. Progression of impedance and phase angle responses [marked (b)] for a porous Pt model electrode with increasing concentration of KOH
electrolyte: (i) 0.5 M, (ii) 1.0 M, and (iii) 4.0 M. (From Bai and Conway.27 Copyright 1993 Royal Society of Chemistry.) -1>0
....
w
414 Chapter 14
1.0
•••••• • • 5
0.11- 0 o 4
-
0 0 0 0
0 0
C\I
• • •
••• • • •
IE 0.4
u
1.L..
3
~
E
-
.......
"0
0.'
<> .0 •
<>
o <> <> <> <> 2
-
-0.2 -
0
Ol ••
-l
• I-
-0.5 I I - 1 I
0.00 -0.05 -0.10 -0.15 -0.20 -0.25
Overpotentiol / V VS RHE
FIGURE 14.23. Double-layer capacitance C(log) of the porous Pt model electrode as a function
of potential for 5 KOH concentrations: (I) 0.1, (2) 0.2, (3) 1.0, (4) 2.0, and (5) 4.0 M. (From Bai
and Conway?? Copyright 1993 Royal Society of Chemistry.)
Electrochemical Behavior at Porous Electrodes; Applications to Capacitors 415
method. 27 It is seen that there is a major favorable change (increase) of Cd! val-
ues with increasing KOH concentration and corresponding conductivity, so that
the evaluated roughness factor (based in this case on a Cdl value of 25 f.lF cm- 2)
depends similarly on the electrolyte concentration (Table 14.3). The effect is a
major one and shows that real areas of porous electrodes can be estimated from Cd!
measurements only with highly conducting invading electrolytes and at low fre-
quencies. For an ac modulation of ± 10 mVat a frequency wHz, the maximum dVldt
would be equivalent to linear sweep voltarnmetry at 10-2 w (Chapter 16).
The porous electrode's electroactive surface becomes unfolded progres-
sively with increasing conductance of the electrolyte. The key factor here is that
the penetration depth of the ac modulation signal (see Ref. 3) becomes larger as
the conductivity of the electrolyte is increased. When the conductivity of the
electrolyte has become sufficiently high, the ohmic resistance elements, R, of
the transmission-line model all become substantially diminished. In other terms,
it is also seen (see Fig. 14.22) that the role of a CPE in the equivalent circuit be-
comes diminished with increasing electrolyte conductance.
stitution and its porosity. Such effects do not seem to have been examined in
studies on double-layer capacitor charging or discharging, or reliability testing,
but it appears that such evaluations are desirable.
REFERENCES
1. C. N. Reilley, Rev. Pure Appl. Chem., 18, 137 (1968).
2. J. Newman, Electrochemical Systems, Prentice-Hall, Englewood Cliffs, N.J. (1972).
3. R. de Levie, Electrochim. Acta, 8, 751 (1963) (in 3 parts); also see A. Winsel, Zeit.
Elektrochem., 66, 287 (1962).
4. J. Crank, Mathematics of Diffusion, Clarendon Press, Oxford (1975).
5. J. Miller in Proc. Second IntI. Seminar on Double-Layer Capacitors and Similar Energy
Storage Devices, S. Wolsky and N. Marincic, eds., Rorida Educational Seminars, Boca Raton,
Ra (1992); also see Proc. Third Inti. Seminar (1993).
6. J. 0' M. Bockris and S. Srinivasan, Fuel-Cells, Their Electrochemistry, Chapter 5, McGraw
Hill, New York (1969).
7. T. Pajkossey, J. Electroanal. Chem., 300, I (1991).
8. W. H. Mulder, J. H. Sluyters, T. Pajkossey, and L. Nyikos, J. Electroanal. Chem., 285, 103
(1990).
9. R. de Levie, Electrochim. Acta, 9, 1231 (1964) (part 4 of the series).
10. J. S. Newman and C. W. Tobias, J. Electrochem. Soc., 109, 1183 (1962).
II. K. Micka, Adv. Chem. Series, 47, 73 (1965).
12. K. Micka and 1. Rousar, Electrochim. Acta, 21, 599 (1976).
13. K. Micka and 1. Rousar, Coll. Czeek. Chem. Comm., 40, 921 (1975).
14. S. Srinivasan and H. D. Hurwitz, Electroehim. Acta, 12,495 (1967).
15. H. Keiser, K. D. Beccu, and M. A. Gutjahr, Electrochim. Acta, 21, 539 (1976).
16. E. J. W. Verwey and Th. G. Overbeeck, Theory of the StabilityofLyophopic Colloids, Elsevier
(1948).
17. C. 1. E. Farina and K. B. Oldham, J. Electroanal. Chem., 81, 21 (1977).
18. A. T. Hubbard, J. Electroanal. Chem., 22,165 (1969).
19. A. T. Hubbard and F. C. Anson, J. Electroanal. Chem., 9, 163 (1965).
20. A. P. Brown, M. Reischmann, and D. Pletcher, J. Electroanal. Chem., 50, 65 (1974).
21. B. Sapoval, Solid State Ionics, 23, 253 (1987).
22. H. Shi in Proc. Fourth Inti. Seminar on Double-layer Capacitors and Related Devices, S.
Wolsky and N. Marincic, eds., Rorida Educational Seminars, Boca Raton, Ra (1994).
23. A. Soffer, D. Golub and Y. Oren, J. Electroanal. Chem., 260, 383 (1989).
24. R. Kotz, M. Sullivan, M. Bartsh, and D. Haas, in Proc. Fourth IntI. Seminar on Double-layer
Capacitors and Related Devices, S. Wolsky and N. Marincic, eds., Rorida Educational
Seminars, Boca Raton, Ra (1994).
25. F. W. Geurts and Z. Horovitz, in Proc. Fourth IntI. Seminar on Double-layer Capacitors and
Related Devices, S. Wolsky and N. Marincic, eds., Rorida Educational Seminars, Boca Raton,
Ra (1994).
26. C. Niu, E. K. Sichel, R. Hoch, D. Moy, and H. Tennent, in Proc. Sixth IntI. Seminar on
Double-layer Capacitors and Related Devices, S. Wolsky and N. Marincic, eds., Rorida
Educational Seminars, Boca Raton, Ra. (1996).
27. L. Bai and B. E. Conway, J. Chem. Soc., Faraday Trans., 89, 235, 243 (1993).
28. For example, see A. W. Adamson, Physical Chemistry of Surfaces, 4th ed. pp. 200-203,
Wiley, New York (1982).
Chapter 15
The relation between power and energy requirements in the operation of "prime
movers" has long been an important topic in the engine industry, starting with
the period of steam and improvements in the efficiency of the Newcomen at-
mospheric steam engine by Watt through his separate condenser, and the inven-
tion of indicator diagrams for recording efficiency.
The power and energy requirements at the wheels for typical urban and
suburban driving in a typical compact car that weighs 2000 lb. are listed in
Table 15.1 based on assessments made in 1967. 1,2 These figures relate to the
power-density (p.d.) and energy-density (e.d.) performance of batteries (or
battery-capacitor hybrids) required for contemporary electric vehicles.
Driving cycles (Federal Urban Driving Schedules, PUDS) in recent years
have been analyzed in relation to the use of electrochemical capacitors in hybrid
battery-capacitor energy sources where the capacitor component provides a
load-leveling function for smoothing and handling the high power drains in-
volved in acceleration or uphill driving. Such studies have emphasized the im-
portance of evaluating the dependence of the achieved energy density on the
operating power density of such systems.
During the past 30 years or so, specific power density (e.g., watts per kilo-
gram) and energy density (watt-hours per kilogram) have been empirically plot-
ted against each other, often on logarithmic scales in "so-called Ragone plots."
These types of plots originated in a conference paper presented by Ragone3 at
417
418 Chapter 15
TABLE 15.1. Power and Energy Requirements at the Wheels for Typical Urban
and Suburban Driving
(Compact Car, 2000 lb)
Power or energy Urban cycle Suburban cycle
Maximum power (kilowatts) 22.1 40.1
Energy per mile (watt-hours per mile) 234 242
Maximum specific power- (watts/lb) 44.2 80
Specific energy for 50 milesa (watt-hours/lb) 23.4 24.2
Source: Data from Commerce Technical Advisory Board. I
1000
AlI/Zn
-
I
CD Li/CIZ
...J
::
.......
a::
LLI
~
0
a..
u 10
u..
[j
LLI
a..
(/)
~ORGANIC
ELECTROLYTE:
11 - - 10 laO 1000
SPECIFIC ENERGY I WH LS- 1
FIGURE 15.1. One of the first Ragone plots published that related specific power to specific en-
ergy for several battery systems. (Reprinted with permission from SAE paper No. 680453 Copyright
1968 Society of Automotive Engineers, Inc.)
INTERNAIL
COMBUSTION
ENGINE
NIICd
j'
CD
-
I
CD
-.J ...J
.......
~
......
a::
w
0: ~
LLI
o
~
a.. 10
a..
ILl
(/)
U a::
ii: o
8 1:
!J5
1~ ____________~~LUL------.------------~
1 10 100 1000
SPECIFIC ENERGY/WH LB- 1
FIGURE 15.2. Ragone plots for batteries, fuel cells, and other motive-power sources in relation
to driving power and range requirements. (Reprinted with permission from SAE paper No. 680453
Copyright 1968 Society of Automotive Engineers, Inc.)
420 Chapter 15
batteries and advanced lead-acid cells together with Zn-air and AI-air batteries
of relatively high energy densities. To these systems must be added the electro-
chemical capacitors which, although of low energy density, can provide attrac-
tively high power densities.
A theoretical basis for the hooked shape of Ragone plots referred to above
was not provided in Ragone's paper,3 but the origin of this shape is easy to un-
derstand qualitatively in terms of increasing electrode polarization (hence dimi-
nution of cell voltage, which determines energy density) as higher power
demands are made on a battery or capacitor at higher rates of discharge (higher
current densities). The principles involved are as follows, noting that electrical
power density is cell voltage (V) multiplied by discharge current density,
i: p.d. = iV. With increasing i, the product iV (the power, P) will tend to
increase, but with further increase in i, V begins to fall due to polarization
losses. These effects are treated in Section 15.2.
The Idaho National Engineering and Environmental Laboratory (INEEL)
compared Ragone plots for advanced electrochemical capacitors and Ni-Cd and
lead-acid batteries (specifications not given) using 1995 data (quoted in
Miller4 .) This comparison is reproduced in Figure 15.3. It will be seen that quite
103 •
DOE·near-..,.. goal
IIU pow" NICe!
IIU pow. P....cld
102
_/
...
Q)
101
UUwall24V org.l8III/-packagtd
~
o
Q.
100
Primary alkali..
WYnO,
high energy densities in the range 7-S Wh kg-I for 3-V nonaqueous solvent,
carbon double-layer-type capacitors and about 1-2 Wh kg-I for I-V aqueous
capacitors (Maxwell Corp.) can be attained. Pinnacle Corp. 2S-V capacitors
(probably of the RuOz mixed-oxide type) lie at about O.S Wh kg, with about 400
W kg-I p.d. rating. The 3-V organic electrolyte solution capacitors lie at about
200 to 3000 W kg-I. The Department of Energy' s (DOE) projected goal is about
1.7 kW kg-I. The currently quoted power density levels are all well above those
estimated for Ni-Cd and lead-acid systems, demonstrating the substantial ad-
vantage of electrochemical capacitors over appropriately chosen batteries when
high power density is the primary requirement. This behavior is observed not-
withstanding the intrinsic problem with high-area double-layer capacitors of
distributed internal pore resistance within the electrode matrices (Chapters 14
and 17). The initial slopes of the Ragone plots for the capacitors (on the log-log
scale) are comparable to those for the battery system data plotted and indicate
the role of similar iR and i2R losses caused by internal resistance (these factors
are analyzed later in this chapter).
until all the active material is consumed in (practice, an unusual situation), then
the energy density is
cessible areas of active materials in batteries or capacitors are usually not accu-
rately known or, in the latter case, depend effectively on the current drain I that
is due to the distributed nature of pore sizes and depths in porous carbon matri-
ces (Chapter 14) or other high-area electrode materials. Thus, power densities
are expressed as W g-I or kW kg-I. Often single values of p.d. are given for par-
ticular designs of batteries or capacitors, but this is not a satisfactory basis for
specifying p.d. for a particular battery cell or capacitor device since the power
that is developed on discharge (or required on recharge) depends, as already
noted, on the rate factor i or I (see Eqs. 15.4 or 15.5) or, for capacitors, as the
particular voltage, Ll V, during discharge at which p.d. is to be expressed (Section
15.2.5).
The density factor in energy density is a more definitely definable quantity,
at least for the case of the maximum theoretical e.d. It derives from the charge,
Q, that is Faradaically available from the cell redox reactions in the case of bat-
tery e.d. and is expressed per mole of active material or, more usually, per gram
or kilogram of such material, according to Eq. (15.2), taking into account the
number, z, of equivalents per mole.
In the case of double-layer capacitor devices, of course, most of the charge,
Q, arises, not from Faradaic charge transfer processes involving changes of the
oxidation state of reagents (and often also changes of phase that lead to irre-
versibility), but from removal (on discharge) or addition (on recharge) of elec-
trostatically accommodated charge (Chapters 2 and 6). In most
double-layer-type capacitor devices, only a small fraction of the total accommo-
dated charge is associated with Faradaic processes (e.g., originating from sur-
face or edge functionalities at graphitic C), as discussed in Chapter 9.
By contrast, in the case of redox-type pseudocapacitance systems [e.g.,
Ru02 or the electroactive conducting polymers (Chapter 12)], an opposite situ-
ation obtains: most of the (pseudo-)capacitance arises from redox Faradaic-type
charge transfer processes plus about 5-10% of the total storable charge from the
double-layer capacitance associated with the usually relatively high real areas
per gram of such materials. These two types of processes usually have different
characteristic relaxation times or equivalent frequencies in pulse or av modula-
tion, and can thus be distinguished. The relative extents of capacitance charge
storage in these materials depend, however, very much on their method of
preparation and electrochemistries.
Returning to the question of the p.d. of double-layer type capacitors, it is
usually considered that no kinetic limitations restrict their p.d.s, as occurs in
Faradaic processes (Tafel-type polarization, Eq. 15.4), since most of the charges
are accommodated purely electrostatically and thus are not subject to kinetic
limitations in the rates of charge or discharge. Fundamentally, however, such ki-
netic limitations can arise to some degree, especially for anion adsorption and
desorption in the case of the more polarizable and donative anions (e.g., Cl-, Be
Energy Density and Power Density of Electrical Energy Storage Devices 425
CNS-), where certain degrees of quasi-Faradaic, partial charge transfer arise (as
known at Hg). This is equivalent to the development of a pseudocapacitance
component in the measurable overall interfacial capacitance. Such behavior can
occur at the edges or faces of graphitic carbon materials (see Chapter 9).
where bs are the Tafel slopes RTlaF of the respective anode and cathode reac-
tions. III Vrev is the ideal power factor for increasing J if Ll Vrev were uninfluenced
by the magnitude of J, i.e., P would increase linearly with I. This is actually ob-
served for sufficiently low J values that the ohmic and Tafel polarizations re-
426 Chapter 15
The rate of change of P with current given by the above differential equation has
several components: (1) an initial linear increase at low currents that is propor-
tional to the voltage, ~ Vrev , provided by the electrochemical power source; (2)
with increasing current drain, a linear rate of decrease in power with current that
is proportional to 2IR arising from the PR term; (3) a rate of decrease in power
that is related to the log of the current (from the I[a + b log i] term); and (4) a
constant term equal to the sum of the Tafel parameters a and b also arising from
differentiating the I[a + b log i] term. In addition (see Section 15.3) there can be
a concentration polarization effect on p.d. Thus the rate of decrease of power
with increasing current (decreasing load resistance) exhibits complex behavior
and, as shown earlier, the p.d. plotted against current or current density exhibits
a maximum that is determined by the polarization parameters, especially R at
high current densities.
The p(max) arises at a current given by
Note that p(max) is determined both by I and In I; thus with increasing I, it is seen
that the rate of decrease in P is actually mainly determined by the ohmic IR term,
which tends practically to be a more important factor than the kinetic polariza-
tion at high I unless R is relatively negligible. However, there is in addition the
constant factor, LAb, which is related to the sums of the Tafel slopes for the an-
odic and cathodic partial reactions of the cell. Also, as expected, better maxi-
mum power is attained when the reversible cell voltage, ~ Vrev' is larger, i.e., for
a bigger open-circuit emf or driving force of the cell. On the basis of the equa-
Energy Density and Power Density of Electrical Energy Storage Devices 427
tions given above, some examples of P plotted against I for several values of the
parameters Rand b have been given in Ref. 5.
Note that at sufficiently high power drain (virtually a short circuit), Ll V will
be reduced to zero so that/eLl V) = Ll V =0, which occurs when (see Eg. 15.6)
= IR + 11(/) (15.12)
Practically, this occurs when I tends to be sufficiently large that the IR drop vir-
tually opposes the reversible cell voltage so that no power is available any more.
An additional factor can sometimes be the concentration polarization in
certain cells, e.g., with soluble redox reagents or fuel cells with soluble fuel,
such as CH3 0H. That is, at sufficiently high current drains, power becomes lim-
ited by mass transport of the reagent or by zero concentration of the reagent at
the reactive electrode surface. An analogous effect can sometimes occur in an
electrochemical capacitor when a high-area electrode material is combined with
a limited volume of electrolyte. Then, upon charging, significant gradients of
ion concentration can arise and most of the electrolyte ions become adsorbed at
the high-area interfaces of the electrodes (see Section 15.3 and Chapter 6).
Eb/I=-R (15.15)
or
Eb=-IR (15.16)
428 Chapter 15
From the above relations for P and e.d., P can be plotted against e.d. for various
increasing values of I, giving theoretical Ragone plots for variously chosen val-
ues of the parameters (Fig. IS.4), as recently calculated in a paper by Pell and
Conway5, which quantitatively evaluates the relative roles of Tafel polarization
and "IR" drop.
In relation to the hook shape of most Ragone plots (Le., e.d. decreasing as
p.d. approaches elevated values), note that the eventual decline in p.d. with in-
creasing I or I1A after its initial increase as I.!l.Vrev' given by Eq. (1S.5), is due
mainly to the term in I squared. That term increases with Ior IIA (depending on
the value of R) more rapidly than IEb In I1A or than (lIA)Eb In /lA, the transcen-
dental term arising from Tafel-type polarization in Eq. (1S.6). See the analysis
given later in Eqs. (1S.31), (IS.32), and (IS.33). For the quasi-3-dimensional
materials constituting electrochemical capacitor or battery devices, the
current density factor, /lA, is more commonly and practically replaced by
the 3-dimensional current density, I per gram or per kilogram, of the ac-
tive material, as noted earlier. Some further examples of Ragone plots for
practical systems are given in Chapter 20.
Power losses caused by polarization were considered in a general way in
Srinivasan and Bockris' monograph 6 on fuel cells, for which the power factor
is as important as it is for large electrochemical capacitors designed for battery
hybrid systems in electric vehicles having high power requirements. The gen-
eral form of the power vs. Faradaic current drain relationship is shown in Fig.
IS.S for an electrochemical power source. A detailed analysis for a series of po-
larization conditions, including IR drops for 1 and 0.01 ohms (as exemplified in
the linearly scaled cell voltage vs. current plots) gave 6 the cell terminal voltage,
E, vs. current, I, profiles illustrated in Fig. IS.6. The kinetic and ohmic parame-
ters used for these calculations are listed in Table IS.2. The exchange current
density, io, and the indicated (Table IS.2) anodic and cathodic transfer coeffi-
cients, aa and a c ' are the relevant kinetic parameters, together with the
diffusion-limited current densities, it. The terminal cell voltages are the
anode-to-cathode emfs remaining after subtraction of all polarization
voltage losses at each electrode. Similar considerations apply to a pair of
capacitor electrodes being discharged against each other.
A generalized set of polarization relations is shown in Fig. IS.7 where the
series of curves representing increasing contributions from the iR drop are plot-
ted on reduced-variable scales: overpotential '1 act + iR expressed as '1 act +
(ioR) X (ilio) ('1 act = kinetic activation overvoltage); current density as ilio and
iR drop expressed as ioR. For zero R, the polarization is purely of the Tafel
type, so the relation is logarithmic in ilio, and curved on the linear ilio scale,
as shown in Fig. IS.7. Conversely, with increasing R, the overall polarization
becomes almost linear in ilio when the iR drop becomes dominant in '1. Arbitrary
to' m
lO·r·~-:--....-.....-........,.......,.---....---.......- :J
(a) (b)
l ~
'0' tOO '<
1,. 1,.
...: ,
, ~
, \ 1/1
i,., tOO _._.-.-._.-.-.-
]!- .,
1ito
<=
.. ~to"
'w
<=
~
\ II
.
~,o-1
b • 0.120. a· 0.60'. :J
\ \
10"1 0.
.....iP
\ \
o
• b· 0.120. a • 0.60" •0
D.. Q.,0·1
\
,0-> \
.,
\ f...
10-4' ,, . 11 ,0-<
10-1 Ut1 .,00 l1t' 10-' 100
Energy-density x O·t (V) Energy-density x 0'1 (VI
~
1/1
~
!a-
IQO~.----~----~----~~----~--~~--~~~ 10-' r.-;:-.....- .....---............... --~-...,.. ............-- m
(c) (d)
...~
-;;-'0-' ':"":"":"''-. [
:J: b = 0.030, a =0.15
~
, b.0.030,a.0.~. _._._'_" m
... -.-.-. -~to~' ....... -.-' , :J
ID
itD-r b = 0.120, a' 0.60 ~ b =0.042, a= 0.21 .... '._'-'- .,
'. ~ b • 0.120, a • 0.6(( ., cO
\
" \
... '<
~ , :1;10-' \
•
t.,10·' ~
D.. , ~
iil
\ \ Ie
\ \ ID
10'4' I • n 10-4' , "' D
10"1 10"' 1~ 1~ 1~ 1~
,-
1.0 ,-
/
,,-
,-/
,-
Ideal power-current /
relation without / Moximum power
'T] losses /
:i: ,- I
,-
,-
"CV... 0.5 ,/
,-
~ I
o I
a.. ,- ,/ Power shutdown
/ due to diffusion
/
,/
/ limitation
/
Cell current I A
FIGURE 15.5. General form of cell polarization as a function of current for an electrochemical
power source involving Faradaic, JR, and concentration polarization voltage losses. (From Bockris
and Srinivasan, 6 based on an analysis of fuel cell performance. Reproduced with permission of the
McGraw-Hill Companies.)
but reasonable values of the parameters io (10- 6 A cm- 2) and b, the Tafel slope,
dlJ/dlog i (= 0.1), were taken. Here, as before, io is the exchange current density.
Note that the behavior illustrated in Figs. 15.5 and 15.7 applies to an elec-
trochemical power source involving a Faradaic process as in a battery, fuel cell,
or pseudocapacitance type of supercapacitor. For the double-layer type of ca-
pacitor device, the activation overvoltage (Tafel) component of polarization
will not normally be involved except on overcharge.
From the analysis by Bockris and Srinivasan 6 it again follows that power
losses depend on energy dissipation caused by ohmic loss (PR) and kinetic po-
larization ilJ where IJ = a + b In i generally, as noted earlier. The dependencies
of power production on current, corresponding to the polarization curves of Fig.
15.6 (conditions as in Table 15.2), are shown in Fig. 15.8. The differential vari-
ation of p.d. with current density will arise from the above two components of
polarization (see Eq. 15.6) as follows:
> 1.5-r---------------------.
.....
W
..J
<!
~ 1.0
'."O-•• .a..
Z 'x "D",O-_-o- __o... __O- 4
w " :c.............x --G---o-n....
-u.
b -,~~
-, ~-6 3 II
--..... ---1:.---6-___A- __t.-"t>n~
_A
I
a.. 0.5
,
~
...J
...J ~
!
W
1 ..........~
U
1.0r----------:-----=----~-__:'-__,
"""0
......
--;; 0.8
-
0::
o
II
=0:: 0.6
-0::
-II
I='"
O~ __ L_~L__ _ _ _~_ _ _ _ _ _~_ _ _ _ _ __ L_ _ _ _ _ _~
I 10 40 60 80 100
ilio
FIGURE 15.7. Effect of combination of linear (ohmic) and exponential (Tafel) polarization con-
tributions on generalized current density (i) vs. potential (17) relations for an electrode process.
=
Scales are in terms of reduced variables: overpotential scale 17 + iR (iR ioR x i/io) (see text) and
=
current density scale normalized to io as ilio. Tafel slope taken as b 0.118 V; i io exp [17lb]. For =
ioR = a (lowest curve), the curve is a purely Tafel relation. linear on a log scale of ilio and curved
(as shown) on the linear scale. (Calculations by the author.)
432 Chapter 15
where a and b are the parameters of the Tafel relation for the kinetics of the
power-producing electrochemical process.
It is seen that the rate of power loss due to the ohmic polarization effect (re-
sistance of the electrolyte solution together with any intrinsic resistance of the
electrode matrix and/or current collectors) increases linearly with the current
density i while the kinetic polarization power loss increases at a rate that is a
constant, -(a + b), together with a logarithmic factor, -b In i, where b is the
0.8
0.6 I
I
I
3:
I
.....
a:: 0.4 ~,c---c-~
W ,..0-
.0' I
3: I
oQ.. I
I
0.2 I
I
I
I
I
a 0.2 0.4 0.6 0.8 1.0
CURRENT/A
FIGURE 15.8. Examples of power production vs. current curves in a cell subject to polarization
behavior according to the polarization curves of Fig. 15.6 and conditions listed in Table 15.2. Num-
bers on curves correspond to calculation numbers indicated in Table 15.2. (Based on calculations
by Bockris and Srinivasan. 6)
Energy Density and Power Density of Electrical Energy Storage Devices 433
Tafel slope (smaller b values give a smaller rate of increase in power loss with
increasing i). With increasing i, the ohmic power loss will tend to increase more
rapidly than that caused by kinetic overvoltage effects, as was seen from Eq.
(15.6) earlier.
It can be seen that the ohmic polarization component of the rate of power
loss with increasing i is dominant when
i2R = ia + i b In i (15.20)
or
iR = a + b In i (15.21)
i.e.,
At small values of i, on the order of 10-4 _10- 6 A cm- 2 , the In term -(bIR)ln i
will be positive and dominate over the linear term in i, but at higher i values the
latter term becomes dominant. This corresponds to the form of Tafel plots at
high current densities (Fig. 15.7) when R is not insignificant. When R is small,
the (bIR) In i term is, of course, numerically dominant (i.e., kinetic polarization
principally determines the power loss), and vice versa when R is sufficiently
large. These conclusions are rather obvious.
3.5 to 4.0 V. Since the energy of a capacitor (see Chapter 2) charged to a plate
voltage difference of Ll V is 1I2CLlV2 , there is an obvious advantage in e.d. with
such nonaqueous embodiments. The power densities achievable are higher but
there are some disadvantages from the higher PR-drop factor in the power that
arises from the usually higher resistivity of nonaqueous electrolytes over that of
aqueous ones at comparable electrolyte concentrations.
Three factors distinguish the e.d. and p.d. characteristics of electrochemi-
cal capacitors from those of battery cells: (1) The capacitor voltage, Ll V, falls
continuously on discharge so the e.d. depends on the level of charge (i.e., the
corresponding Ll V) at which the e.d. is calculated; overall, the e.d. must be cal-
culated by means of an integration of Q.d(Ll V) over the range of voltage on dis-
charge, as with a battery cell having a declining voltage on discharge, e.g., with
Li-TiS2 or Li-MoS2 intercalation systems, or with Li ion cells. (2) Because of
the fall of Ll V with the extent of discharge of a capacitor device, the power den-
sity attainable from such a capacitor depends intrinsically on the fractional state
of discharge JQIQ since Ll V(JQ) = (oQIQ)/C. Thus, for a given controlled dis-
charge current, I, the p.d. progressively declines during discharge. Usually the
initial power density at the beginning of discharge is referred to, i.e., when Ll V
has its highest value. With a capacitor system, constant current discharge is only
attainable with a progressively adjusted load resistance, diminishing in propor-
tion to the falling Ll V of the capacitor device undergoing discharge.
In the above equations for e.d. and p.d., it is seen that the same polarization
terms, IR and Lb In I1A, enter into the relations for e.d. and p.d., diminishing the
electric potential difference, Ll V, from its maximum value, Ll Vrev , with increas-
ing I. Hence, formally, a simple ratio, r, of p.d. (= I.Ll V) to e.d. (= Q.Ll V) can be
written (or equivalently with i) as
~= r= I.LlVIQ.LlV= I1Q
(15.23)
e.d.
Also, Q = I.Llt if Llt is the duration of passage of constant current I required to
discharge the capacitance. Hence
Thus the relation between p.d. and e.d. is, in the simplest analysis, just the rate
factor, lILlt for the discharge, as might be intuitively apparent; the shorter the
duration of discharge for a given Q, the greater the power delivered in that dis-
charge. This ratio, it is seen, is actually independent of the polarization factors
that diminish both p.d. and e.d. individually but equivalently in the same way,
at least for the ideal simple conditions considered above.
The third factor that characterizes the behavior of capacitor energy storage
devices is that the internal (equivalent series) resistance is not a simple series re-
Energy Density and Power Density of Electrical Energy Storage Devices 435
sistance but a distributed one, as discussed and illustrated in Chapter 14. Thus
power is not simply defined by I multiplied by the potential difference between
the plates (at a given level of discharge) minus the IR drop since the effective
value of the latter quantity depends on the rate of discharge. At high rates, es-
pecially in pulse regimes, only the outer regions of the porous matrix, bearing
the double-layer charge, are accessed, while at low rates most of the whole of
the double-layer charge, including that from inner surface elements of the ma-
trix, can be accessed. Thus the quantification of the power density of carbon-
type double-layer capacitors is more complex than that for most battery
systems. However, some similarities exist since a distributed pore and matrix re-
sistance also arises in a number of battery systems (e.g., the Zn-Mn02 primary
battery) and in Li-SOCI 2 cells, which employ porous electrode materials. Then
the distribution of ohmic resistance and double-layer capacitance is equivalent
to that for the porous electrode case treated by de Levie and co-workers 7 as out-
lined in Chapter 14. Similar considerations apply to most fuel cells. 6
A further point with double-layer capacitors is that the kinetic polarization
terms ILb In IIA do not appear in the p.d. or e.d. equations in most cases, leaving
only the IR drop term to diminish available voltage on load. However, as men-
tioned earlier, the IR drop is itself a complex quantity since the effective R de-
pends on the time scale of discharge or of potential modulation in the case of
evaluation of such capacitor devices by impedance spectroscopy over a wide
range of frequencies.
Because in purely electrostatic charge accommodation there are ideally no
kinetic limitations to p.d., double-layer capacitor devices are perceived to pro-
vide high power densities, substantially larger than those available from most
battery-type systems. However, as discussed in Chapter 14, there are unavoid-
able power limitations of other kinds associated with the complex distributed
series resistance of pore structures and the electrolytic pathways within them.
These give rise to a power spectrum within which only a fraction of the charge
is accessible at high power levels, or with short-period pulses or high-frequency
av modulation.
A different kind of kinetic limitation (of a non-Faradaic kind) can, how-
ever, arise in microporous double-layer capacitors having large real areas of the
charge-accommodating material. When large distributed areas of porous elec-
trodes are charged, there is the requirement that appreciable quantities of the
ions (anions and cations) of the electrolyte must become separated and migrate,
respectively, to the surfaces constituting the positively and the negatively polar-
ized electrodes of the device. This can involve a kinetic limitation associated
with the ionic mobilities (equivalent conductances) of the anions and cations. A
net separation of anion and cation charges between the two capacitor electrodes
must take place since a double-layer capacitor is constituted of two double lay-
ers distributed over the large real areas of two separated high-area electrodes im-
436 Chapter 15
for a given constant discharge current i (= dq/dt = C dV/dt), and, for C invariant
with potential, dV/dt = constant for a given fixed i. Here C is in units of farads
cm- 3 .
In another way, we can write the charge remaining on the capacitor at a
time t beyond some initial condition (i) when the charge was qi as
(15.26)
so that the power density at time t after the start of discharge at i A cm- 2 will be
i
(p.d·)t = Vi - if ~ dt (15.29)
o
t
(15.30)
= i (Vi - J~ dt)
o
i
which eventually becomes zero when fb -c dt =q/C == Vi.
Alternatively, a capacitor device could be discharged under conditions of
constant power, iV = constant. For such a situation, as charge is being with-
drawn and V declining, it would be necessary to arrange instrumentally that i
= =
will be increasing in order to maintain the product iV constant, K. Then i =
K V-i so that the condition
(15.32)
(15.33)
i.e., i increases as V decreases, which is the basis ofthis case; see Section 15.4.3.
These relationships show that evaluation of power density for a capacitor is not
as simple as for an ideal battery.
In addition, as for a battery, the p.d. will decline (at a given degree of
charge, qt, held by the capacitor) with increasing discharge current density when
there are ohmic polarization losses. This will certainly be the case with porous,
high-area capacitor electrodes, especially when less conductive nonaqueous
electrolytes are employed, as in the higher operating voltage double-layer ca-
pacitors. In the case of electrochemical capacitors utilizing redox or adsorption
pseudocapacitance, additional Faradaic (Tafel-type) polarization losses will oc-
cur, as discussed earlier for the case of p.d. vs. e.d. relations (Ragone plots) for
batteries. As with battery systems, the rated power density of capacitors will de-
pend on the current drain at which the rating is evaluated; it will also depend on
the state of charge in the capacitor case, as explained above, much more so than
for most battery systems except for Li intercalation types, where quasi- or
pseudocapacitor behavior can occur (Chapter 10).
An important difference between capacitor and battery power rating is the
relation between p.d. and e.d. for these two types of electrical energy storage
systems. We have seen from Eqs. (15.23) and (15.24) that there is a direct rela-
tion between p.d. (iV) and e.d. (qV) for a given initial cell voltage since for both
cases the factor by which the cell voltage is diminished by polarization effects
with increasing current density is at least theoretically the same. However, in the
case of capacitors, the density of stored energy (for a given capacitance, C)
scales with the square of the voltage attained at the end of charge (Chapter 2)
while the power density remains linear in that voltage, although for both prop-
erties the voltage can be controllably raised (unlike the thermodynamic voltage
of a battery cell) up to or just below the practical decomposition limits for the
potential in an electrolyte solution, i.e., ca. 1.3 V for aqueous solutions or ca. 3.5
V for nonaqueous aprotic solvent solutions. This statement implies that the ratio
of e.d. to p.d. for a given capacitor is a function of potential on charge, i.e., this
ratio increases toward completion of charging, which is not normally the case
for battery cells except for the Li intercalation type and to some extent for
Ni·O·OH-Zn or Ni·O·OH-Cd battery cells. Some examples of Ragone plots cal-
culated5 for capacitors are shown in Fig. 15.9.
Power densities attainable with electrochemical capacitors vary consider-
ably, depending on the constituent materials and electrode and current-collector
design, but state-of-the-art figures are now in the range of 5 to 15 kW kg-I,
Energy Density and Power Density of Electrical Energy Storage Devices 439
104
10'
102 ----"\
..........
....
b
10'
~ R-a.t.O - - - -
Z!'
iii
c 100
~
CD R-'.D.O - - - _
...."\ '" ....
CD 10"
-=0
tI..
R-fa.o.O········· .•.
'.
10'2 C-a.UFkf'I
10"
10"
10'2 10" 100 10'
Energy-denslly (kWh kIT')
FIGURE 15.9. Calculated Ragone plots for fully charged electrochemical capacitors having a
constant Q = 1 MC kg- 1 and varied nominal C values (= 2,1,0.5, and 0.1 MF) and varied ohmic
polarization (esr = 0.01,0.1, and 1.0 ohm). Reprinted from W. Pell and B. E. Conway, 1. Power
Sources, 63, 255 (1996), with permission from Elsevier Science.
which is substantially larger than figures being quoted 4 or 5 years ago. Corre-
sponding energy densities are in the range of 8 to 20 Wh kg-I. Some ad-
vanced mixed-oxide capacitors are claimed to provide p.d.s on the order of
1000 W cm- 3 ! However, this figure seems unrealistic.
Recent performance figures from Maxwell Corp. are 3-10 kW kg-I, al-
though some other claims in the literature go as high as 15 kW kg-I. Using deri-
vatized poly thiophene conducting polymers, the Los Alamos National
Laboratory groupll has achieved a p.d. of 35 kW kg-I. For electric vehicle ap-
plications in hybrid configurations with batteries (Chapter 19), requirements for
energy density projected by the automobile industry are currently 16 Wh kg-I.
It is interesting to examine this requirement in terms of absolute electron
density per atom, assuming a carbon-based capacitor; 16 Wh kg-I is equivalent
to 16 x 3600 C kg-I at 1 V operating potential. For a 1000-m2 g-I (= 1010 cm2
kg-I) porous carbon powder capacitor electrode, this energy density at 1 V is
equivalent to a charge storage of (5.76 x 104/105 ) x 6 X lOz3 electrons per 1010
cm2, or to (5.76 x 104/10 5) x 6 X 1023/10 10 electrons per cmz, i.e., about 0.035
electrons per atom, taking the real surface of carbon to contain about 1015 atoms
per cm- z.
440 Chapter 15
Ie = zFDA(dcldx) (15.34)
where D is the diffusion coefficient, A is the electrode area, and z faradays per
mole are involved in the electrode process taking place at a diffusion-controlled
current of Ie The onset of concentration polarization at high current densities,
in addition to activation polarization, represented by a linear log Tafel plot, is
illustrated in Fig. 15.10.
The concentration gradient is established over a distance of 0.1 to 0.01 mm,
approximately, out from the electrode surface into the solution. This distance,
the diffusion layer thickness (), can be appreciably diminished by rapid stirring
or forced solution flow or, with particular convenience, by means of a rotated
Energy Density and Power Density of Electrical Energy Storage Devices 441
.
...J
<t
i=
z
lJJ
b
0..
0::
W
~ LOG [limiting-current densities, it]
I I I
I I I
RT (15.35)
Yf c = zF In(cz/c e)
iri (15.36)
C!Cb = 1 - iii/=- -.-
tl
This equation is an important basis for the development of equations for the
electroanalytical technique of polarography. Thus, as i ~ i l (the onset of full
442 Chapter 15
z
o
~
a::
I-
z
W
u
z
8
~
~
U
<t
W
a:
energy of the cell in W aU-hours, n is the E rate at which the cell was rated, and
M is again some fraction or multiple of E. Thus the power level at 0.5 EO.2 or
EO.212 for a cell rated as 1200 mWh of capacity at the 0.2 E or EI5 rate is 600
mW.
It was mentioned that the practical charge capacity is usually substantially
less than the theoretical capacity of the actual electroactive materials calculated
according to the open-circuit thermodynamic potential difference between the
anode and the cathode together with the number of gram-equivalents, i.e., the
number of faradays deliverable per mole on discharge. A histogram illustrating
this difference for a number of anode-cathode combinations is shown in Fig.
15.12.
1000
~
Level
A
~
Level
100 B
.1&&!..8
Theoretical capacity (active materials only)
~
Theoretical capacity of a practical battery
~
Actual capacity
FIGURE 15.12. Theoretical and practical charge-capacity values for battery systems shown as
histograms. 1, Leclanche dry cell; 2, alkaline-Mn02; 3, magnesium-cuprous chloride; 4, zinc-mer-
curic oxide; 5, Li-Mn02; 6, lithium-S02; 7, magnesium-cuprous chloride; 8, lead-acid; 9, nickel-
cadmium; 10, zinc-silver oxide; II, Li-Mn02. Level A, theoretical capacity (active materials only);
level B, theoretical capacity of a practical battery; level C, actual capacity. (From Linden. 12 Repro-
duced with permission of the McGraw-HilI Companies.)
Q(Ah)
1= - h - = Q (A), then P = I x V = Q x V watts; (15.37)
and
. Q(AH) 1 .
l = - h - x Tg = Q (A g-l), then p.d. = l x V = Q x V watts g-l, (15.38)
1OQ(Ah) (15.39)
1= h = 10 Q (A), then p.d. = 10 Q x V watts;
and
. IOQ 1 i x V 10QV
l=~Ah) x--= Q (A g-l), thenP=--=--= Qx V watts g-l
h 10 g 10 g 10 g
(15.40)
Energy Density and Power Density of Electrical Energy Storage Devices 447
These examples show again that on an absolute basis, different power values
arise for a given C-rate, depending on the quantity of electrochemical reactive
material. On a bulk per gram basis, the C-rate corresponds to a particular spe-
cific power, i.e., a power density related to a current density expressed on a bulk
per gram basis, I g-l, == i. This latter representation of power density in terms of
C-rate is preferred.
In practice, C (the rated capacity) is the charge determined at a specified
current (time to complete discharge down to a defined cut-off potential); unlike
an ideal situation, V will not normally remain constant and depends on the state
of charge and current density. Also, the practically available charge, Q, is usu-
ally less than the expected theoretical value according to Faraday's laws (Fig.
15.12). The cell voltage is normally a function of the state of the charge (as is
that of a capacitor for more fundamental reasons) and current density, and in-
cludes terms related to iR drop and other sources of polarization as discussed in
Section 15.1.
The activation overvoltage contribution is usually expressed in terms of
current density on a per square centimeter basis. For a 1-g sample of reagent,
nominally in a cubic form, and a density of 1 g cm- 3 , the surface area would be
q cm2 ; ~or a corresponding lO-g sample, the surface area would be 27.8 cm 2
({10 x ill x 6). Then the external-surface current densities would be, re-
spectively, for the
. IOQ(A)/1O g _ -2 (15.42)
lO-g sample. 27.8/10 g - 0.36 Q (A cm ).
terials, however, the real surface area in m2g- 1 of the starting material(s) is usu-
ally known, at least approximately, so a real current density, expressed per
square centimeter, could ideally be stated for some defined operating condi-
tions. Even then, though, a real current density evaluation is elusive since by no
means all of the pores of such porous matrices are accessible to the electrolyte
and thus to electric current (Chapter 14). The same limitation also applies to a
number of battery systems (e.g., Ni-metal hydride) in which powder-material tech-
nology is involved, and also to fuel cells where three-phase, gas/liquid/metal inter-
faces occur.6
The general situation is that the overall density of current, i, expressed on
a bulk per-gram basis for the active material, will not usually scale with the real
current density on a per square centimeter basis, especially with bulky, densely
packed electrode structures, since the fraction of available active area that is ef-
fective for passage of current will depend on current density in the case of po-
rous electrodes. The conclusion here is then that the relation between rates of
discharge (or recharge) expressed as C-rates and power levels depends on how
the involved current densities are expressed, namely, per square centimeter of
reactive surface area (or that available for double-layer charging) of the reactive
material, or per gram or kilogram of the active material, or per cubic centimeter
or meter.
100 r - - - - - - - - - - - - - - - - - - - - ,
~
(,!)
a:: BATTERY HYBRID
w 10--r-----.:;-~- - - - - - - - - - - - - - - __ _
Z "
W ' \
U \
~ \
U CAPACITOR I
~
~
(,!)
9 0.1 +------'---,.-----+------r----~
1 10 100 1000 10000
LOG [SPECI FIC POWE R 1
FIGURE 15.13. Hypothetical Ragone working diagram to illustrate the optimization of system
requirements for a capacitor-battery hybrid (schematic). Lower curve for capacitor. upper for bat-
tery component. (From Miller 4 )
10
,.--.
\
0
>-
<.!)
a::
w
z
w
u
G: , r
u
r
IJJ
Cl.
~
<.!)
9
0.1 I
0.1 1 10
LOG [SPECIFIC POWER]
FIGURE 15.14. Ragone plot for a hypothetical energy storage device depicting typical energy-
power tradeoffs in practical technology. Point a is the point for an energy-power ratio of 5. Point
b is the optimal operating point for an application requiring a nominal 25 units of energy at 25 units
of power. (From Miller. 4 )
450 Chapter 15
cally below point c where any further attempt to obtain higher power density
leads to a rapid roll-off of energy density.
When it is desired to determine the minimum size of an energy storage sys-
tem to support a constant power load, it is necessary to locate on the Ragone
curve the point that has the required energy-to-power ratio (Eq. 15.17). The
Ragone plots in Fig. 15.15, based on data from Murphy and Davis, 14 give per-
formance information on various types of capacitor and battery systems. One
proposed energy-to-power ratio for an electric vehicle has been given as 1.4
MJ/40 kW, i.e., a 36-s time response. Then the optimum operating points (see
Figs. 15.14 and 15.15) are found as the coordinates of the intersection points of
the 35-s time response discharge line with the respective Ragone plot for the de-
sired capacitor system.
100
I
,
I
I Max power '/
r--- Ni~d
NiCd 1/
/
'"---- t-- /
.-.../ I
Pb-acid -I"-
IMax power
Pb-acid DOE a~vanced goal
10
--
Maxwell
~ 3Vorganic
odE 1/ " I·~ -.;..
~ear-te~m g~, ' ..... 1
Maxwell 24V j>rg. Maxwell
24Vorganic
•
I Semi-Pac;aged
"I~
Maxwel~b r-, r-
~
1 1Vaqueous
I
'"- I
? I
Pinnacle
28V aqueous /
.1 iI
10 100 1000 10000
Wlkg
FIGURE 15.15. Ragone plots for various electrochemical capacitor and two battery systems. A
time response of 36 s for electric vehicle operation is represented by the 45° straight line, intersec-
tions of which with the Ragone relations (see also Fig. 15.13) provide the respective points for op-
timum operation of each type of system. (From Miller,4 based on data of Murphy and Davis. 14)
Energy Density and Power Density of Electrical Energy Storage Devices 451
Miller4 has also treated the problem of optimizing the hybridization of a ca-
pacitor with a battery, the essence of contemporary approaches for development
of electric vehicle power systems. 15
Figure 15.13 shows hypothetical Ragone plots for a battery and a capaci-
tor. The plot for the battery represents good energy density, much larger than
that of the capacitor, but with the latter capable of delivering energy at much
larger power densities. The aim of combining the capacitor with the battery is
to extend the energy-power performance rating of the system to that represented
by the dashed line in Fig. 15.13. This has the effect of allowing the battery's en-
ergy to be delivered at the capacitor's (higher) rate.
The capacitor must, however, be adequately decoupled from the battery in
order to achieve the possible benefits of this combination. This requirement ex-
ists because the battery's voltage during discharge varies much less than that of
the capacitor, whose voltage must diminish almost linearly with the state of dis-
charge (V =qlC), as discussed in Section 15.2.5. The required decoupling can
be achieved by dc-dc converters or resistors; in some cases just the esr of the bat-
tery itself suffices. 4
A significant improvement in battery systems other than those for electric
vehicles can be achieved, e.g., for improvement of the operating lifetime of bat-
tery power sources for a telephone. As an example, a 1.3-F capacitor connected
in parallel with an Li ion battery achieved a fivefold improvement in operating
lifetime.
A model calculation, also by MiIler,4 showed that a capacitor having a
volumetric energy density as small as 0.1 % of that of the coupled battery en-
abled the operating time of a phone (as load) to attain a maximum (Fig. 15.16)
when about 20% of the energy storage volume was used to accommodate the
capacitor component. With less capacitor volume, power deficiencies occur, so
operating time is diminished. The same trend occurs on the other side of the
maximum: when the capacitor volume is larger; then in the combined system
there is depletion of energy delivery capability. This approach by Miller pro-
vides a useful basis for optimization analyses of the behavior of capacitor-battery
hybrid systems that will have increasing importance in future technologies.
The effect of hybridizing rechargeable, high-performance batteries with
Polystar's "Aerocapacitor" was demonstrated by Juzkow, Gold, and Kraemer 17
in a series of Ragone plots. Such diagrams showed that for hybridization with
an Li ion, an Ni-MH, and an Ni-Cd battery, the inclusion of a coupled electro-
chemical capacitor has a clear and major influence in allowing high-power
drains to be achieved without the usual corresponding diminution of energy
density as a result of polarization effects. It provides a clear demonstration of
the value of hybridization of capacitors with batteries to level load and obtain
power performance much improved over individual battery systems.
FIGURE 15.16. Operating time for discharge from 4.1 to 3.0 V of an organic electrolyte capacitor
vs. fractional volume of capacitor as exemplified by use in a digital telephone unit. (From Miller. 4)
----~ 1~lc-------
where Rs is a series resistance (e.g., an esr) and any parallel leakage resistance
is infinite. A discharge current of I will lower the initial potential Vi to a value
V= Vi-IRs (15.43)
i.e.
r=
,.......,
S 0.1
E
0-
......
6
C>
ooJ
O.Ol;------,r-----.------,~--__;
o 2 4 6 B
.=t/RsC
FIGURE 15.17. Normalized power (PIPmax) plotted against the time constant T = tl RsC. The pa-
rameter r is the ratio of load resistance (RL) to series (esr) resistance Rs. (From Miller. 4)
-
c
(5
W
....... 0.1
Q)
"0
W
0.01~----------------~-----------------"
0.01 0.1
P ave/ P max
FIGURE 15.18. Delivered energy (relative to total energy) vs. normalized average power
(PavIPmax ) for a series RC circuit discharged at constant current from an initial voltage Vi to V;l2.
(From Miller. 4)
Energy Density and Power Density of Electrical Energy Storage Devices 455
0.8
"ii 0.6
"0
W
......
<II
"0 0.4
W
0.2
------ - - - ----
--- - .... "-
,
\
\
--
\
c \
\
0
\
0.1 \
W
\
"- \
Qj
"0 I
FIGURE 15.20. Ragone-type plot for reduced delivered energy vs. reduced average power for the
five-unit distributed Rand C network shown above. The behavior of the series RC circuit is shown
by the dashed line. (From Miller. 4)
0.8
Qj
-0 0.6
W
......
II)
-0 0.4
W
0.2
FIGURE 15.21. Relative dissipated energy curve vs. reduced power for the five-unit distributed
Rand C equivalent circuit. The dashed line is the behavior of the series RC circuit (cf. Fig. 15.20).
(From Miller. 4)
3. Constant power: The current during the discharge increases as the bat-
tery or capacitor voltage decreases, thus discharging the system at a
constant power level (power = current x voltage) (see Section 15.4.3).
c
t I
~ Constant power :
a) ~ ....C....onstant curre~~'),..- .. )..;
~~~----~-~~~~~
~ ~onslanl resislonce> ........ ~
0'------------"'-
Discharge t i m e -
b)
i . .~-~-:.~.:..::.::::.'-. .:>. :
'0 Conslonl currenl / ~
> I
Q) Conslont resislance I
u
Discharge time_
onslonl resistance I
t. . .... / I
'~.... Constant power I
~~-- \ I
c) ,,-,,-,,- -'~::-"-"I
FIGURE 15.22. Discharge profiles under different discharge modes for the same average current:
(a) current profile during discharge, (b) voltage profile, and (c) power profile. (Based on plots
shown by Linden 12 ; schematic.)
charge. Under such a condition, the service or discharge time is about the same
for each mode. From an application point of view, the most realistic case is the
assumption that the power under all three modes of operation is the same at the
end of the discharge.
On a scale of power density plotted against the logarithm of the current
density, the falloff of p.d. with increasing current density is very sharp. This
happens, of course, when the sum of the polarization terms becomes comparable
with, but still smaller than, the iV product for high i values. On a linear scale of
i values, the drop off of p.d. looks less abrupt. When the polarization terms be-
come equal to iV, a power shutdown occurs since there is effectively no voltage
available in the system; a kind of short-circuit current still passes but at a voltage
V ~ 0; hence power formally becomes zero.
Note that for a battery cell containing two electrodes, the Tafel polarization
term, i(a + b log i), in the p.d. equation is composed of two terms, one for each
cell half-reaction; the a and b Tafel parameters are not normally identical for
such a combination, and one half-cell process may also be subject to concentra-
Energy Density and Power Density of Electrical Energy Storage Devices 459
tion polarization more than the other, depending on the electroactive reagents,
their concentrations, and the electrode-process mechanisms that obtain.
IV=K (15.50)
The time-dependent current is
1= CdVldt (15.51)
and therefore must increase as V declines (dVldt negative) during the discharge.
This situation therefore differs from the constant power discharge of an ideal
battery. The power will be given by
I x V =-CVdVldt =K (15.52)
or
-CVdV=Kdt (15.53)
Integrating
CV2 (15.54)
--=-Kt+c
2
CV[ (15.55)
c=--
2
Then
(15.56)
so that
(15.57)
(Vi> V)
is the condition for the variation of potential in time for constant power dis-
charge of a capacitor, the specific capacitance of which has been assumed to be
independent of V, an ideal case. It is seen from the above final result that for a
given constant IV power product (= K), the variation of (Vr - V2) with time
scales with 2KIC, i.e., at larger constant power drains, a shorter time scale for a
given C value will obviously be required to discharge the capacitor at that con-
stant K, compared with a smaller K rate.
It is seen that Eq. (15.57) can be rewritten to represent the difference of en-
ergy stored initially at Vi and that at V, after some time t, divided by that time.
This difference is an overall power quantity (energy divided by time for deliv-
ery), represented by the selected K rate.
The variation of current with time must be the inverse of the variation of
potential for constant power discharge conditions, i.e.,
and
of discharge through a load leakage resistance when V ---7 0 only as t ---7 00 (see
Chapter 18).
The cutoff time needed for the potential V across the capacitor to reach the
cutoff value of zero at a constant power drain of K watts is easily found from
Eq. (15.56). Thus, for V = 0:
(l/2)CVr = Kt (V = 0) (15.60)
i.e.,
=G/K (15.62)
where Gi is the initial (electrostatic) Gibbs energy stored by the charged capaci-
tor. As expected, t(V = 0) becomes smaller as K, the constant power drain, be-
comes larger.
In practice, a cut-off time on a test may be chosen for V to be above zero
but it should be some limit V less than Vi, namely, Vi > V> 0, commonly V =
0.5 Vi. The cut-off time for complete discharge is obviously the time corre-
sponding to exhaustion of all the initially stored (l/2)CVr free energy, con-
sumed at a constant power drain of IV watts (see Eqs. 15.52 and 15.61).
Related to the analysis given above for the power density of capacitors,
Rudge et al. ll made an empirical power-density evaluation of a poly-3-(4-
fluorophenyl) thiophene (PFPT) conducting polymer-based pseudocapacitor by
dividing the experimentally determined energy density of the system by the de-
termined RC time constant (= 4 s) calculated from the results of charging and
discharging a pair of electrodes made from the above material. A figure of 35
kW kg-I resulted, which is substantially larger than current goals for electro-
chemical capacitor performance for electric (hybrid)-powered vehicles. I8 These
polymers are thus very promising capacitor materials (see Chapter 12), pro-
vided electro-organic degradation side reactions do not limit their cycle life,
which should be >105 . Equation (15.56) evidently represents the difference of
stored energy in the capacitor as V declines from Vi during a time interval, t,
down to a cut-off limit when V = 0, i.e., for all the stored energy to have been
consumed in the constant power discharge regime.
In the galvanostatic mode, the situation is simpler since I = constant and V
declines with time according to the charge remaining on the capacitor after the
J
charge l.dt has been consumed. The power associated with the discharge proc-
ess is then [(constant) x Vet), which declines continuously according to the de-
cline of Vet) with t given by
462 Chapter 15
I
(15.64)
= [q(initial) - f I.dt)/C
o
S=-dGldT (15.69)
For a given value of Von charge, it is only C that can have a temperature de-
pendence, i.e., a derivative with respect to T.
It was shown in Chapter 6 that the double-layer capacitance is a complex
quantity determined by the geometry of the compact Helmholtz layer, the size
and solvation of cations and anions, and the field-dependent orientation of sol-
vent dipoles in the interfacial field, as well as electronic effects connected with
potential-dependent electron-density overspill (Chapter 7). The solvent dipole
orientation effect can be formally treated in terms of an interphasial dielectric
permittivity K which will be temperature dependent, usually diminishing with
increasing temperature. 19,20 This mainly reflects diminishing orientational di-
electric polarization with increasing temperature in a given interphasial field.
Since C is represented formally as
(15.70)
per unit area, where the dielectric constant, B, is the relative permittivity KIKo,
with KO being the permittivity of free space referred to in Chapter 5. Therefore,
with B tending to decrease with increasing temperature and d, the effective
thickness of the compact layer, tending to increase due to thermal fluctuations
of the structure of the interphase, C will usually tend to decrease with increasing
temperature.
Therefore, at a given voltage on charge, the electrostatic energy of the dou-
ble layer will tend to decrease with temperature so that dGldT will be negative.
464 Chapter 15
Hence, with Eq. (15.69), the electrostatic entropy of the double layer21 - 24 will
tend to increase with temperature. This can be interpreted in a qualitative way
as the result of higher temperature opposing ordered electrostatic orientation
and electrostriction2o,25,26 in the double layer. There will also be an entropy con-
tribution from the series diffuse double layer capacitance, but for the strong
electrolyte solutions usually used in the operation of electrochemical capacitors,
the reciprocal contribution (Chapter 6) of this diffuse-layer capacitance will be
negligible in the overall interfacial capacitance.
Various theoretical treatments of the entropy of the double layer at elec-
trode interfaces have been given in the literature 21 ,22 and are based on the sol-
vent dielectric properties in the interphase and the related dipole orientation
behavior in the interphasial field. This area is, however, outside the scope of this
chapter. Suffice it to say that the entropy of the double layer is some 20 to 40 J
K- 1 mol- l more negative at appreciable charges than at the potential-of-zero
charge and depends on whether anions or cations are preferentially populating
the double layer.23,24 These figures correspond to T/)"S quantities in G of about
6 to 12 kJ mol-I, a not-insignificant contribution.
Some practical attention has, however, been given to the entropy of the
double layer as a function of extent of charge. By analogy with the phenomenon
of adiabatic demagnetization (the relaxation of magnetic dipole polarization)
employed to attain very low temperatures near zero K, it has been suggested that
a similar effect could be utilized for cooling (but not near zero K) an electrolyte
by allowing the interphasial dielectric polarization in large-area double-layer
capacitor devices to relax adiabatically with the expected absorption of heat
from the surroundings, determined by a T/)"S quantity. However, unlike mag-
netic dipole relaxation, the relaxation of electrostatic dipole orientation polari-
zation in a double layer must be coupled with relaxation of accumulated ionic
and electronic surface charges at the interface. Forced discharge to achieve rapid
decay of interfacial polarization, leading to absorption of heat, will tend to be
opposed by inevitable [2R losses generating joule heating in opposition to the
cooling caused by dielectric depolarization.
(15.71)
Thus, in a series stack, say, often IF capacitor units,(1/C);= 10 x (1/1) so that the
overall C is only 0.1 F! However, for a I-V rating of each unit, a 10-V combination
results and the energy stored in each unit at 1 V is 112 x 1 F x (1 vi;= 0.5 J, inde-
pendent of the series connection. Were the 10 units connected in parallel, the stored
energy would be 10 x 112 x 1 F x (1 V)2;= 5 J, the same as the total for the se-
ries-stacked combination. This is a requirement of the principle of conservation
of energy since energy cannot be lost or gained by switching a charged parallel
combination of capacitors to a series one.
In the case of electrolytic capacitors, the operating voltage can be up to 200
V per unit having a capacitance of, say, 100 flF. The stored energy at 200 V in
such a unit would be 100 X 10-6 F x (200 V)2 x 112;= 2 J, which is not too much
different from that for the example of the 1-F electrochemical capacitor charged
to the nominal potential difference of 1 V!
With a parallel combination of many such high-voltage electrolytic capaci-
tors and each combination being coupled severalfold in a high-voltage series, a
good e.d. system could be constructed. The practical problem for EV applica-
tion would probably be the volume required using this arrangement, compared
with that for multiply stacked electrochemical capacitors of much higher intrin-
sic specific capacitance but much lower voltage rating, Ll V. Any advantage for
the electrolytics, apart from disadvantageous volume requirements depends, in
order of magnitude, on how 10-6 (i.e., on the order of microfarad units) com-
pares with (Ll V)2 based on Ll V being on the order of 100(V) at least. Of course
even 100-mF electrolytics are today not too large.
Another aspect of the electrical behavior of electrolytic capacitors is their
quite low equivalent series resistance (the esr discussed in Chapters 14 and 16
for porous capacitor electrodes). This means that they have a good high, as well
as low-frequency response behavior without the limitation of large RC time
466 Chapter 15
constants (Chapter 16) for inner surface area regions that are electrically, rela-
tively isolated by appreciable electrolyte resistance in interparticle pores (see
Chapter 14). Then the power-density performance aspect of electrolytic capaci-
tors will be expected to be superior to carbon double-layer embodiments. This
is another significant advantage over the latter type of capacitors, especially for
situations where short-pulse transient behavior is technologically desirable in
certain applications. Applications substituting electrochemical capacitors for
high-voltage operating requirements will, however, have to avoid the intrinsic
polarity associated with electrolytic capacitors, but that could be advantageous.
Further evaluations of these possible advantages are desirable.
Finally, in the context of this section, the development of the so-called
"Hybrid" capacitor by the Evans Corp. must be mentioned. This rather original
device is a hybrid combination (U.S. Pat. No. 5,369,547) of an anodic oxide film
electrolytic capacitance (anode electrode ofTa-Ta20s) together with a relatively
high electrochemical capacitance (the other pole) of the oxide film (RU02) type
as cathode pole. A high potential difference is sustained across the thin, anodi-
cally formed, barrier-layer oxide film and a low potential difference across the
other capacitative film so that no significant electrolyte decomposition can set
in. Good capacitance values (e.g., 0.68 F) in a small, thin disk device are
achieved with operating voltages of 100-150 V. With scaleup, these devices
may offer some opportunities in the EV power-train field.
The advantageous basis of the Evans "Hybrid" capacitor has to be consid-
ered in relation to the common technology of fabrication of Ta or Al electrolytic
capacitors. Such devices employ a thin, inSUlating, anodically formed oxide
film on the electrode metal, e.g., Ta or AI. Usually, these capacitors are asym-
metric, employing dissimilar anode and cathode materials. In these the dielec-
tric oxide film on the anode is the thickest and sets the working voltage of the
unit. In preparation of the oxide films, the support metal is anodized at a certain
voltage and the oxide film grows to a certain thickness at that voltage, until the
rate of further extension of the film becomes negligible. The growth follows one
of the logarithmic laws of oxide film development. 27 ,28 Typically, the anodic
oxide films at Al or Ta can sustain a potential difference of 100 - 200 V across
them in the final quasi-steady state.
The complementary cathode usually has a higher capacitance because of
its greater surface area, but the masses are commonly similar. Manufacturers use
the highest specific surface area materials for cathodes because these materials
are ,best for low voltage anodization.
The thinner dielectric film at the cathode and its substantial real surface
area cause the cathode capacitance (Cc ) to be higher than the anode capacitance
(Ca ). Then since the overall capacitance, C, is determined by the series equiva-
lent circuit of the device, namely,
Energy Density and Power Density of Electrical Energy Storage Devices 467
1.=_1 +~ (15.72)
C Ca Cc
and since Cc »Ca , the overall C is determined by the Ca across which the high
voltage can be sustained. The device capacitance always approaches the smaller
value of the two component electrode film capacitances owing to the nature of
the relation (15.72).
Because the electrochemical capacitor cathode in the hybrid requires little
volume, available space can be used to double the size of the anode. The result,
in the Evans device, is a capacitor with four times the original energy density.
A Hybrid capacitor occupies about one-fourth the volume and needs only about
one-fourth the amount of raw material required for a production electrolytic ca-
pacitor.
The anode is a pressed-sintered disk made from high capacitance density,
high-purity, commercially available tantalum powder. Formation of the tanta-
lum pentoxide dielectric was done electrochemically in the usual way. This
yields a high specific-surface-area porous electrode pellet with an integral di-
electric oxide coating. The high-capacitance pseudocapacitor cathode was pre-
pared on titanium foil according to a recipe developed to yield electrodes having
about 6 mF cm-2 of electrode area.
A complex-plane, impedance spectroscopy plot for this device is shown in
Fig. 15.23 and exhibits the typical frequency response of a transmission-line,
multiple time-constant (RC) system. The device becomes almost purely capaci-
4
.100 flHz
•
(/)
E
.c.
•
0
: ......
2- .200
N
I •
0400
.o:soo
0
••' 1600
(,9.4 kHz
I
0 2 4
Z'lohms
FIGURE 15.23. Complex-plane impedance for the Hybrid electrolytic capacitor of the Evans
Corp.
468 Chapter 15
90
0~
.......
CI)
(.)
c 80
0 '0.
+-
'u
0
0.
0
U Large particles
70
u
OJ
N
0
E
.... '0..
0 60 -
z
"'0
500
FIGURE 15.24. Achieved relative capacitance vs. discharge current in a double-layer capacitor
fabricated from small D or large 0 particles. (From Reichman and Msotek?9)
Ragone-type plots were constructed for four resistance values ("0.0", 0.5,
and 1.0 ohm cm2) associated with a capacitance of 5.5 F cm-2 (F cm-3) (Fig.
15.26). The power range was ca. 70 to 1580 W kg-I. The Ragone characteristic
curves were derived29 according to the following equations:
with
i == [C dVldt]/[RCIdt + 1] (15.75)
or
C (15.76)
dt = --;-. dV - RC
I
470 Chapter 15
o~
.....
W
u (c)
2
~
U
~
<t
U 75
w
>
i=
<[
-I
W
0::
60
o 2
FIGURE 15.25. As in Fig. 15.24 but for (a) low 0, (b) medium 0, and (c) high <> electrolyte con-
centrations (esr effect; concentrations unspecified). (From Reichmann and Msotek. 29 )
Note that their Eq. (15.73), with 112, does not seem correct as written. The re-
lation for R = 0 is the vertical line in Fig. 15.26 since no diminution of operating
voltage with increasing current (power), i.e., no iR drop, occurs in this case.
Another practical aspect of the importance of internal resistance is as fol-
lows. As in battery construction, the maximization of volume energy density of
electrochemical capacitors is required, together with the minimization of esr.
This would normally be achieved by compaction of the matrix material under
mechanical pressure during some stage of the manufacture. However, while
compaction will help to minimize interparticle resistance in carbon-based
double-layer capacitors, compression can have the effect of squeezing out
the electrolyte, thus diminishing the active pore area accessible for inter-
facial charge accumulation. Hence careful optimization of fabrication con-
ditions is required in the construction stages of capacitor devices.
Typical battery and capacitor e.d. and p.d. requirements for electric vehicle
applications have been examined by Haskins and Dzieciuch30 for the U.S. Ad-
vanced Battery Consortium and are summarized in Tables 15.3 and 15.4. Circuit
response equations were solved numerically for both constant-power pulses and
for the FUDS cycle dynamic-load profile. Figure 15.27 shows pulse power re-
sults plotted in a way that allows general relative sizing of capacitors for a range
of power requirements. The effects of finite esr are included in this figure. Be-
low about a 2-to-l ratio of peak pulse to sustained power, esr does not strongly
Energy Density and Power Density of Electrical Energy Storage Devices 471
1600
1200
Ie> 800
.><:
::......
....
Q)
~
0
a.. 400
A typical response of the circuit to that part of the FUDS profile with the
maximum overall power is shown in Fig. 15.28. The achieved diminution of re-
quired battery peak power is apparent; also, the fact that the battery is not re-
quired to accept any high-rate regenerative power is an advantage; such
transients are mostly accepted by the capacitor. This situation contributes posi-
tively to the operating life expectancy of many traction batteries.
Burke31 reported a useful comparison of battery power drain in kilowatts,
amperes, and volts in an electric-vehicle FUDS test conducted at INEL with a
w
)( ~
wI- ESR/BATTERY RESISTANCE = 0.2
U W
ZIIl
3
0.1 ~
<t-1
I-=>
!Q(l.
Ill'
W w 2
a:u
~~
wI-
I-u
I-<t
<t(l.
1D<t
u 0.5
1.5 2 2.5 :3
PEAK PULSE POWER/SUSTAINED POWER
FIGURE 15.27. General results for capacitor sizing for three esr capacitor-battery resistance
ratios, r, in a hybrid electric vehicle application. (From Haskins and Dzieciuch. 30 )
Energy Density and Power Density of Electrical Energy Storage Devices 473
60
50
s::.
~40
"-
fJ 30
1JJ
Q.
en 20
10
:=
~
"-
a::
1JJ
:=
~ 0f--"-t+-------"--4J++-It-.-F=-
FIGURE 15.28. Typical response of a battery-capacitor hybrid energy delivery system to maxi-
mum overall power requirement in the FUDS cycle. (From Haskins and Dzieciuch. 30)
capacitor-battery hybrid power source. The watt-hour energy capacity was SOO.
The resulting advantageous behavior is clearly shown in [Fig. 1S.29(b)], with
the capacitor in comparison to the battery behavior without capacitor load lev-
eling [Fig. IS.29(a)]. The power-drain spikes for acceleration or hill climbing
were up to ca. 50 kW, while with the coupled capacitor they did not exceed 14
kW [Fig. 1S.29(b)]. Capacitor power spikes reached about 30 to 4S kW. Pulsed-
power systems are envisaged for such capacitor-battery hybrid coupling.
The advanced electric vehicle goals that have stimulated large, high-power
electrochemical capacitor design and construction (e.g., by Maxwell Laborato-
ries at Auburn University), were as of 1991: energy density 100-200 Wh kg-I;
peak power density, lSO-300 W kg-I, distance life, SO,OOO-lOO,OOO miles. The
cost was estimated at $100-150 per kilowatt-hour. These requirements are now
revised upward, but with cost estimates lower.
Continuing, possibly similar, electric vehicle requirements in up to eleven
northeast states and the District of Columbia have led to a 1991 projection by
Automotive News for annual sales of electric vehicles to be over 100,000 starting
in 1998, rising to over SOO,OOO by the year 2003. However, in the year this was
written (1996), the first projection seems now to be either exaggerated or opti-
mistic, and can depend on the contemporary political and economic climate.
More recent estimates (1998) by the Electric Vehicle Association of the Ameri-
cas for sales in Japan and the US of electric vehicles and hybrid electric vehicles
474 Chapter 15
60 o} Without supercopacitor
Battery
Power/kW
Amps
Volts
100
Time or distance-
b} With supercapacitor
30 (Wh) cap = 500
Battery
Power/kW
Capacitor
Power/kW
Time or distance--
are 17,500 and, in Asia, greater than 25,000 electric motor scooters. In Europe
(France), electric vehicle sales in 1998 have been around 6000.
It has been realized for some time that energy can be stored by electrome-
chanical transduction using a flywheel coupled to an electric/motor generator.
The system then becomes an electromechanical battery with the state of charge
determined by angular momentum; this is easily recordable in terms of angular
Energy Density and Power Density of Electrical Energy Storage Devices 475
2.5r----------~1---r-------,.----------------------/~--------.
I University of Texas / /
I
I Center for Electromechanics. /
I
I
,I /
/
I I
I /
2.0 P/E~ 2 /
I PIEI =100 /
I I /
I I I
I PIE = 50
-'
I
I
I
I ,I /
/
I I I /
I I I /
....... I I
WOfid P/.E =25-
>-
f-
(fi
Z 1.0
I
I " I I
I
I
Flywheel
/Consortium --
W
o
Magn~t
M9t~r
/
LI
•
:,,-,..--_~-=-- ______ -:;-::"-~-----
nique-'
a: I •
w / / . / • Mobility
II / PIE -10-
0.5
~ Rocketdyne
II / -' -' •
-
United Technologies
- - - - -American
0.. IX/ / -,' -~ Research C~t~r __
1/1/"' ... , - - ---
• Flywheel Systems
~ . .:----
o 10 20 30 40 50 60
ENERGY DENSITY / Wh kg~l
FIGURE15.30. Ragone-type diagram for power density vs. energy density for selected flywheel
systems. (From Belager. 32)
REFERENCES
1. Report of the Panel on Electrically Powered Vehicles to the Commerce Technical Advisory
Board, U.S. Dept. of Commerce, October 1967. (Library of Congress Code: TO 886,5 U.S.
1967, V; I.)
476 Chapter 15
2. The Automobile and Air Pollution, Part II, Sub-panel Report to Panel on Electrically Powered
Vehicles, Commerce Technical Advisory Board, U.S. Department of Commerce, December
1967. (Library of Congress code: FC US 1 DC, 67A71.)
3. D. V. Ragone, in Proc. Soc. Automotive Engineers Conference on Rev. of Battery Systems for
Electrically Powered Vehicles, Society of Automotive Engineers, Warrendale, PA. (1968).
4. J. Miller in Proc. Fifth IntI. Seminar on Double-Layer Capacitators and Similar Energy
Storage Devices, S. P. Wolsky and N. Marincic, eds., Florida Educational Seminars, Boca
Raton, Fla. (1995).
5. W. Pell and B. E. Conway, J. Power Sources 63,255 (1996).
6. J. O'M. Bockris and S. Srinivasan, Fuel-cells: Their Electrochemistry, McGraw-Hill, New
York (1969); see also S. Srinivasan and H. D. Hurwitz, Electrochim Acta, 12,495 (1967) .
7. R. de Levie, Electrochim. Acta. 8,751 (1963).
8. B. E. Conway in Proc. Fifth IntI. Seminar on Electrochemical Capacitors and Related Energy
Storage Devices, S. P. Wolsky and N. Marincic, eds., Florida Education Seminars, Boca
Raton, Fla. (1995).
9. 1. D. Bernal and R. H. Fowler, J. Chem. Phys., I, 515 (1933).
10. B. E. Conway, 1. O'M. Brockris, and H. Linton, J. Chem. Phys. 24, 834 (1956).
11. A. Rudge,l. Raistrick, S. Gottesfield, and J. P. Ferraris, Electrochim. Acta 39,273 (1994).
12. D. Linden, ed., Handbook of Batteries, 2nd. ed. McGraw-Hill, New York (1995).
13. D. V. Ragone, B. M. Barnett, and 1. M. Bentler in Proc. Twelfth Inti. Seminar on Primary and
Secondary Batteries and Applications, Florida Educational Seminars, Boca Raton Fla. (1995).
14. T. C. Murphy and P. B. Davis, Extended Abstracts, Battery Division, 188th Electrochemical
Society Meeting, pp. 112-113, Electrochemical Society, Pennington, N.J. (1995).
15. A. F. Burke, in Proc. Fourth IntI. Seminar on Double-Layer Capacitors and Similar Energy
Storage Devices, S. P. Wolsky and N. Marincic, eds., Florida Educational Seminars, Boca
Raton, Fla. (1994).
16. 1. R. Miller, Extended Abstracts, Battery Division, 188th Electrochemical Society Meetings,
pp. 106-107, Electrochemical Society, Pennington, N.J. (1995).
17. M. Juzkow, S. Gold, and B. Kraemer, in Proc. Sixth IntI. Seminar on Electrochemical
Capacitors and Related Devices, S. P. Wolsky and N. Marincic, eds., Florida Educational
Seminars, Boca Raton, Fla. (1996).
18. A. F. Burke, in Proc. Second IntI. Seminar on Double-Layer Capacitors and Similar Energy
Storage Devices, S. P. Wolsky and N. Marincic, eds., Florida Educational Seminars, Boca
Raton, Fla. (1992).
19. 1. B. Hasted, Aqueous Dielectrics, Chapman and Hall, London (1973).
20. B. E. Conway, Ionic Hydration in Chemistry and Biophysics, Elsevier, Amsterdam (1981).
21. B. E. Conway and L. G. M. Gordon, J. Phys. Chem., 73, 3609 (1969).
22. H. D. Hurwitz, S. Sanfeld, and A. Steinchen-Sanfeld, Electrochim. Acta, 9,929 (1964).
23. G.1. Hills and S. Hsieh, J. ElectroanaI. Chem, 58, 289 (1975).
24. G. J. Hills and R. Payne, Trans. Faraday Soc., 61, 326 (1965).
25. B. E. Conway, 1. E. Desnoyers, and R. E. Verrall, J. Chem. Phys., 43, 243 (1965).
26. 1. Padova, J. Chem. Phys. 40,691 (1964).
27. N. F. Mott and H. Cabrera, Rept. Prog. Phys., 12, 163 (1948).
28. L. Young, Anodic Oxide Films, Academic Press, New York (1961).
29. B. Reichman and R. Msotek, in Proc. First IntI. Seminar on Electrochemical Capacitors and
Similar Energy Storage Devices, S. P. Wolsky and N. Marincic, eds., Florida Educational
Seminars, Boca Raton, Fla. (1991).
30. H. 1. Haskins and M. A. Dzieciuch, in Proc. First IntI. Seminar on Electrochemical Capacitors
and Similar Energy Storage Devices, S. P. Wolsky and N. Marincic, eds., Florida Educational
Seminars, Boca Raton, Fla. (1991).
Energy Density and Power Density of Electrical Energy Storage Devices 477
31.. A. Burke, in Proc. First Inti. Seminar on Electrochemical Capacitors and Similar Energy
Storage Devices, S. P. Wolsky and N. Marincic, eds., Florida Educational Seminars, Boca
Raton, Fla. (1991).
32. M. Belager in Proc. Sixth Inti. Seminar on Double-Layer Capacitors and Similar Energy
Storage Devices, S. P. Wolsky and N. Marincic, eds., Florida Educational Seminars, Boca
Raton, Fla. (1996).
Chapter 16
AC Impedance Behavior of
Electrochemical Capacitors and Other
Electrochemical Systems
16.1. INTRODUCTION
and any potential-dependent Faradaic resistance (Eq. 16.5) the system may ex-
hibit, to be separately evaluated. The evaluation of esr for various electrode
structures and choices of electrolyte (Chapter 13) is especially important for de-
vice design and optimization of power density. In addition, for favorable con-
ditions, the pseudocapacitance of an electrode can be distinguished from
double-layer capacitance over a range of frequencies, which is sometimes a mat-
ter of practical significance.
Since some applications of electrochemical capacitors are for low-frequency
electrical filtering and for other uses in electronics, ac impedance measurements
give direct information on device performance for such purposes. In the regime of
response behavior to time-dependent potentials, the method of so-called "alternat-
ing current" (ac) impedance spectroscopy has become a principal procedure for ex-
amining fundamental and applied aspects of electrochemical capacitor
behavior. Experimentally, however, it is the potential that is modulated (typi-
cally by i> 5 mV) over a wide frequency range. The term "spectroscopy" has be-
come used in this field because the electrical and kinetic response of
electrochemical systems is determined over a wide range of frequencies that are
applied to modulate the system, and various kinetic or associated electrical "re-
laxation processes" can be characterized as in other types of spectroscopy. For
example, there are close analogies to dielectric absorption spectroscopy and di-
electric relaxation, as in the work by Cole and Cole. l Basically the magnitude and
phase relation of an ac current generated in response to an applied low-amplitude
(5 mV) alternating voltage (av) is evaluated and recorded by some phase-sensitive
recording device or other kind of apparatus. Two commercially available instru-
ments currently used for this purpose are the Solartron Frequency Response Ana-
lyser system, made in the United Kingdom or the EG and G system, available
in North America. Various other systems are produced in Germany or the
United Kingdom. The principle of operation of the Solartron system differs
from that of phase-sensitive, "lock-in" instruments.
The analysis and interpretation of the ac response behavior of an elec-
trode/solution interface, i.e., the "impedance spectroscopy" of the system, as in
an electrochemical capacitor, is usually carried out by one or another of the fol-
lowing procedures:
recognized on the basis that: (1) an ohmic resistance, R, component has a fre-
quency-independent impedance, Z' = R, with a phase angle of zero while (2) a
pure capacitance component, C, has a frequency-dependent imaginary imped-
ance Z" = l/jOJC == -j/OJC with a phase angle of 90° at all frequencies with zero
impedance as OJ -t 00 and infinite impedance as OJ -t O. Combinations of Rand
C components have a complex dependence of their Z on OJ and exhibit a fre-
quency-dependent phase angle.
A useful summary of the frequency-response behavior of various equiva-
lent circuits has been given by Gabrielli in a publication of the Solartron Instru-
mentation group titled "Identification of Electrochemical Processes by
Frequency Response Analysis" (1980). *
Electrode-solution systems, especially those involving porous, high-area
materials, as in electrochemical capacitors or batteries, have complex combina-
tions of C and R components and also some pseudoinductive (L¢!) behavior. For
electrode-solution systems, the interfacial impedance is associated with (1) a
double-layer capacitance, Cdl (ubiquitously present-see Chapter 6); (2) a so-
lution resistance, R s ' in series with the electrode interfacial impedance; and (3)
a Faradaic impedance, ZF, associated with any potential-dependent Faradaic
charge-transfer resistance, RF (see later discussion) and pseudocapacitance, C¢!.
This latter can arise when the electrode/solution interface is not ideally po-
larizable so upon polarization, some potential-dependent Faradaic current
passes, leading in some cases (e.g., for cathodic H2 evolution) to a pseudoca-
pacitance associated with potential-dependent coverage by adsorbed species
(H) involved in the Faradaic reaction. The distinction between ideally po-
larizable, purely capacitative electrode interfaces and Faradaically leaky inter-
faces (also exhibiting double-layer capacitance) was explained in Chapter 6.
An electrochemical double-layer capacitor would have an ideally capaci-
tative (i.e., ideally polarizable) double-layer capacitance. However, in practice
this is rarely the case, so real systems have some ohmic solution resistance,
some ohmic interparticle contact resistance, and often (at high potentials on
charge) some Faradaic leakage resistance due to overcharge or to Faradaic redox
reactions caused by impurities (see Chapter 18).
The impedance associated with a Faradaic reaction arises as follows. The
current density, i, as a function of overvoltage " is given by the Butler-Volmer
equation (Chapter 3)
"The author's address at that time was CNRS Laboratoire GR4 Physique des Liquides et
Electrochimie, Universite Pierrre et Marie Curie, 4 Place lussieu T22, 75230 Paria Cedex 05,
France. The addrews of Solartron, the publishers of this useful short monograph, is The Solartron
Electronic Group Ltd., Famhorough, Hampshire, GU 147 PW, England.
AC Impedance Behavior of Electrochemical Capacitors 483
where io is the exchange current density passing in both directions of the reac-
tion at equilibrium (zero overpotential '7) and fJ is a barrier symmetry factor usu-
ally near 0.5 for simple electron transfer processes. (More generally, fJ may be
replaced by the transfer coefficient, a, for more complex reaction mechanisms.)
....
The tw~ terms in the brackets, multiplied by i o, are the forward (i) and back-
ward (i ) components of the net current density, i:
~ <- (16.2)
i=i-i
Sufficiently near equilibrium (i.e., for small overvoltages of 5 m V), the expo-
nentials ofEq. (16.1) can be linearized to the first term of a Taylor series expan-
SIOn, glVlng [for fJ'7F1RT or (l-fJ)'7F1RT« 1) (cf. Eqs. 3.20 to 3.23 in
Chapter 3)]
i.e.
i = io'7F1RT (16.4)
Rs
484 Chapter 16
more complex equivalent circuits (considered later in this chapter and in Chap-
ter 17 for porous electrodes), and for an electrode process or a Faradaically leaky
interfacial capacitance (double-layer capacitance as in a double-layer type of
electrochemical capacitor).
RF as written above is the Faradaic resistance at the reversible potential.
However, the rate ofthe Faradaic leakage, according to Eq. (16.3), is dependent
on the overvoltage, ", so RF has other potential-dependent (lower) values at fi-
nite "s.This can also be verified through impedance experiments conducted at
various finite, potentiostatically controlled, dc-level overpotentials where the
electrode process is no longer at equilibrium. When such an experiment is con-
ducted, the diameters of the semicircles of the Z" vs. Z' complex-plane plots for
a range of frequencies decrease with increasing" since RF is decreasing. This
change corresponds (when logs are taken) to a Tafel plot for the electrode proc-
ess. An example is shown schematically in Fig. 16.1.
Far from equilibrium (" FlRT» 1), only the first term in the brackets of
Eq. (16.1) is significant (or for opposite polarization, the second); then the Tafel
equation in exponential form is recovered. Thus,
av modulation can still be applied around some imposed 1] value that is associ-
ated with the current density i'l. Then, for a small modulation of /:l.1] to 1] + /:l.1],
say, and for non-small" values,
i
FIGURE 16.1. Complex-plane plots of -Z" vs. Z for a parallel RFC circuit (with series resistance,
Rs) where RF changes with potential for a Tafel-type Faradaic process; schematic.
AC Impedance Behavior of Electrochemical Capacitors 485
For sufficiently small D.17, linearization of the exponential term in D.17 gives
(16.9)
ilJ+!l1J can be represented by ilJ + D.i, the latter being the response current-density
increment due to D.11, i.e.
Then
so that
(16.13)
Since i" is greater than io by the Tafel exponent, RF,IJ < RF , i.e., for '1 =°at equi-
librium. In fact, since ilJ = io exp P'1FIRT for appreciable '1 values,
(16.14)
(16.15)
FIGURE 16.2. Rotating vector (2) representation of time dependence of an alternating voltage
signal at frequency f rad s-I, =wl2n Hz.
AC Impedance Behavior of Electrochemical Capacitors 487
Hence
so that I(t) is in phase with V(t), i.e., I and V are related in the same way as for
a dc circuit.
Figure 16.3 shows the relations of I and V(t) as functions of t. The corre-
sponding rotating vector diagram for this situation for a resistance is shown in
Fig. 16.3(c). Note that V(t) and I lie on the same vector in wt.
In the case of a capacitance C (Fig. 16.4), such as a pure, ideally polarizable
electrochemical double-layer capacitance, the instantaneous charge q on the ca-
pacitor is
The corresponding charging current, i.e., the rate of passage of charge q with
time t, will be
1= dq I dt = wCVocos wt (16.21)
Alternatively,
l.w
-------- t
c R b
lo) l c)
FIGURE 16.3. Relation of I and V to time in an alternating voltage signal across a resistance R:
(a) circuit, (b) signals, and (c) rotating vector diagram.
488 Chapter 16
I.w
1 ------
FIGURE 16.4. Relations of I and V to time in an alternating voltage signal across a capacitance
c: a) circuit; b) signals; c) rotating vector diagram (lout of phase with Vby -90°).
I(t) = CdV(t)/dt
=wCVocos wt (16.22)
and the maximum current Imax (or current amplitude) is evidently then
and define an impedance Zc as lIwC. Because the current I is out of phase with
the voltage V, we write the impedance Zc as IljwC where j =-{1 or
(16.25)
IZI
w
FIGURE 16.5. Relation of ZR. Zc. and ZL to frequency compared.
the real and imaginary components of Z (designated Z' [real] and Z" [imagi-
nary D. This is usually performed by a so-called "rationalizing" operation on the
overall expression for impedance as a function of w (see later example). The re-
lationships among Zc, ZL, and ZR(= R) are illustrated schematically in Fig. 16.5.
In summary, it can be stated that the instantaneous potential differences in
a series circuit addressed by an av add algebraically, as for a dc circuit, but the
voltage amplitudes add vectorially. Formally, for any RCL circuit, its imped-
ance can be defined as the ratio of the voltage amplitude to the current ampli-
tude, corresponding to Ohm's law: R = VII.
~ ~
fay =_1_
t2 - t1
f f(t)dt or fav(t2 - t1) =f f(t)dt (16.26)
~ ~
For a sinusoidally varying current I(t) = Isin wt, the average value of current
over a half-cycle (0 to n) from t = 0 to t =n/w will be
490 Chapter 16
_L..J-
1ov _.2.l~~~~
- 7r """
FIGURE 16.6. Average value of a sinusoidal current over a half-cycle (211n, Eq. 16.27).
n/w
lay = w
n
f lsin wtdt =2l1n (16.27)
o
as illustrated in Fig. 16.6; thus, the average current is 21n (about two-thirds) of
the maximum current and the area under the rectangle in Fig. 16.6 (area =
2l1n x n/wis equal to the area (i.e., a charge) under one loop (half-cycle) of the
sme curve.
In the case ofrms current or voltage, Fig. 16.7 is used to represent the situ-
ation. If let) =lsin wt
12 (16.8)
[I(t)]2 =12sin2 wt =-(1
2
- cos2wt)
,., /
/
I " /
,-","
FIGURE 16.7. Average value of the square of a sinusoidally varying current over any number of
cycles is PI2 (root-mean-square value = 112).
AC Impedance Behavior of Electrochemical Capacitors 491
12 12 (16.29)
=-2 - -cos
2
2wt
The average value of P, or the mean square current, is equal to the constant term
12/2 since the average value of cos wt over any number of cycles is zero; thus
(16.30)
The root-mean-square current is the square root of this average squared current,
i.e.,
where I is the maximum current, written earlier as Imax. Similarly, the rms value
of a sinusoidal av is
(16.32)
For a meter reading on a rectifier ac ammeter of, say, 1 A, the corresponding rms
value would be 1.11 A. The average value of the rectified current, in any number
of cycles, is the same as the average current in the first half-cycle in Fig. 16.7
or it is 2/n times Imax. Thus, if an ac ammeter deflects full scale with a current
10 through it, the same deflection will occur when the average value of the rec-
tified (ac) current, 21/n, is equal to 10 . The current amplitude, I, for such full-
scale deflection is then
1= n1012 (16.33)
Circuit 1
R
The overall impedance Z is a function of frequency w. The components of the
impedance are:
Combining the Zs for the two components of the circuit with parallel, i.e., re-
ciprocal addition,
w2R2C2+ 1 (16.39)
= R(jwRC+ 1)
Therefore
The first term on the rhs of Eq. (16.40) is identified as the imaginary component
of Z (to be denoted by Z") since it contains j, while the second term is the real
component (to be denoted by Z'). It is the two terms Z' and Z" representing the
real and imaginary components of Z that are plotted against each other in a com-
plex-plane (Nyquist) diagram for various values of w.
In most systems of practical significance, an additional series resistance,
Rs, representing the ohmic resistance of the solution and separator, and any in-
ternal resistance of the electrode materials, must be included. The latter compo-
nent is called the equivalent series resistance and is discussed in more detail in
Chapter 17.
We can now proceed to demonstrate the geometrical form of such a dia-
gram.
For w in Z' we can write
(16.41)
i.e.,
(16.42)
Also
(16.44)
=R - Z .R2-(RIZ't2
Z
It is seen that this is the equation for a circle when Z" is plotted against Z' (com-
plex-plane plot), with the circle having a radius RI2, and two intercepts on the
Z' axis for zero Z" having values of zero and R. The impedance behavior for this
case is therefore represented by a semicircle with positive Z' and negative Z"
values (Fig. 16.8).
If the circuit is
.------1 I-C - - ,
Circuit 2
R
i.e., including a resistance Rs (representing solution resistance or esr), the semi-
circle becomes displaced along the Z' axis by Rs. There are now two finite in-
tercepts on the Z" axis for Z" = 0, i.e., when Z' = Rs and Z' = Rs + R.
Two limiting cases for circuit 1 are easily recognized. In the equation for
Z as/(w):
1. When w ~ 00, Z ~ Z" =-j/we, i.e., the Z" is small and Z is determined
by the e, which provides the main ac current pathway (-jlwe « R)
since the circuit is a parallel combination of Rand C.
2. When w ~ 0, Z" ~ 00, so the only (then dc) current pathway is through
R andZ ~ Z' = R.
(()
((),=1/RC
,
~
\
":-'
.
,,
'R/2
(()
0 R
i
FIGURE 16.8. Complex-plane impedance plot for the simple parallel RC circuit 1 showing top-
point characteristic frequency COr = 1IRe.
AC Impedance Behavior of Electrochemical Capacitors 495
The complex-plane plot for the parallel Rp-CdJ circuit 1 is shown in Fig.
16.8. A similar analysis can be performed for a series RC circuit
-----~~--~llrc------- Circuit 3
for which
=R-j/wC
This requires no rationalization so that ZIt is -j/wC. Limiting cases are obvi-
ously
w~oo,Z~R;
(0
z'
FIGURE 16.9. Complex-plane impedance plot for the series RC circuit 3.
496 Chapter 16
: 1/R
:{
y'
FIGURE 16.10. Admittance (Y) plane plot for the series RC circuit 3. (Compare Fig. 16.9 for the
parallel circuit Z plane plot.)
Denoting
Then
=0
l.e.,
OJ,RC = 1
or
lIRC has the units of reciprocal time (s-l) so that RC itself is a characteristic
time constant of the circuit for the response to av modulation, as for the Z case
(see Section 16.4).
RC is represented by r = 1/OJ" as before. OJ, is also called the "charac-
teristic frequency" of the circuit. Similar conditions apply to the frequency re-
sponse of the parallel RC circuit considered earlier in this chapter.
Since for a well-defined semicircular complex-plane plot, the top point can
be identified as the point of intersection of a perpendicular erected from the Z'
axis at RFI2 on the Z" vs. Z' curve, then OJo can be evaluated. Since the RF at this
point is also known, the top-point identification leads to a convenient way of
evaluating C, provided it is not frequency dependent.
At any time:
(16.58)
(16.59)
so that ~ VRIV = exp( -tIRC), i.e., in a time scale of t reduced by division by the
time constant RC.
The time-dependent current let) through R and into C cannot be explicitly
written; thus, in terms of charge acquired by C,
or
V (16.64)
let) =Rexp(-tIRC)
This meets the boundary condition requirements since let) = VIR when t = 0 and
l(t) ~ 0 as t ~ 00. The response function for the charging current variation in
time is seen to be scaled in tIRC, as expected for problems of this kind. These
relations are to be regarded as having general significance for RC circuits.
An alternative treatment of the problem in terms of accumulated charge, q,
on C, is as follows:
(16.65)
Rearranging,
RC dq =dt (16.66)
(CV- q)
and integrating
Hence
so that
V (16.71)
I =Ii exp[-tIRC]
In this case, the discharge current from C (= -CdVJdt) is equal to the current
through R, namely, VJR. Thus,
so that
1 (16.73)
V· dVcldt= -lIRC
c
Integration gives
giving
1 1 1 (16.77)
-=-+-
Z R Zc
for the parallel addition of impedance; that is, introducing win Zc,
(16.78)
l/Z=.l+ jWC
R
as discussed earlier.
value, the capacitance will be charged from a given applied voltage, Ll V, at a rate
inversely related to R; similarly, the larger the C, the longer will be the time re-
quired for the capacitor to acquire the applied voltage difference, Ll V, between
its plates with the charge being admitted through a given R.
Formally, the significance of RC as a characteristic time can be seen by ref-
erence to the units oftheRCproduct. Thus R == [voltage] [currentr l (Ohm's law)
or [voltage] [charger I [time]. Correspondingly, C == [charge] [voltagerl. Hence
RC == [time] or reciprocal frequency. The same result arises if Rand C are ex-
pressed in the fundamental units of mass, length, and time (mIt); then it is found
thatRC== t, a time quantity. Thus RC == (Ke} t-It) x (Kot) == t where KO is the per-
mitivity of free space discussed in Chapter 4.
16.5.1. AC Bridges
The oldest procedure is based on the use of ac bridges, an ac variant of the
classic Wheatstone bridge for measuring resistance. An elementary circuit of
such a bridge is shown in Fig. 16.11.
Generator
FIGURE 16.11. Elementary four-arm bridge balancing circuit for resistance (R) or impedance
(Z) measurements. Test cell is labelled as C (not necessarily a capacitance).
AC Impedance Behavior of Electrochemical Capacitors 503
(16.79)
i.e.,
(16.80)
Normally, such bridges are difficult to balance for frequencies ~1O Hz. In early
work, a WOO-Hz sine wave modulation generator was used and audiodetection
was employed in D, or D was a tunable detector with a multiscale, null-reading
meter.
and
z =IZlexp(-jtP) (16.83)
504 Chapter 16
AA'
IZI = 88'
. DO'
Sln¢ = AA'
Lissajous figures
e(t) =6E Sinwt X of osci Iloscope
FIGURE 16.12. Lissajous figure generated between the y and x-axes of an oscilloscope or X-Y
I I
recorder in relation to the impedance vector magnitude z and the phase angle, I/! (schematic).
This method is specially applicable to low frequencies, say <1 Hz, but today is
not commonly used although it is a useful procedure for visually demonstrating
(on an oscilloscope) the phase relation between voltage and current in RC cir-
cuits.
tems are also used in other ways, e.g., in detecting reflectance or optical absorp-
tion changes at electrodes brought about by sinusoidal or square-wave, low-am-
plitude modulation of electrode potential. This arrangement allows major
improvements in signal-to-noise ratios to be achieved.
T (16.84)
f
Z' =~ S(t)sin wt·dt
o
and
T (16.85)
f
Z" =~ S(t)cos wt·dt
o
r--------------------------,
I I
I I
I Generator 1---'--- 1m
I
I
I 7T" / 2 ~=-'--'
I o ~L---:-,-_+---I
I---'--'--Re
I
I
IL _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ...JI
x(t)
S(t)
System
under
test
FIGURE 16.13. Simplified block diagram of the Solartron Frequency Response Analyser system.
506 Chapter 16
where Set) is a cell response signal that may include some noise, and T is a signal
response integration time. Longer integration times, analogous to a signal-aver-
aging procedure, lead to better noise rejection, but they also can lead to prob-
lems of changes of state in electrode surfaces during prolonged integration
periods. Total noise rejection is achievable in principle if T ~ 00, but this is not
a practically attainable condition. In the case of the Solartron model 1250, a fre-
quency range of 10-4 to 6.5 x 104 Hz can be covered in a frequency scan of an
electrode process or capacitor behavior.
Normally, the frequency scan must be conducted at an electrode or a ca-
pacitor polarized at a potentiostatically-controlled potential or held at a control-
led potential difference, respectively. The frequency scan should be performed
over a range of various controlled potentials or potential differences, which may
be a quite time-consuming process. This is why care must be exercised in inter-
preting results at capacitors or electrodes at which some irreversible changes of
state might take place over periods of an hour or more. A comparison between
scans of frequency response in the upward and downward directions of fre-
quency change can be useful in evaluating such time-dependent effects, e.g.,
due to impurity adsorption or electrode deactivation.
The use of scans at various potentials within the operating range of elec-
trochemical capacitors is very desirable in establishing a full evaluation of ca-
pacitor performance. This is because the specific interfacial capacitance of
many metal electrode materials, and of carbons of various types (see Chapter 9),
is often appreciably dependent on potential (relative to some reference electrode
probe), as is also Hg, the classic case for metals (Chapter 6).
'\
\
,,
\
\
o
i
FIGURE 16.14. Complex-plane impedance plot for a Faradaic process involving transition to dif-
fusion control at low frequency, w, associated with the presence ofthe Warburg impedance element,
W, exhibiting a 45° phase angle.
with W in parallel with the double-layer capacitance is called the "Randles cir-
cuit" after Randles' paper in Discussions of the Faraday Society, 1947. 2
ell
Randles
circuit
Rs
In that discussion, Erschler8 presented a closely related paper. One ofthe earliest
papers on ac determination of double-layer capacitance was that by Proskurnin
and Frurnkin9 in 1937, while ac applications in polarography (ac polarography)
were made in an important paper by Breyer and Gutmann, 10 with later develop-
ments by Smith. II ,12
The superimposition of an av modulation on the slow sweep of potential is
used in polarography experiments to generate a response signal that is the dif-
ferential coefficient of the polarographic wave, giving a maximum at the half-
wave potential, EI/2, of the polarographic wave where the concentrations of
reduced and oxidized species are equal at the electrode interface; this allows a
maximum in the redox electron exchange rate to occur. This has relevance to the
evaluation of double-layer capacitor behavior where impurities in redox sys-
tems may lead to attenuation of ideal polarizability and the appearance of leak-
age currents, causing self-discharge (Chapter 18).
When diffusion control is a limiting factor in the kinetics of an electrode
process, the Warburg impedance, W, representing the diffusion behavior under
AC Impedance Behavior of Electrochemical Capacitors 509
av modulation, gives rise to a 4SO straight line in the complex plane plot of Z"
vs. Z'. A transition from the semicircular Z" vs. Z' plot to a 45° line is often ob-
served in the scan of OJ toward low frequencies, as illustrated in Fig. 16.14. The
Warburg impedance exhibits a frequency dependence on square-root of OJ-I
both in Z" and Z'; hence the 45° straight line. The square-root of the OJ relation
arises for quite general reasons connected with the dynamics of diffusion where
the time factor in semi-infinite diffusion leads to Wbehavior in one form or an-
other (OJ-1 12 in ac impedance, t l12 in time dependence of concentrations, square-
root of rotation rate in rotating-disk electrode studies). The t ll2 relations arise for
fundamental reasons originating from the Stokes-Einstein equation for the
mean-square displacement, :x 2, of particles diffusing in a concentration gradient:
:x 2 = 2Dt or (:x2)112 =...J2Dt where D is the diffusion coefficient of the diffusing
species. Diffusion problems are dealt with through Fick' s two laws (differential
equations) representing the dynamics of diffusion:
where dNldt is the number N of moles of a solute diffusing per second (flux)
across a laminar of area A normal to the concentration (or chemical potential)
gradient, dc/dx, along the x direction, the vector of diffusion in the solution.
It should be noted here that a phase angle of 45°, independent of frequency,
can also arise for quite different, nondiffusional reasons when a distributed RC
network arises in a porous electrode (Chapter 14). The frequency response is
then like that of a transmission line that also has a linear Z' vs. Z' plot with a
45° phase angle. This is experimentally observed in some high-area, porous,
carbon-based double-layer capacitors as was discussed in Chapter 14.
.- .
I - Iss + !Ji
dE (E - E) l,d 2i (E - E)2
ss + 2 d£2 ss + ..... .
(16.89)
510 Chapter 16
~ . . di It
I = I - Iss = dE (16.90)
Therefore
(16.91)
(16.92)
kl (16.93)
H 20 + M + e- +-7 MHads + OH- (step 1)
k_1
(step 2) (16.94)
k, i (16.95)
2 MHads ~ Hz + 2M (step 3)
Vz =kz(}exp(jJFEIR7) (16.97)
and
(16.98)
(16.100)
e = !:.eexp(jwt) (16.101)
and
de (16.102)
-=jw7)
dt
with
Tl = f(E,e)
Hence,
TO = TO,ss (ar,)
+ dE 11 (E - Ess) + de(a" 1co -
'E Oss) (16.103)
and
Tl = Tl,ss
(a,,)
+ dE 11 (E - Ess) + [ar,]
ae 'E(0 - Oss)
(16.104)
(16.106)
.,. (arol-
aE E+ (aro]
IIF= - -
ae e- (16.107)
'E
with
- (arll-
(qllF)jwe = aE E+ (aro)-
ae 'E e
(16.108)
(16.109)
and
(16.110)
-(~)o (~;l E
o r(~i) -~Jwl
E
and
(16.112)
Note that Oss can be calculated by setting Eq. (16.100) equal to zero, i.e.,
(qtfF)(d8!dt) = VI - V2 - 2V3 = 0, the usual steady-state condition.
16.6.4.1. Methodology
A commonly applied procedure for study and evaluation of the behavior
of electrochemical capacitors is linear voltage sweep voltammetry or, when ap-
plied in a repetitive mode, cyclic voltammetry. In this procedure, the time and
potential-dependent currents, l, which arise in response to modulation of an
electrode in solution by a potential linearly varying in time at a constant rate
s =±dVldt (16.113)
(16.114)
let) = C (~~)= Cs
or
l(t)/s =C (16.115)
The direction of current will depend on the sign of dVldt, which is periodically
reversed in cyclic voltammetry at the ends of the voltage excursion, Ll V, i.e., the
amplitude.
If C is constant with potential, cyclic voltammetry generates a rectangular
current response record, as illustrated in Chapter 3, which is symmetrical around
the zero-current line if the same s is applied in each direction of the voltage
sweep. For many systems, however, C is not constant with V in the sweep and
may not be constant with sweep rate when kinetic or diffusion limitations to cur-
rents arise, e.g., when C represents a pseudocapacitance (Chapter 10).
When a pseudocapacitance Cp is involved' (see Chapter 10), the following
equivalent circuit represents its behavior to a first approximation:
Rs
L..JIINVIMr-.
J-
:
dl
l__ ~---]
P:
Pseudocapacitance
circuit
RF
'Here the symbol Cp is used for the pseudocapacitance for consistency with the impedance
literature (cf. C", in chapter 10).
AC Impedance Behavior of Electrochemical Capacitors 515
i =CCdVldt) (16.116)
}""=jeoC (16.117)
where the frequency eo introduces and represents the time-dependent factor in
the current response. The question then is: can some relation between the time
dependence of currents in Eqs. (16.116) and (16.117) be formulated? Since the
modulation in time of potential in Eq. (16.116) is discontinuous at the sweep-
reversal potential in cyclic voltammetry, while sinusoidal modulation of poten-
tial in impedance measurements is continuous, it is clear that there can be no
rigorous direct comparison between these two procedures over the whole span
of amplitude excursions involved in these two procedures. However, the follow-
ing points can be usefully made in order to demonstrate some comparative fea-
tures of the two methods, and the respective response-current behaviors under
particular conditions.
Normally cyclic voltammetry is conducted in a repetitive cyclic manner
(hence the name of this procedure) so that there is some repetition rate, r, of the
±dVldt signals addressed to the electrochemical system that has some analogy
to frequency. r is obviously determined by the reciprocal of twice the time Llt 1/2
of each half-cycle, which is the scanned potential range LlV divided by dVldt
i.e., when the response current is a maximum and the voltage crosses the
half-amplitude value (see later discussion). Thus, some correlation between
the current-response behavior of a system to cyclic modulation of V by re-
petitive linear sweeps over a constant voltage range and the current response
in av modulation can be realized, if not exactly in an analytical way, then
conceptually. The situation is illustrated schematically in the working diagram
shown as Fig. 16.15. Simplistically, from Eq. (16.121), the ratio of equivalent
sweep rate, s, to w in av modulation is
v(tl
/\ ----r'
,, ,,
vltl " l!.v -h~;-:-+--#---\----+-~
\.L I
\
\ (dV/dtl mox
I (dV/dtl mox \
\
C.V. a.V.
FIGURE 16.15. Working diagram illustrating relation between a sinusoidal voltage signal and a
cyclic voltammetry voltage signal in relation to frequency and dV/dt in the half·cycles.
518 Chapter 16
(16.123)
(compare Eq. 16.121), noting that the impedance is Z" = -j1wC or the admit-
tance
e
age, H in the above reaction, of the electrodeposited species, or that of the con-
centrations of Ox and Red species in a redox reaction. Cp = ql deldV in the gen-
eral case where ql is the charge required for formation or desorption of the
species or for the total interconversion of Ox to Red in a redox process. A small
but significant solution resistance, R" is usually combined in series with the
Faradaic impedance involving RF and Cpo The circuit elements are combined as
follows:
eel
(a)
·z"
10
(b)
FIGURE 16.16. Complex-plane impedance plots for a Faradaic pseudocapacitance. (a) with no
desorption resistance (UPO case), and (b) with desorption resistance, RF (OPO case).
520 Chapter 16
lected parameter values for the circuit elements involved, taking Cd1 typically as
20 flF cm- 2•
The interfacial part, Z, of the overall impedance is given by
(16.126)
(16.127)
and Z is combined in series with Rs. From Eq. (16.127) it can be seen that two
limiting cases arise:
(16.128)
i.e., Cd1 and Cp are effectively added as in a simple parallel arrangement and the
measured C =Cd1 + Cpo
2. at sufficiently high frequencies (jwRFCp » 1)
(16.129)
(16.130)
or
(16.131)
(16.132)
(16.133)
z= l/jwCd! (16.134)
II
11
Rs
"
RF
lie
1>
(16.135)
and
(16.136)
(16.137)
or
(16.138)
1 1 (16.139)
Z=--+--
jwCz jWCd1
i.e., the Cd1 and C2 combine (reciprocally) as a pure capacitance of Cd1 and C2
in series, as is obvious from the above equivalent circuit when w ~ 00, [Z (Cdl>
C2)« R F ]·
At sufficiently low w, Rp(jwRFCd1 + 1) becomes RF and Z is then the im-
pedance of RF in series with Cz, namely,
(16.140)
AC Impedance Behavior of Electrochemical Capacitors 523
together with any solution resistance, if significant. This gives a rising vertical
plot of Z" in the complex-plane with decreasing W having an intercept of RF on
theZ'axis(Fig.16.16).
After rationalizing the denominator, the overall impedance, not including
an R" is given by
(16.141)
(16.142)
from which the real and imaginary components of Z are recognized. The above
relation reduces to the limiting cases for W -4 0 or W -4 00 identified above.
Note that unlike the equivalent circuit
REFERENCES
1. K. S. Cole and R. H. Cole, J. Chem. Phys., 9, 341 (1941).
2. 1. E. B. Randles, Disc. Faraday Soc., 1 (1947).
3. M. Sluyters-Rehbach and 1. Sluyters, Rec. Trav. Chim., P.B., 83, 217, 581, 967 (1964).
4. For discussion of Kramers-Kronig relations, see, e.g., 1. M. Ziman, Principles of the Theory
of Solids, p. 222, Cambridge Univ. Press (1964), and A. H. Morrish, The Physical Principles
of Magnetism, pp. 88, 209, Krieger Publ. Co., Huntington, N.Y. (1980).
5. A. N. Frumkin and R. Melik-Gaikazyan, Dokl. Akad. Nauk. S.S.R., 77,855 (1951).
6. R. D. Armstrong and M. Henderson, J. Electroanal. Chem., 39, 81 (1972).
7. M. Keddam, O. R. Mattos, and H. Takenouti, J. Electrochem. Soc., 128, 257 (1981).
8. B. V. Erschler, Disc. Faraday Soc., 1 (1947).
9. B. Proskumin and A. N. Frumkin, Trans. Faraday Soc., 31, 110 (1935).
10. M. Breyer and F. Gutmann, Aust. J. Sci., 11,96 (1948).
11. D. E. Smith, Anal. Chem., 35, 1811 (1963); 36, 962 (1964).
12. D. E. Smith, in Electroanalytical Chemistry, A. 1. Bard, ed., vol. I, pp. 1-155, Marcel Dekker,
New York (1966).
13. A. Sevcik, Coil. Czech. Chem. Comm., 13, 349 (1948).
14. F. Will and C. A. Knorr, Zeit. Elektrochem., 64, 258 (1960).
15. A. Eucken and B. Weblus, Zeit. Elektrochem., 55, 114 (1951).
16. B. E. Conway and E. Gileadi, Trans. Faraday Soc., 58, 2493 (1962).
17. E. Gileadi and B. E. Conway, J. Chem. Phys., 31, 716 (1964).
18. E. Gileadi and S. Srinivasan, Electrochim. Acta, 11,321 (1966).
19. 1. Klinger, H. A. Kozlowska, and B. E. Conway, 1. Electroanal. Chem., 75, 45 (1977).
20. H. A. Kozlowska and B. E. Conway, J. Electroanal. Chem., 95, 1 (1979).
21. B. E. Conway, H. A. Kozlowska, and E. Gileadi, 1. Electrochem. Soc., 112,341 (1965).
22. H. A. Kramers, Atti. Congo Fisica (Como), 545 (I927) and R. Kronig, J. Opt. Soc. Am., 12,
547 (1926).
Chapter 17
In earlier chapters it has been emphasized that the high-area, porous carbon
structures that provide large specific (per gram) capacitance values (in practice,
5 to 50 F g-l) cannot be represented by a simple capacitance or even by a simple
RC circuit. The diagrams in Fig. 17.1 represent a hierarchy of equivalent cir-
cuits, from those for a simple capacitor through those involving simple combi-
nations of a capacitor element with either one or two ohmic or equivalent ohmic
resistors, to more complex equivalent circuits involving distributed capacitance
with ohmic elements in series or parallel coupling with the capacitative ele-
ments and, for some conditions, with Faradaic leakage resistances in parallel
with the capacitative elements. The latter may also include contributions from
pseudocapacitances associated with surface redox functionalities (Chapter 9) on
the interfaces or edges of carbon particles or the main pseudocapacitance asso-
ciated with redox oxide capacitor materials (Chapter 11). In some cases, con-
sidered later, the equivalent circuit may also include an inductive element, L.
'This Chapter owes much to the derivations and analyses given by Dr. Miller at the various
Deerfield Beach (Florida) seminars on electrochemical capacitors held in recent years.
525
526 Chapter 17
a) Simple capacitor b)
----1 ~
Capacitor with equivalent
or real series resistance
A
C
~ RF
FIGURE 17.1. Hierarchy of equivalent circuits, from that for a pure capacitor, with no esr, to that
for a porous electrode with distributed C and R components.
analogous to Ohm's law, where Vet) = Vo sin wt and /(t) =10 sin (rot + rp), are the
time-variant voltages and currents that are modulated according to the fre-
quency w, as expressed earlier. Z(w) may include ohmic (R), capacitative (C),
and sometimes inductive (L) elements; the latter two are dependent on fre-
quency according to Z(w) = l/jwC and Z(w) = jwL, respectively, as displayed
below.
The elements of equivalent circuits and their respective dependences on
frequency are as follows:
Element Z(w)
Resistor, R R (dR/dw=O)
Capacitor, C l/jwC=-jwC
Inductor. L jwL
where j, as usual, is ~.
In a series arrangement of n impedances
n
(17.2)
~otal =IZ;
;=1
so that for this case, the smallest of the Zs principally determines the overall Z.
In electrochemical systems the same R, C, and L elements can be recog-
nized as in hardware circuits, except that C is a double-layer electrostatic ca-
pacitance or a pseudocapacitance (Ct/J; see Chapter 10) and L is a
pseudoinductance, usually of connecting wires the effect of which is usually
small except at high frequencies or rapid transients. Another qualitative excep-
tion is the existence of a so-called Warburg impedance element (represented by
W) that arises when an electrochemical process is or becomes diffusion control-
led. The element W contains two components, a diffusional capacitance and a
diffusional resistance (see Chapter 3), each of which is dependent on the square-
root of frequency. In the material that follows, the behavior of various elemen-
tary RC and RCL equivalent circuits will be examined, including the case of
distributed capacitance and resistance elements that represent the behavior of
high-area porous electrodes.
528 Chapter 17
which tends to Z(w) = esr at infinite w. This result usually provides the formal
means of evaluation of esr of a capacitor device. Thus, in complex-plane plots
of the imaginary (Z") vs. the real (Z') components of the impedance vector (Z)
at various frequencies (Chapter 16), the effective esr (including any series elec-
trolytic resistance) is revealed as the intercept on the Z' axis as w ~ 00.
The involvement of an esr in electrochemical capacitors is a factor of major
importance in their electrical behavior, especially their power performance
(Chapter 15). The presence of significant esr restricts the rate at which the ca-
pacitance can be charged or discharged upon application of a given voltage dif-
ference between the electrodes or the alternating currents that can be generated
at a given moment by applying an alternating voltage at a given frequency. The
esr limits the power at which the device can be operated from a given direct or
alternating voltage, and is thus one of the most important properties of a super-
capacitor, in addition to its capacitance density in F g-l or F cm-3 . The imped-
ance of the capacitor device then differs from that of a pure capacitor because a
frequency-dependent phase angle (less than 90°) is developed between the al-
ternating voltage and the resulting ac modulation, as indicated earlier on the ba-
sis of general principles. Power loss and energy dissipation then ensue.
In the case of electrochemical double-layer capacitors, the esr situation is
usually substantially more complex than that illustrated in the equivalent circuit
here. As explained in Chapter 14, distributed electrolytic, interparticle, and in-
traparticle resistances arise because of the porous, particulate nature of the elec-
trode matrix. Rather similar behavior can arise with oxide-type redox
pseudocapacitors (e.g., Ru02) having high-area microporous matrices.
In the above case there is no unique esr except the component of resistance
ofthe external solution. The impedance behavior, plotted in the complex plane,
exhibits a 45°, almost linear relation at elevated frequencies (transmission-line
effect; Chapter 14), with an intercept on the Z' axis as w ~ 00, corresponding to
the resistance of the solution and any separator external to the outer surface re-
gion of the porous electrode matrix.
In state-of-the-art double-layer-type capacitors, effective esr values are in
fractions of milliohms up to a few tens of milliohms. The higher values occur
when electrochemical double-layer capacitors are designed for higher voltage
operations using nonaqueous electrolyte solutions, which have intrinsically
lower specific conductances.
The minimization of esr is obviously desirable in constructing electro-
chemical capacitors that are intended for operation at elevated power levels (see
Chapter 15).
530 Chapter 17
tcutoff = Resr xC
(17.5)
The initial voltage and current drawn at the start of discharge and hence
their product, the power, P, depend on the energy, E, stored in the capacitor de-
vice so that6
1000
'r
100
10
LL
......
Cl)
u
C
g 0.1
u
0
a.
0
U 0.01
0.001
FIGURE 17.2. Impedance plots for ten commercial capacitors showing cutoff of capacitance
with decreasing esr component. I Soleq 470 F; 2 Soleq 70 F; 3 Maxcap 1 F; 4 NEC 0.47 F; 5 Maxcap
0.47 F; 6 Maxcap 0.22 F; 7 NEC 0.1 F; 8 Maxcap 0.1 F; 9 Maxcap 0.047 F; 10 Sprague 0.022 F.
(From Eisenman. 6)
Treatments of Impedance Behavior of Various Circuits 531
The physical construction and materials of the capacitor determine PIE, while
the actual capacitance and maximum charging voltage do not enter as vari-
ables. 6 The current U.S. Department of Energy goals specify a PIE ratio of
0.0278 s and a cut-off time of 72 s, i.e., twice the 36-s timeline of the tests. Then
the power at the time of the short circuit would be (after a revision of the Equa-
tion in Ref. 6):
(17.9)
The d.f. = Z'IZ" = wRC and dJ. = 1 when w = lIRC or/ = 1I2nRC (2n/ = w).
where/is the frequency in radians/s.
Similar considerations apply to the parallel RC circuit treated in Chapter
16 in order to demonstrate the origin of semicircularity in the complex-plane
plots. For this case, the impedances of the components add up reciprocally:
Z = _R_(1_---'l:-·w...".R_C:'-) (17.12)
1 + w2R2CZ
and
(17.13)
(17.14)
and
(17.15)
while Z' and Z" combine, as shown in Chapter 16, to give the complex-plane
plot
RF (1 - jwRFC) (17.17)
Z=Rs+ w2 2CZ
1 + RF
where RF is a Faradaic, parallel leakage resistance that may be potential depend-
ent according to a Tafel exponential factor. In this case, a semicircular plot of
Z" vs. Z' is retained, but it is displaced along the Z' axis with an intercept of
Rs. The equation for the semicircle is then
RF jwR~C (17.19)
Z =R + --"----
s (1 + w2R~CZ)
from which Z' and Z" are directly recognized and distinguished. The phase angle
tan ifJ = Z"/Z' is found as
534 Chapter 17
-jwR~C (17.21)
For this case, note the limiting results that for w --t 0, tan t/J --t 0; and
for w --t 00, tan t/J also --t 0, so there is a maximum in tan t/J, as is commonly
observed. When Rs --t 0, then tan t/J = -jwRFC, which varies from 0 to 00 with
0< w < 00, i.e., there is no maximum with increasing w. This is the situation
in dielectric relaxation plots 7 of the real and imaginary components of the di-
electric constant as a function of frequency.
When RF --t 00 (no leakage currents), the circuit becomes that for a series
RC connection. For tan t/J = 00, t/J = n12, the phase-angle for a pure capacitance,
while for tan t/J = 0, t/J = O.
Although most circuits involving electrochemical capacitors do not in-
clude any deliberatley added inductances, except perhaps for some resonance
purposes, adventitious inductance can be introduced that is significant, e.g.,
when large current pulses are employed in charge or discharge. Then it is the
wiring of the circuit that can introduce a significant self-inductance.
In some other cases, however, where special types of electrode processes
(e.g., metal oxide film formation and passivation) are involved, an intrinsic
pseudo inductance may be exhibited in the impedance frequency response. This
type of situation can arise when inhibition of an electrode process leads to Tafel
behavior that corresponds to a negative resistance (current decreasing with in-
creasing overvoltage), or when surface coverages by some adsorbed intermedi-
ates decrease with increasing overvoltage. In the case of corrosion processes
involving onset of passivation, very complicated Z' vs. ZIt complex-plane plots
appear in two or three quadrants, where reentrant curves arise and ZIt enters the
positive quadrant. This is usually due to a situation of decreasing current with
increasing potential, i.e., a negative resistance arises.
In a series R, C, L circuit
(17.24)
with
Treatments of Impedance Behavior of Various Circuits 535
Rs
two semicircles can arise in the complex plane plot with a high-frequency inter-
cept on the Z' axis of Rs (Fig. 17.4).
In another case for a series/parallel combination, namely,
the complex-plane plot has the form shown in Fig. 17.5, where a single semi-
circle becomes transformed to a vertical line in the -Z" direction with decreas-
ing frequency; the intercepts on the Z' axis are Rs + R1, and Rs at high frequency.
536 Chapter 17
N
W
U ESR
Z
<1
o /
I
W I
a. \ /
~ \ I
\ I
\ /Z
\1
Y
FREQUENCY
FIGURE 17.3. Frequency dependence of the impedance Z of an RCL series network involving
an equivalent series resistance. Rs. that is finite or zero. (After Miller. 1,2)
The vertical element of the plot corresponds to the impedance (ZII) of a pure ca-
pacitor (Cl ) as w tends to zero. When w becomes large enough for Zc, to be
small compared with Rs, then the behavior approximates that of the simpler Rs,
R 1 C2 series/parallel circuit considered earlier. Curves of the type shown in Fig.
17.5 are commonly found in a number of studies of the frequency-response be-
haviors of electrode systems where some film capacitance becomes coupled
with a Faradaic impedance, R 2C 2 in parallel, as in the series double CR circuit
on p. 535.
Miller 2 has considered the behavior of the general RCL capacitor circuit
for various conditions. For the combination
-Z"
FIGURE 17.4. Complex-plane impedance plot for two parallel RC equivalent circuits in series
with each other. and in series with an esr of Rs.
Treatments of Impedance Behavior of Various Circuits 537
.:(0
-1:'
FIGURE 17.5. Complex-plane impedance plots for a series and parallel equivalent-circuit com-
bination, with transition to purely capacitative behavior (vertical line) at sufficiently low frequen-
cies.
fr = l/[2nCLC)112] (17.27)
Then a practically important property emerges: such a device will store electri-
cal energy efficiently only for frequencies less than/r . This emphasizes the im-
portance of minimizing design and circuit features that could introduce
significant series inductance. Sincelr is determined by CLC),-1I2 it obviously fol-
lows that the condition I <Ir for optimization of energy storage is more easily
attained when L is small. The four- component circuit above reduces to a sim-
pler series circuit for the conditionf <fr and when RF» Rs' the practical desid-
eratum referred to earlier. Large RF , of course, will reflect good charge storage
over time since RF determines the self-discharge kinetics of the parallel RFC
combination, it being generally required that RF be maximized or ideally 00 for
an ideally polarizable double-layer capacitor, C.
Figure 17.6 shows test data from Miller2 for a typical practical electro-
chemical capacitor based on evaluation of Z' and Z" over a wide frequency
range between 1 mHz and 1 MHz showing a self-resonant frequency of 15 kHz.
538 Chapter 17
lk.----------------------------------. lk
,
2 .. 100
2
10 10
E
.c
".. ............ .
- _____________ ____ :.1.uu~ •••••••••••••••••••
E
.c
0
0
....... 100m
'- "- .......
100m =N
N "-
10m
1m
'" '- '- 10m
1m
'-
'-
100 Ik lOOk 1M
FIGURE 17.6. Impedance spectra of a typical practical electrochemical capacitor. The real and
imaginary parts of the impedance are shown. The dashed lines show the behavior of an ideal resis-
tor-capacitor series combination. Self-resonance frequency, 15 kHz. Original figure based on ca.
100 points. (From Miller?)
The dashed lines show the behavior of an ideal resistor-capacitor series combi-
nation, which clearly illustrates the deviation of the practical capacitor from
such ideal behavior.
Rs
----
Vo
Treatments of Impedance Behavior of Various Circuits 539
Pmax
(17.28)
For the matching load situation (Rs =RL), the maximum power is found as
(17.30)
i.e., it arises at V = V012 or half the potential for full discharge. Note that when
RL = 0, P = 0, and when RL = 00, PL also is zero, while a maximum in P arises
between these conditions for the load resistance. This situation is similar to that
found in the theoretical analysis for Ragone plots of power density vs. energy
density (Chapter 15).
For a series RC circuit with a resistive load, the power supplied in relation
to the maximum power utilized (P max) is given by
where Pmax = V6/4Rs, as shown earlier. The parameter r =RL/Rs is the ratio of
the load resistance to the series or equivalent series resistance. r = 1 is referred
to as the "matched load" condition. The time parameter r = tiRsC, where RsC is
540 Chapter 17
the time constant of the Rs' C combination. r is thus a reduced time scale, as
arises in other related problems (Chapter 16, Section 16.3.2).
For a voltage range of Vo (the initial voltage), down to Val2, analytical re-
sults calculated by Miller 1•2 are shown in Fig. 17.7. It is seen that when r = 1
(matched load), PIPmax (ordinate scale of the plot) becomes unity since (l + r)2
is then 4 and exp[-2r/(l + r)], when r = 1 and t =0, is also unity. The supplied
power, P, is equal to the maximum power when r = 1, the matched-load condi-
tion.
The origin ofEq. (17.31) is as follows. Consider a capacitor of capacitance
C having an esr of Rs discharging into RL from an initial voltage, Vi, and a volt-
age during discharge of Vt across the capacitor. Then, at any time,
(17.32)
where the latter two Vs are the voltages developed across Rs and RL, respec-
tively, when a discharge current I(t) passes.
The current for discharge of the capacitor is:
1/ = Ii exp[-tIRC] (17.33)
also
(17.34)
and
)(
c
E
a.. 0.1
.....
..J
a..
r =10
0.01 o/O""'----'---....L2--~--_i--_t- . -=6""""----'--7--~
T=t/RsC
FIGURE 17.7. Behavior of a series (esr) RC circuit with power delivered into a resistive load
(RL) for discharge from initial voltage Vo down to VoI2 based on results analytically calculated by
Miller. I•2) Parameter r =RL/ Rs and r = 1 is a matched load.
Treatments of Impedance Behavior of Various Circuits 541
(17.35)
(17.36)
4Pmax (17.43)
P =- - . exp[-2tlC(Rs + R L)]
1+r
4Pmax (17.44)
= - - . exp[-2r/(1 + r)]
l+r
(17.45)
4rPmax (17.46)
= 2 . exp[-2r/0 + r)]
(1 + r)
4Pmax (17.47)
Ps = 2 . exp[-2r/(l + r)]
(1 + r)
The power drawn from the capacitance minus that lost in Rs is the power
developed across the load, i.e.,
O+r) 4Pmax
Peap - Ps = 4Pmax 2· exp[-2r/(1 + r)] - 2· exp[-2r/(1 + r)]
(1 + r) (1 + r)
(17.48)
4Pmax r (17.49)
= 2 . exp[-2r/(1 + r)]
(1 + r)
which is the required time dependence of power developed in the load from the
discharge of the capacitor.
The behavior of several RC or RCL systems that may be equivalent to that
of any practical capacitor has been simulated in calculations by Miller. 2 A first-
order model for any capacitor is (cf. p. 537), in the simplest analysis:
Rs
L
where Rs and Rp are series and parallel resistive components coupled with C. L
mayor may not be significant. Rp can be a Faradaic (potential-dependent) reac-
tion resistance when C is a double-layer capacitance. Rp is much greater than
Rs for practical capacitors except when Faradaic leakage currents arise, leading
to self-discharge (see Chapter 18). Z is then (cf. Eqn. 17.23)
Treatments of Impedance Behavior of Various Circuits 543
10
II) II)
E E
.c .c
0 100m o
: ...... ......
N 10m 10m N
I
1m 1m
FIGURE 17.8. Z" andZ' components ofthe impedance of the RCL equivalent circuit as a function
of frequency over a wide range (log scale) for a constant real component of I ohm. (Resonant fre-
quency,JR = 1I[2n(LC)1I2) is ca. 3 x 102 Hz). (From Miller?)
544 Chapter 17
Zp = ~ ~ j) x coth [t -J wC
2nn r KWC ! Kr
d ! (1 + j)]
(17.51)
d
where n is the number of pores in the electrode, r is the radius of a typical pore,
assumed to be cylindrical, K is the conductivity of the electrolyte, w is the an-
gular frequency as usual, Cd! is the double-layer capacitance per unit area, and
t is the length of a typical cylindrical pore. Details of the treatment of imped-
ance of a pore, based on de Levie's analysis, were given in Chapter 14.
Obviously this model is seriously oversimplified since, e.g., there is a dis-
tribution of pore lengths and diameters and there may be fractal structures that
represent the pore geometries better than a simple cylindrical one. However,
only with such a simplified model can an analytical result for Zp be derived and
that, it is seen, is already quite complex. More complex geometries were treated
by Keiser, Beccu, and Gutjahr4 (Chapter 14).
Nevertheless, two limiting cases are informative and useful:
1. the high-frequency limit
Z- (l-j) (17.52)
p - 2nn ...J r3KWCd!
and
2. the low-frequency limit
(17.53)
=-j/wC (17.54)
since C is the overall double-layer capacitance for a total surface area of S =2nr
t nand C =SCdl .
The complex impedance of an electrode composed of uniform pores (as
an approximation) is as shown in Fig. 17.9 in which Q is the ionic solution
resistance within the porous structure (typically tens of milliohms or less in
well-engineered capacitors) and Rs is the (external) equivalent series resis-
tance. It is seen that at low enough frequencies the impedance behavior be-
comes that of a pure capacitor, with Z" increasing as l/wC in a vertical line
having an extrapolated intercept on the Z' axis for infinite w of Rs + Q, while
the actual experimental high-frequency intercept is Rs at the high-frequency
limit of the 45° line, corresponding to transmission-line behavior below the
knee of the curve. The distance between the two intercepts in Fig. 17.9 gives an
estimate of the internal resistance Q, which can then be optimized to maximize
good power output performance.
Treatments of Impedance Behavior of Various Circuits 545
J
:
N
I
_ I~ ________- L_ _ _ _L -_ _- L_ _ _ _ ~ _ _~
FIGURE 17.10. Five time-constant equivalent circuit for a porous electrode situation with indi-
cated selected values of R and Cd', and with L =0.1 JlH. Various other circuit models are possible.
(From Miller. ',2 Reproduced by permission of The Electrochemical Society, Inc.)
546 Chapter 17
~---------------------------------------, 100
.....
III
III E
.s:::.
E .... .1........................................ ...... 10 o
.s:::.
o
.......
N 100m 100m
o
10 m 10m
...CIJ
N
100m 10 100 1k 10k lOOk IN
Frequency / Hz
FIGURE 17.11. Frequency-response behavior of the five-time-constant network of Fig. 17.10.
Original figure based on ca. 100 points. (From Miller. 1.2 Reproduced by permission of The Elec-
trochemical Society, Inc.)
I k ----------------------------------------~ lk
100 100
10 10
E E
.c. ~
,~ 100 m 100m 0
_......
N
N
10m 10m
1 m 1m
.~
-~ ..,.
'N\ ,.
'"oM.
-- .'.'~ .,
FIGURE 17.12. Frequency-response of a memory backup electrochemical capacitor and the cor-
responding five-element equivalent circuit which gives a good fit to the frequency dependence of
the impedance components 2' and 2". (From Miller. 1,2 Reproduced by permission of The Electro-
chemical Society, Inc.)
Treatments of Impedance Behavior of Various Circuits 547
element, C (Z" = lIjwC), while the ascending part is due to the inductive ele-
ment, L, for which Z" =jwL. The minimum (at the self-resonant frequency) cor-
responds to a phase angle of zero where the opposing contributions of C and L
to Z" cancel. Then the impedance is just that due to the ohmic component, R.
Even with L = 0.1 ,uH, because C is very large, the self-resonant frequency is
relatively low, in the range 1 to 10 kHz.
where Vet) is the voltage after time t and Vi is the initial voltage before discharg-
ing starts. Equation (17.55) is a general one expressed in terms of a reduced time
scale, tIRC, as explained earlier.
Note that the time constant for each capacitative element is calculated by
multiplying the capacitance of that element by the series sum of all the resistive
elements from that RC element to ground, i.e., CR = C x ER (to ground). The
RC elements furthest from the load (Fig. 17.12) have the longest time constant
and hence the slowest frequency response. The fastest response is given by the
RC element directly coupled with the load resistance.
This circuit has a fairly wide range in its frequency response-on the order
of 0.5 kHz to ca. 0.05 Hz. Since all the C elements are accessed through a series
548 Chapter 17
2.9 6.3
13.7 2.4
23.2 0.40
37.8 0.19
Load
22.4 0.070
(At)
FIGURE 17.13. Cumulative capacitance of the five-element equivalent circuit required to simu-
late the wide-band frequency response of an Evans Capattery device. (From Miller?)
Treatments of Impedance Behavior of Various Circuits 549
where
(17.57)
Here a' = aAtS where A = cross-section of pore in cm2 and S = surface area per
unit length of pore. At sufficiently high frequencies, w ~ 00 or Imtl ~ 00; the
coth term ~ 1 so Eq. (17.57) becomes reduced to the Warburg form (i.e., analo-
gous to the frequency dependence of the Warburg diffusional impedance):
1- j (17.58)
Z( w ~ 00) =---.:---
(2SCd1w)
1 12
550 Chapter 17
I 00-+0
FlfliIe I
Porous
Eleclrode I IPlanar I
I
I
I
I
I
:: I
N I
I
z·
FIGURE 17.14. Comparative impedance plots for a redox pseudocapacitance in the complex
plane for a planar electrode (ideal case), and finite porous and semi-infinite porous electrodes.
(From Tilak and Chen. 5)
giving rise to a phase angle of 45°. However, this result arises because of the dis-
tributed resistance of the equivalent circuit representing the porous electrode
(transmission-line model) rather than any involvement of diffusion.
A wide-ranging series of forms of the complex-plane plots can arise for a
simple redox reaction, depending on pore length, conductivity in pores, magni-
tude of the Faradaic charge transfer resistance, and the associated pseudocapaci-
tance. The resulting behaviors represent several features of the frequency
response of RuOz pseudocapacitor electrodes.
In Eqs. (17.56) and (17 .57), p is the Laplace transform variable; S is the
t,
surface area of a pore of length per unit length; (J' is the specific conductance
of the solution (ohm-1cm- 1); A is the cross-sectional area; Rt is the Faradaic
charge transfer resistance of the electrode process, related reciprocally to the ex-
change current density, io; and RI is (io nF)/(RT) (l + q*/nf) where q* is deter-
°
mined by the component variations of the charge density on the metal with the
°
surface excesses of the redox species and R in the n-electron redox process,
i.e., q* is related to the electrosorption valencies of the and R species.
Treatments of Impedance Behavior of Various Circuits 551
4r-------r-~------------------~
I
1
1
I
3 1
1
1
1
. 2 CT' =- 100
1
11.0
N
1 1
1
1
2 3 4
Z'
FIGURE 17.15. Typical plots of impedance for imaginary vs. real components for a porous elec-
trode based on Eqs. (17.56) and (17.57), used in the calculations of Tilak and Chen5 for three values
of conductance, (1', of the solution and two values of the pore length, l
~
-62 -62 -130 -370
R=30 R-loo
R-5 R-10 -320
-52 -110
~
-270 u
-90
.
-42 -42
~ -220
" u -70
. i.
-32
-170
-50
-22 -22
-120
-30
-12
u
f
-2 -2
o 10 15 20 o 10 20 o 20 40 o 50 100
o
::r-
III
FIGURE 17.16. Series of complex-plane plots for a Faradaic pseudocapacitance with various values of the charge transfer
resistance, RF in ohms, and the pseudocapacitance, C.p, illustrating transition from an RC frequency response to a pure C re- ~...
sponse with decreasing frequency. (Calculations by Qian and Conway, unpublished.) (RF shown as "R"). ....-..I
-I
·90 ·90 m
·80 ·80 3
R=30 (1)
-70 -70 ::J
-60 -60
It
-50 -50
9-
-40 -40 3"
-30 -30
-20 -20
I
AI
::J
(')
-10 -10 (1)
0 0 m
(1)
10 100 1000 10000 100000 10 100 1000 10000 100000
::J"
AI
<
-90 -90
o·
...
-80 -80 R=100
o
-70 -70
~
-60 -60
-...
o·
-50 -50 c:
1/1
-40 -40 o
-30 -30 a"
-20 -20 c:
-10 -10
~
C_2000~F
0 0
10 100 1000 10000 100000 10 100 1000 10000 100000
FIGURE 17.17. Series of plots of phase angle vs. log frequency in hertz corresponding to the four series of
complex-plane plots in Fig_ 17.16 for the same four RF values. (Calculations of Qian and Conway, unpublished.)
C11
C11
Co)
554 Chapter 17
o z'
3. Interfacial capacitance with Rs
and parallel ohmic leakage
resistance. R
-z"
ro=o
Rs R --..40~/
'--!!_ _ _ _
R
ro-co z'
4. Interfacial capacitance with Rs
and parallel Faradaic leakage
resistance. RF a I(V)
-z
Rs ~~---+~~~~~
ro=o
ro __ co
FIGURE 17.18. Hierarchy of equivalent circuits of increasing complexity and their correspond-
ing frequency-response behaviors plotted in the complex plane. (RF and R~ in circuits 4 and 7, re-
spectively, have potential (V)-dependent values). (Diagrams are schematic).
Treatments of Impedance Behavior of Various Circuits 555
:z:'
~
RFf(V) (UPO case)
11
R, L __ R,\jl
-Z'
As
o
i
[Low co, -Z"-- -Z"(Cdi + Cq)J
7. Interfacial capacitance with Rs and
Faradaic pseudocapacitance Cq charged
via a Faradaic resistance, RF a f(V), with
Cq leaked by, a desorption Faradaic
resistance RF (OPO continuous reaction case)
As
REFERENCES
1. J. Miller and B. E. Conway, notes for an Electrochemical Society short course on
electrochemical capacitors at the Electrochemical Society meeting, Chicago, II. October 1995,
Electrochemical Society, Pennington, N.J. (1995).
2. J. Miller, in Proc. Second IntI. Symposium on Electrochemical Capacitors and Similar Energy
Storage Devices, S. P. Wolsky and N. Marincic, eds., Horida Educational Seminars, Boca
Raton, Ha. (1992).
3. R. de Levie, Electrochim. Acta, 8, 751 (1963).
4. H. Keiser, K. D. Beccu, and M. A. Gutjahr, Electrochim. Acta, 21, 539 (1976).
5. B. V. Tilak and Y. Chen, in Proc. Second Inti. Seminar on Double-Layer Capacitors and
Similar Energy Storage Devices, S. P. Wolsky and N. Marincic, eds., Horida Educational
Seminars, Boca Raton, Ha. (1992).
6. E. T. Eisenmann, in Proc. Fifth Inti. Seminar on Electrochemical Capacitors and Similar
Energy Storage Devices, S. P. Wolsky and N. Marincic, eds., Horida Educational Seminars,
Boca Raton, Ha. (1995).
7. K. S. Cole and R. H. Cole, 1. Chem. Phys., 9, 341 (1941).
Chapter 18
Self-Discharge of Electrochemical
Capacitors in Relation to that at Batteries
18.1. INTRODUCTION
Charged capacitors, like charged batteries, are in a state of high free energy
relative to that of the discharged state, so there is a pseudo-driving force for their
self-discharge. The driving force is thermodynamically the same as that which
provides current and power when the capacitance is discharged through a load
resistance, but then the resulting process is one of controlled discharge, which
is different from that for spontaneous self-discharge on open circuit. The ther-
modynamic situation of instability (high free energy) of the charged state is il-
lustrated in Fig. 18.1. The same kind of considerations apply to self-discharge
of battery systems, where a similar phenomenon is well known.
The phenomenon of self-discharge of an electrochemical capacitor dimin-
ishes its performance characteristics (e.g., power and energy density) because
there is a decline in voltage on open circuit after charging. This introduces an
unreliability factor in energy storage by a capacitor, depending on the type of
use to which it is put. The self-discharge characteristics of a capacitor device are
important in evaluating its performance and commercial specifications. Knowl-
edge of the mechanisms of self-discharge and their control is therefore impor-
tant for evaluation and improvement of such devices.
When capacitors or batteries are charged and then left on open circuit for
some time, a certain degree of self-discharge can set in, depending on the chem-
557
558 Chapter 18
istry and electrochemistry of the system, the purity of reagents and electrolyte,
and, significantly, the temperature. The rate of self-discharge, which usually di-
minishes with time, determines what is called the "shelf life" of batteries, which
is especially important in the case of primary cells, which are sold in the charged
condition and then stored as inventory in retail or wholesale outlets to the bat-
tery market. Some battery systems have excellent shelflife (e.g., Li-SOCI 2 pri-
maries); others, such as Ni·O·OH-Cd or Ni·O·OH-Zn (which are usually
employed as secondary rechargeable systems) have a substantially poorer life-
time in the charged state because of the self-discharge processes that occur, es-
pecially at the nickel oxide cathode or zinc anode.
Similar self-discharge can arise in the case of electrochemical capacitors
in the charged state, but for somewhat different reasons, in detail, and with dif-
ferent mechanisms from those for the case of charged batteries. However, the
practical result is the same: after the capacitor stands for some period in the
charged condition, the charge may become lost and the interplate voltage dimin-
ished, causing the capacitor to approach a disfunctional condition, (e.g., where
"standby" voltage and power are required), necessitating use of a large capaci-
tance for these purposes. Thus, the self-discharge behavior of electrochemical
capacitors is a matter of major practical significance in their operation and the
types of function they may be required to fulfill. However, to date, very little
work has been done to elucidate the mechanisms of self-discharge of capacitor
devices, although self-discharge rates are often measured and specified.
Charged electrochemical capacitors usually exhibit greater rates of self-
discharge than do most battery electrode or battery cell systems at a given tem-
perature. This difference of stability of voltage is attributable to the fact that the
potentials of battery electrodes (in the charged state) are usually thermodynami-
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 559
1. The first is if the capacitor (or battery cell) has been overcharged be-
yond the respective (plus or minus potential) decomposition limit of the elec-
trolyte. Then the self-discharge is really the spontaneous decline of the
overcharge overpotential, which will not decay further than the respective re-
versible potential for the H2 or the O 2 evolution reactions in water if the latter
is the solvent. This spontaneous decline of the overvoltage, 11, which is due to
the overcharging current, occurs on account of continuing discharge across the
double layer until 11 ~ O. The mathematical representation of this situation and
its consequences is treated later in this chapter.
The leakage process corresponds to a Faradaic, potential-dependent charge
transfer reaction. Its rate therefore tends to progressively decrease as the self-
discharge continues-exponentially with the declining potential according to a
Tafel relation, as indicated below. In terms of equivalent circuit representation
of the behavior of the electrode interphase of the double layer, the charge leak-
age process corresponds to a potential-dependent Faradaic resistance, RF , oper-
ating in parallel across the double-layer capacitance, its value increasing with
declining potential (Chapter 3).
2. If the capacitor material, and/or its electrolyte contains impurities that
are oxidizable or reducible over the potential range corresponding to the poten-
tial difference attained at the capacitor on charge, then the capacitor becomes to
some extent nonpolarizable, again with Faradaic charge leakage currents that
are potential dependent. If these impurities are present in only small concentra-
tions, then the self-discharge redox process(es) is (are) diffusion controlled. For
some impurities, their effect can be like that of a shuttle, with "Red" and "Ox"
species interchanging and diffusing in both directions between the positively
and negatively charged matrices of the electrochemical capacitor. Trace quan-
tities of transition metal ions (e.g., Fe3+, Fe 2+) can commonly occur as impurities
in some carbons as well as in redox-active organics. Also, oxygen, which is usu-
ally adsorbed on carbon materials, can be reduced to H 20 2 or HOi, which can
then be either reduced or reoxidized, providing a shuttle.
3. In the case of double-layer capacitors, self-discharge can also occur by
internal redox reactions involving some of the functional groups, e.g., those of
quinonoid kinds, commonly residing on the edges of graphitic particles. The
types of groups present have been identified (as reported by Kinoshita2) and are
listed in Chapter 9. However, since such reactive groupings are sparsely distrib-
uted on a molar or per gram basis of the active carbon material, and some are
not redox active, their reaction on self-discharge could hardly consume more
than about 2 to 5% of full charge at, say, a 1.3-V potential difference between
the plates in an aqueous electrolyte.
4. In case (l), if H2 and O 2 are generated as a result of adventitious over-
charge at the negatively and positively polarized half-cell electrodes, then situ-
ation (2) can be set up, with cross diffusion of H2 (to the positive electrode) and
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 561
O 2 (to the negative one). Depending on the electrocatalytic properties of the ca-
pacitor electrode material, H2 or O2 mayor may not be easily oxidized or re-
duced, respectively. At carbon, any evolved O 2 can be reduced to H 20 or
HOl: ion (or H 202> depending on pH), which can then behave either as an oxi-
dizing or reducing agent in subsequent shuttle depolarization reactions, leading
to self-discharge, as noted in (2). This mechanism is probably an important one
since O2 from the air is commonly adsorbed on high-area carbons and thus in-
troduced into the capacitor device unless the material is vacuum degassed when
the capacitor is being constructed.
5. If there are adventitious ohmic leakage pathways between the two elec-
trodes of a charged capacitor cell (e.g., through fibrils passing through separator
films, or on account of shunt leaks around the seals of bipolar electrode plates
in capacitors based on bielectrode configurations) then self-discharge will take
place as though the capacitor were discharged slowly through a load resistor.
recording instrument in such cases will distort the desired measurement. This is
a simple but important point.
Another simple and practically convenient procedure, as noted earlier, is
to apply a float current after charging that will maintain the full-charge potential
difference across the capacitor cell electrodes. This float current then just
matches the self-discharge rate at that potential. Similar measurements can be
made at lower potentials down the discharge curve. However, this procedure
gives no information about what is going on at one electrode or another. Table
18.1 contains a summary of the preferred methods for measuring self-discharge.
slope of the electrode polarization (Tafel) relation between YJ and log i, and also
the slope of the self-discharge relation (see later discussion).
In the simplest case, the self-discharge process is a continuation of the
overcharge reactions (e.g., generation ofH 2 and O2 from the solution above its
decomposition voltage), which cause a discharge of the double-layer capaci-
tance, Cd}, by the continuing passage of charge across the double layer until the
driving force (the overvoltage, YJ) declines to zero. This occurs as a result of the
self-discharge of the polarization across the double layer that is associated with
the collapse of the charge separation in this layer. If the rate of decline of YJ with
time is -dYJldt, it then follows that 1,3-5
obtains where the right-hand term is the Tafel function (Eq. 18.1) for the poten-
tial dependence of the current passing. For integration, the above equation is re-
arranged to
io (18.4)
-exp(-aVFIRndV = - . dt
C
RT io io [ t+-.
-exp(-aVFIRT)=-t+r=-
aF C C ~
cr] (18.5)
RTC +In (
-aVFIRT=ln [ aFiO] t+To crl (18.6)
Hence,
Thus the potential V declines with log t (Fig. 18.2) plus a term involving the in-
tegration constant, r. It should be noted that the slope of this relation is the nega-
tive of the Tafel slope, RT/aF, of the initial polarizing process. The result in Eq.
(18.7) applies only if C is independent of V or 11 over the potential range of the
observed self-discharge.
If the Faradaic depolarization current is a parasitic impurity current rather
than an overcharge current, the same analysis still applies as long as the kinetics
are activation controlled in that process (i.e., a Tafel relation obtains), but are
different from those for the Faradaic charging current leading to overcharge
(cases 1 and 2).
The integration constant r can be evaluated from the initial condition at t
= 0, where V = Vi and i = ii, the initial polarization conditions. Then
RT
r =-aF exp(-aV;lRT) (18.8)
FIGURE 18.2. Time dependence of potential on open-circuit self-discharge (Faradaic process in-
volved). Vj =initial potential at t =0 (log t =-00). Linear and log plots in time, Eq. (18.7).
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 565
r=(RT)~
aF Ij
(18.10)
or
c¢ = K exp(±VFIRT) (18.13)
It should be noted here that the potential dependence of coverage, fJ, by an in-
termediate that gives rise to this potential dependence of the pseudocapacitance,
C¢ (Chapter 10), is exactly the same effect that leads to a change of Tafel slope
e
for a desorption-controlled reaction step as increases from a small value to
near unity with increasing overpotential.
Introducing this V-dependent C¢ in Eq. (18.3) instead of the constant C
gives
where a¢ may differ from the a of Case 1, depending on the mechanism of the
Faradaic process (Chapter 3). When the latter involves appreciable V-dependent
coverage by the intermediate, a¢ = 1 + a for low 8 and a¢ =a for 8 ~ 1 (see
Chapter 3).
Rearranging Eq. (18.14) to combine the exponential terms gives
io
-[exp(±VF-a¢VF)IRT] ·dV= K·dt (18.15)
or
io
-[exp(±1 - a¢) VF IRT] . dV = K . dt (18.16)
- RT io KT)
io [ t+-.-
exp(±I-a¢)VFIRT=Kt+T=K (18.17)
(±1- a¢)F 10
(a¢+ 1) VFIRT=-ln [
(a¢ + 1)
RTK
Fio] -In [t+f;
KT] (18.18)
so that
and for large evalues (~ 1), -ve sign in Eq. (18.19), and a¢ = 112, Eq. (18.19)
gives
it is seen from the Nernst relations that when PH 2 and Po 2 are below their standard
values, the H2 potential will move to more positive values and the Oz potential
to less positive values, diminishing the difference in potential required for water
decomposition.
The buildup of Hz and O2 can then lead to self-discharge by the Faradaic
diffusion-controlled mechanism discussed earlier in this chapter, and the
achievable energy density is thereby diminished. A Ragone-type plot for a sym-
metric capacitor having 50-,um thick electrodes was constructed. 6
The extents of buildup of Hz and Oz were calculated for a duty period of
1000 cycles over a voltage range of 1 V, and the cumulative amounts were 0.218
and 0.008 mol m-z, respectively. These quantities translate into amounts that ex-
ceed the solubility of the two gases in the electrolyte in a 125-,um-thick capaci-
tor device, so appreciable gas partial pressures can be generated.
The equivalent circuit for a leaky regular capacitor is (there may also be an
equivalent series resistance, esr, Rs):
(18.20)
-C dV = i through R = ~
dt R
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 569
(18.21)
or
dV dt (18.22)
--v=RC
and then
or
Load current
logV/V\ diminishing
t
-ve
FIGURE 18.3. Time dependence of potential on discharge of a capacitance into a load resistance.
Vi =initial potential at t =O. Log [potential) is linear in t, Eq. (18.25).
that for solvent stability. This situation corresponds to cases (2) and (4) identi-
fied earlier.
In this case the leakage current is not io exp [a VFIRT], but a diffusion-lim-
ited current
(18.27)
dV (18.28)
-Cdt =zFD (dCRldx)
The solution of this type of equation is more difficult than for Case I (Eq.
18.3) since CR and dCRldx are time dependent so that
dCR) . dt (18.29)
-G- dV=zFD [d;
CR and dcRldt can be obtained by solution of Fick's equations, say, for semi-in-
finite diffusion to a plane capacitor electrode. Solutions for porous bodies or
within a cylindrical pore are more complicated, but the diffusion path length
will generally be small, on the order of microns or less in such electrodes.
The time dependence of CR and dCRldx at a particular distance x from a
plane electrode is generally an inverse square-root in t, so that integration ofEq.
(18.29) would lead to a self-discharge relation for the t dependence (decline) of
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 571
(18.30)
Most problems involve solutions to Fick's second law for particular boundary
conditions. Fick's second law, as a partial differential equation, is
(18.31)
where Co = c(x,t) = 0 and erf represents the error function integral (also arising
in statistics) defined by
A (18.33)
erflAI =_2_
;rr112
f exp(-Z2) . dz
o
and is to be found in tabulations of mathematical functions. Note that erf W ~
o as A ~ 0 and erf IAI ~ 1 as A becomes large. Z is an auxiliary variable.
A diffusion-controlled current under semi-infinite diffusion conditions at
an electrode of area A is
572 Chapter 18
or
(contrast Eq. 18.29) where Co is now the initial concentration in mol cm-3 of the
depolarizing impurity.
Integration of the above equation leads to
(18.37)
is the potential decay relation for self-discharge under linear (semi-infinite) dif-
fusion-controlled conditions. Thus the potential decline Vi - V (at time t) in-
creases with t l12 (Fig. 18.4).
The mathematics for the reaction at a cylindrical electrode have also been
worked out and involve Bessel functions. This case is relevant to a porous elec-
trode made, e.g., of carbon fibers. The results are
(18.39)
1=
zFADco
r
[1 Y
In(4t/J) - 2y - [In(4t/J) - 2y]2 ...
1 (18.40)
for large t/J values, where t/J is the dimensionless factor Dt!? and y = 0.57722; r
is the radius of the cylinder. The time variable for this case is in the parameter
t/J.
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 573
'-r-
Self-discharge
current
diminishing
FIGURE 18.4. Decline of potential in time, as (112, for a diffusion-controlled self-discharge proc-
ess (semi-infinite diffusion model; Eq. 18.38).
Again, the current I can be combined with -CdVldt and a self-discharge re-
lation for V(t) can be derived by integration. This is easy for the case of small
values of ¢ (short times), but is more complex for large ¢s since t is then an im-
plicit function in the inverse log term. Numerical evaluations are then easier.
The above functions are dealt with in Delahay's well-known monograph.lO
In the case of impurity-controlled self-discharge, it should be noted that the
reversible potentials for the respective impurity redox processes will be well
displaced from their standard (EO) values, probably up to about 360 mV (e.g., 6
magnitudes multiplied by 2.3 RTIF for a Ie redox reaction), owing to the dilu-
tion of the species. For a reduction reaction (e.g., from to Fe3+ to Fe2+), this dis-
placement would be in the positive direction in the initial virtual absence of
Fe 2+. However, the redox potential will actually depend on the ratio of activities
of the oxidized and reduced forms of the redox couple species.
(18.41)
the opposite of self-discharge, while for the ideally polarizable electrode or ca-
pacitor, iF = 0 and i == i e •
For optimum behavior, iF should be a minimum over the whole range of
potentials that correspond to the charging process over the operating potential
range of the capacitor: practically, this is about 1.3 V for aqueous electrolytes
and 3.0-3.5 V for nonaqueous, aprotic solvent solutions. If iF is appreciable to-
ward the end of the charging half-cycle of a capacitor, there will be a corre-
sponding appreciable self-discharge leakage current (at least initially) following
termination of charging when the overall i is cut to zero.
-r1~
I
I
~
I
h- I
RF(1) RF(2)
where RF.1 may not be the same as RF.2, not to mention that one side of the ca-
pacitor will be a positively charged and polarized electrode while the other will
be complementarily negati ve, so that different types of Faradaic leakage current
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 575
interfacial regions in the absence of current flow. This will also be accompanied
by diffusive ionic transport processes as the distributed interfacial charge den-
sities relax to a common value within the matrix. The principle involved in this
situation can be represented in an elementary way by a simple equivalent circuit
with three or four capacitative and resistive elements, as shown below.
+
WE CE,(a)RE
Cl
I
C2
I
{3
I
C4
I
I
Upon charging by a voltage ~ V applied from an external circuit connected at (a)
and (b), capacitor 1 will tend to be charged in a shorter time than that of capaci-
tor 2 (or 3, ... ). The model assumes the same values of successive Rs down the
network. If the time allowed for charging is less than the (practical) time re-
quired for complete dc charging as a result of the application of ~ V, capacitors
2 and 3, ... will be less charged than C\.
Conversely, if the charging is interrupted during incomplete charge, the
more extensively charged capacitor 1 at the interface will relax its polarization
by transferring some of its charge to capacitors 2, 3 ... through R 1, R2, etc. This
will appear phenomenologically as an apparent self-discharge of the capacitor
network, as observed in relation to potential measured at the external interface
of the network. This charge redistribution will continue throughout the CR net-
work until the open-circuit potential distribution becomes uniform within the
matrix. Experiments on a small hardware network of capacitors and resistors,
simulating an element of a transmission-line model have been carried out to re-
produce this situation. Figures 18.5 and 18.6 show the results.
Figure 18.5 shows the relaxation of potentials across four capacitors 1, 2,
3, and 4 in a four-unit network, following charging at 50 J.1A. It can be seen that
the potentials across a and b decline with time on open circuit (apparent self-dis-
charge); b declines after a short rise, while at c and d, the potential recovers due
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 577
11
+
10
~ RI
.!!! 9
I. .. ..
"0
>
8
~~):
7 ~ H.u
6
~ . , ~~ ~::. ~:~:~:~':~'::~-_": •.,,·.... '110·,.·,.·
5
('J,:.::::>.. charge curren! 50
Al -! Oak
R2 a 99k
IlA
4
R3: 99k
/(d) Cl·C2 o C3-C.·135 IJF
3
o 20 40 60 eo 100 120 140 160 180 200
lime I seconds
FIGURE 18.5. Time variation of potentials on open circuit across four capacitors in a transmis-
sion-line type of network following charging at 50 /lA. Experimental responses on a hardware R-C
network. (From Pell and Conway, in press, 1. Power Sources, 1999).
20
-< 10
:1.
.:;
!:!
'u 0
i:
'"0
0.
:r~.,..:
c:
0 '10
c
~
:; charge curranlSO IlA
u ·20
2
t-t.
RI·'OOk
-u
<II R2-S9k
0.
<II ·30 R3-99k
t---5:~
u
CI "C2-C3·C.~1351JF
·40
0 10 20 30 40 50 60 70 80 90 100
time I seconds
FIGURE 18.6. Time variation of charging currents on open circuit after charging at 50 /lA for
70 s; calculated from C. dVldt from the responses in Fig. 18.5, of the capacitors at (a), (b), (c), and
(d). (From Pell and Conway, in press, 1. Power Sources, 1999).
578 Chapter 18
so that log leT) is a linear relation in liT, the slope of which gives -MtlR.
For Faradaically controlled self-discharge processes, M+ is on the order
of 40 to 80 kJ mol-I, while if they are diffusion controlled, Mt is around 16 to
20 kJ mol-I, corresponding to the activated motion of the depolarizing impurity
or redox shuttle species in the bulk of the solution toward the electrode surface.
Covalent Associates, Inc., for example, report an E+ for self-discharge of 28 kJ
mol- 1 for one of their capacitors. This is one of the few data available. The gen-
eral and important practical consequence of the temperature effect is that self-
discharge of charged capacitors or batteries is a much more serious problem at
60-70°C than it is at 0-25°C.
With an activation energy of, e.g., 40 kJ mol- 1 (a typical value), the ratio
of self-discharge currents at 70°C compared with O°C is easily calculated from
Eq. (18.42), i.e.,
= 37 or 101.56, (18.45)
OH- + MH ~ M + H 2 0 + e (18.46)
with
2MH~2M+Hz i (18.48)
and do not need any electron transfer to or from the external circuit, as is re-
quired for a self-discharge process. Simultaneously, the charge on the double
layer becomes reduced in relation to the declining potential of the electrode on
open circuit. The same applies to all battery-type self-discharge processes; they
must be able to be written equivalently as chemical reactions not involving any
net flow of electrons. At a double-layer capacitor electrode, however, it is suf-
ficient that a direct single electrode process occur leading to self-discharge, e.g.,
S[z-] + Fe3+ ~ S[(z-)-l] + Fez+ where S is, say, a negatively charged surface
580 Chapter 18
ofthe electrode (its double layer) having its charge density, ze, diminished here
by Ie owing to reaction with a redox species such as an Fe3+ ion or more com-
monly 02 and H 20 2.
This situation was analyzed in detail in papers by Tilak and Conway4 and
by Harrington and Conway. 11 The relation between the decline of potential with
time and that of coverage by the electro active species is illustrated in Fig. 18.7.
First the potential declines with discharge of the double-layer capacitance until
a potential is reached where the buffering effect of the mixed process causes an
arrest of potential for a period during which the two coupled processes operate
to discharge the pseudocapacitance.
In the case of pseudocapacitance associated with the potential dependence
of the oxidation states of an oxide 1 such as Ni·O·OHJNi0 2 or PtOlPt0 2, a similar
mixed potential situation can arise, leading to 02 evolution on open circuit, if
the oxidation state upon completion of the charge corresponds to attainment of
an anode potential above the reversible potential for 02 evolution. Conway and
Bourgault! analyzed this situation in terms of coupled electron transfer between
Ni4+ and Ni 3+ states in the surface region of thin oxide film on Ni, and electron
transfers in the steps of electrochemical 02 evolution. The reaction scheme also
requires coupled proton transfer in the hydrous oxide lattice between OH- and
02- ions. It is illustrated in Fig. 18.8.
0.5 1.0
A
0.4 0.8
0.3 0.6
CD
> <1l
0'
~ ...
0
0.2 0.4 Q)
>
0
0
FIGURE IS.7. Relation between decline of potential (curve BCD) and change of coverage (curve
A) by an electroactive species, giving rise to a pseudocapacitance, Cp, when the latter is self-dis-
charged. 11 p is the plateau potential associated with discharge of Cpo B is the Cdl discharge region.
Ip is the time to onset of Cp discharge. Reprinted from D. A. Harrington and B. E. Conway, 1. Elec-
troanal. Chern., 221, 1 (1987), with permission from Elsevier Science.
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 581
COUPLED WITH:
OVERALL:
Ni(IIl)'Ni(IV)(0)3'OH + Hp .. 2Ni(1ll)·0·OH + OH'
40H' .. 2H10 + 01
FIGURE 18.8. Schematic diagram of the processes of coupled electron and proton transfer in the
self-discharge of an Ni(III) or Ni(IV) oxide electrode. (Based on Conway and Bourgault. I)
(18.49)
(18.50)
the potential being determined by the oxidation and reduction potential profile
as a function of reduction charge, e.g., as known from cyclic voltammetry ex-
periments. 14
Processes such as the above two can also be represented as mixed, coupled
electrochemical reduction and oxidation reactions; thus:
(18.51)
(18.52)
or correspondingly
582 Chapter 18
(18.54)
each of which pair adds up to the chemical steps shown in Eqs. (18.49) and
(18.50). Note again that no transfer of electrons need take place to or from the
external circuit.
In the case of RuOz films, and probably other transition metal oxides, it is
observed that some self-discharge also takes place. In the case of overcharge to
above the O 2 evolution potential, the self-discharge arises for well-understood
reasons, like that with nickel oxide. 1However, below the O2 reversible potential
and in the absence of molecular H2 (cf. Shibata13), self-discharge still seems to
arise, a phenomenon that is not so easy to explain except in terms of reactions
with some other reducing impurity reagents, adventitiously present, or inhomo-
geneity in the initial state of oxidation of RU02 after charging; see later discus-
sion.
With oxide films that are generated over several oxidation states, as with
nickel oxide (Niz+, Ni 3+, and probably Ni4+), a gradient of oxidation state of the
oxide film can be developed from the outer surface into the bulk. On termination
of charging, some relaxation of this gradient by a diffusion-controlled mecha-
nism can occur, leading to an apparent decline in the oxide film potential (at the
outside of the film) with time on open circuit, following termination of charg-
ing. Such a mechanism could also occur with Ru02 where Ru z+, Ru 3+, and Ru 4+
(or even Ru 6+) states are involved in the anodic development of RuOz films (see
Section 18.15).
18.14.1. Introduction
Experimental measurements on rates of self-discharge of electrochemical
capacitors or of corresponding float currents are common in the technical litera-
ture on the subject, but few, if any, reports are available on single electrode stud-
ies. Most commercial tests are made on packaged devices, so an overall effect
involving at least two electrodes is recorded.
In work by Conway, with Pell and Liu,15,16 self-discharge studies have
been made on single electrodes made from Spectracorp carbon fibers in aqueous
acid solution and on individual charged and discharged RU02 electrodes made
both electrolytically (at Ru metal) and by the thermal DSA procedure. Com-
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 583
parative experiments were also made on a packaged "Gold Cap" Panasonic unit
of 3.5 F. The results are outlined and discussed in the following paragraphs; in
particular, the diagnostic tests derived earlier (Table 18.2) were applied to the
results.
The carbon electrodes studied were prepared from high-area activated
carbon fiber fabric (Spectracorp Spectracarbon 2225, surface 2500 m2/g). The
apparent surface area of the electrode used in this work was 0.15 cm2. The elec-
trochemical behavior of the films was characterized by evaluation of the anodic
and cathodic reduction charge in voltammograms or by dc galvanostatic charge,
discharge, and recharge cycles at given currents.
Self-discharge and potential recovery measurements were conducted in a
three-compartment electrochemical cell containing 0.5 M H2S04 prepared from
high-purity Millipore water. The solutions were bubbled with Orfree Nz
throughout the experiments, some of which were continued for a number of
days. Galvanostatic charging of carbon electrodes was conducted up to various
potentials in the range 0.5 to 1.25 V and then the open-circuit decline of voltage
was recorded through a high input impedance electronic instrumentation sys-
tem.
Cathodic discharging was also conducted at controlled currents with po-
tential being taken down to limits of 0.30 or -0.10 (RHE). After completion of
such discharge curves, the electrodes were held on open circuit and recovery of
potential was observed.
Vln" 1.24 V
1.2 0.7
~ 1 .1 0.6
(5
> 1.06 V ~
'0
1.0 >
0.5
0.9
O.B
~ - 0.90 V
-33 mV
0.4
0.3
43 mV _ ...... -..•.••
0.7 ......... -~~.;- 0.2
0.1 0 _________ ••••••••••••
~
.. --" ............
0.6 0.1
10 2 3 4 5 10 3 3 4 5 10 4 . 3 4 5
time I seconds
FIGURE 18.9. Potential decay and recovery behavior at a charged and discharged carbon felt sin-
gle electrode plotted logarithmically in time. (From Pell, Liu, and Conway. 16)
2
(3
> 1.2 2
(3
4.5 1.0 .::
-
CI)
OJ
4.0 0.8 cU
r
(3
3.5 0.6 >
>..
3.0 0.4
iii
>
o
-
u
2.5 0.2 ~
Q)
(/)
2.0 L......J.._~-'---~--'-~--'-~--L-~-'500.0
o 10 20 30 40
time / hours
0.75 r-r~-.------r~--,--.......~--,--.,.........,.~-,-.,....,--r"1
.-..
CI)
(b 1.2
C) 0.70
Q)
..
~
(3 0.65 OJ
> 0.6 ~
... o
CI)
0.60 >
...
C)
cU >..
.r: 0.55 0.0 CI)
u
(/) >
o
:0 0.50 u
CI)
(
Q)
CD
3.5 0.6 >
~ >-
.r:. Q;
u 3.0
.~ 0.4 >
0
--
'C U
2.5 0.2 ~
(j)
en
2.0 0.0
0 100 200 300 400
time 1/2 / seconds1/2
--.
.~
3.0 0.4 >
'C 0
U
2.5 0.2 ~
(j)
en
2.~ 00 0.0
101 102 103 104 105
time / seconds
18.15.1. Background
It was shown in Chapter 11 how ruthenium oxide (Ru02) has attracted a
lot of attention as a possible electrochemical supercapacitor material since its
electrochemical behavior was recognized as being like that of a capacitor (e.g.,
under cyclic voHammetry study) by Trasatti and Buzzanca,17 and Galizzioli,
Tantardini, and Trasatti 18 and following our own investigations of that system
(cf. Refs. 19 and 20).
The large specific capacitance (many farads per gram) of Ru02 prepared
either electrolytically as films at Ru metal 19.20 or thermally from RuCl 3 or
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 587
1.5
w (a)
:c
a:
1.2
'"
>
>
~ 0.9
c:
--- - -
Q)
-
-
'0
c-
0.6
=>
~
.~
c=
Q) 0.3
c-
o
0.0
0 2 4 6 8 10 12 14
Time I hours
1.5
(b)
w
:c
a: 1.2
'"
>
>
~ 0.9 -- - --
"E
Q)
-
(5
c-
0.6
'5
~
'u
C:
(l) 0.3
c-
o
0.0
0 2 4 6 8 10 12 14 16 18 20 22 24
Time f hours
FIGURE IS.11. Open-circuit potential decay following anodic charging to 1.40 V (RHE) and
open-circuit potential recovery following cathodic discharge to 0.1 V (RHE) for (a) thermally pre-
pared RU02 and (b) electrochemically prepared RU02 electrodes in 0.5 mol dm- 3 H2S04 at 298 K.
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 589
as that attained in potential decay from the charged state. Similar recovery be-
havior was observed at the electrolytically formed films [Fig. 18.11(b)].
Plots of decaying or recovering potential (even after inclusion of the inte-
gration constant time r; cf. Ref. 1 and Eq. IS.6) vs. log [time] are not linear, in-
dicating that a Faradaic process of self-discharge, of the kind treated in Refs. 1
and 4 and examined earlier here, is not applicable.
3. The most remarkable observation is that following the recovery of the
potential to ca. 0.6 V, a further cathodic discharge down to 0.10 V, involving
passage of an appreciable further cathodic charge, can be conducted; then, fol-
lowing that further discharge, the potential again recovers to near the 0.6 V
value [Fig. IS.12(a)]. This discharge-potential-recovery cycle can be repeated
many times and the successive recovery potentials remain almost the same. A
"perpetual" source of charge is, of course, impossible, so presumably there is a
sufficient bulk reservoir of oxidized Ru to maintain a surface region, which is
evidently potential determining and sufficiently oxidized that (through diffu-
0.8
(a)
0.6
w
:::c
a:
en
>
>
0.4
Cii
'E
Q)
'0
c...
0.2
o 2 4 6 8
Time I hours
FIGURE 18.12. Multiple potential recovery transients at RU02 in aq. H2S04 at 298 K following
successive galvanostatic discharges, without interim recharging: examples of successive recoveries
of potential at (a) a thick, thermally formed RU02 film;
590 Chapter 18
In order to test this point further, similar successive discharge and recovery
cycles [Fig. lS.12(b)] were carried out at a much thinner film of oxide formed
thermally on Ti. Then the final rest potentials after successive recoveries were
found eventually to decrease, discounting the apparently indefinite source of
cathodic charge indicated by the results obtained with thicker films.
This remarkable succession of recovery-redischarge cycles [Figs.
lS.12(a) and lS.12(b)] must arise through a "diffusion of oxidation state", fol-
lowing discharge of the surface region, back to the surface from inside the bulk
of the RU02' The following succession of processes can be suggested as indi-
cated below:
+e +e
Ru lV ~ Ru IIl ~ Ru ll
0.8
(b)
0.6
w
:x:
II:
en
>
>
0.4
cti
~
Q)
"0
a..
0.2
probably involving electron and proton exchange (cf. Ref. 1); and also
Coupled with such redox processes must be adjustment of the local distribution
of 0 2- and OH- ions in the lattice by proton transfer, namely
Proton transfer equilibria with H30+ and H 20 in the surface region even-
tually will also be involved
established. It is about 0.7 V, or 0.9 V, RHE, as seen in Fig. 18.11, differing be-
tween the thermally and electrolytically formed RU02 films.
In order to elucidate what kinds of equilibrium redox processes might be
involved in establishing these potentials, the pH dependence of the steady po-
tentials was determinedY The results are shown in Fig. 18.13 from which
dE/dpH = -30 m V was reproducibly found for the thermally formed film com-
pared with -60 m V for the electrochemically formed one. These data provide a
pH/potential kind of Pourbaix relation for the potential-determining processes
at the two oxide materials following self-discharge and potential recovery. Evi-
dently the oxide in its supposedly RU02 state at 1.4 V (or at 1.3, 1.2, 1.1 V) is
not stable in aqueous solution at any pH between 0 and ca. 10 (Fig. 18.13), and
prefers to establish a substantially less positive steady potential. While a -30-
m V dependence on pH has not previously been reported, Siviglia, Daghetti, and
Trasatti 23 found that the open-circuit potential of a thermal RU02 electrode ex-
hibited a -60-mV dependence on pH.
In Fig. 18.13 the potentials asf(pH) have been corrected for the 60-mV pH
dependence of the hydrogen reference electrode used, so the pH dependence of
the potentials plotted can be interpreted in terms of half-cell processes involving
two oxidation states of Ru in the potential-determining process, together with a
stoichiometric number of involved protons and a corresponding number of elec-
trons.
0.9
w • thick film of electrolytic RU02 on Ru
::r: 0.8
:z • thick film of thermal RU02 on Ru metal
en
>
> 0.7
'"
:;:;
c
Q)
0.6
"0
-0.
::>
.~
0.5
0.4
u
'c..=
Q)
0.3
0
0.2
a 2 4 6 8 10 12
pH
FIGURE 18.13. pH dependence of open-circuit decay and recovery potentials after approach to
steady values for _ thermally and. electrochemically prepared thick film of RuOz on electrodes.
Reprinted from Pell et aI., Electrochim. Acta, 42,3541 (1997), with permission from Elsevier Sci-
ence.
594 Chapter 18
involving hydrated oxides (on the lhs and rhs) of the type suggested by Burke
et a1. 25,26
These quasi-thermodynamic considerations indicate interestingly that the
redox equilibria at the anodically formed oxide film and at the thermally gener-
ated one must be quite different. It may be significant that it is the -30-mV slope
that arises with the thermal film that still retains some hydrous character pro-
vided the thermal treatment is not at very high temperatures. The slope value of
-30-mV can be accounted for only by the above process involving a hydrous
structure of some kind. Other hydrated Ru02 phases require the same numbers
of electrons and protons in the redox equilibria, e.g.
Self-Discharge of Electrochemical Capacitors in Relation to that at Batteries 595
The unambiguous difference between the Nernstian slope for the thermally
prepared compared with the electrolytically generated Ru02 film is of consid-
erable interest in relation to the chemical constitution of the surfaces (or bulk as
well, in the case of the electrolytic film) of the two materials despite the quali-
tative similarity between their respective potential decay and recovery behavior
(Figs. 18.11 and 18.12).
The above thermodynamic and potential decay information indicates that
the self-discharge process does not originate (as it does at Ni·0·OH-Ni02 elec-
trode surfaces I) from continuing O 2 evolution since (1) the potential decay proc-
ess continues down to ca. 0.75 V rather than 1.23 V (the OrH20 reversible
potential) and (2) it is also observed from several initial potentials below that
reversible potential. Hence the potential decay process must involve readjust-
ment of Ru redox couples in the surface region of the oxide. The same argument
also applies to the process involved in potential recovery following cathodic
discharge down to 0.1 V, or other potentials less than 0.75 V.
REFERENCES
1. B. E. Conway and P. L. Bourgault, Can. J. Chem., 37, 292 (1959); Trans. Faraday Soc., 58,
593 (1962).
2. K. Kinoshita, Carbon: Electrochemical and Physicochemical Properties, Wiley, New York
(1988).
3. 1. A. V. Butler and M. Armstrong, Trans. Faraday Soc., 29,1261 (1933).
4. B. V. Tilak and B. E. Conway, Electrochim. Acta, 21, 745 (1976); 22,1167 (1977).
5. B. E. Conway, in Power Sources, vol. 16 (Brighton Power Sources Conference Proceedings)
(1997), Inti. Power Sources Symposium Ltd.
6. B. Pillay and 1. Newman, J. Electrochem. Soc., 143, 1806 (1996).
596 Chapter 18
7. O. S. Ksenzhekand V. V. Stender, Dokl. Akad. Nauk. SSSR, 106, 487 (1956); see also Russian
1. Phys. Chem., 27, 1089 (1963).
8. 1. Crank, The Mathematics of Diffusion, The Clarendon Press, Oxford (1956).
9. H. S. Carlslaw and J. C. Jaeger, Conduction of Heat in Solids, Oxford Univ. Press, Oxford,
(1947).
10. P. Delahay, New Instrumental Methods in Electrochemistry, Chapter 3, Interscience, New
York (1954).
11. D. A. Harrington and B. E. Conway, 1. Electroanal. Chem., 221, I (1987).
12. S. Shibata and M. P. Sumino, Electrochim. Acta, 20, 739 (1975).
13. S. Shibata, 1. Electroanal. Chem., 89, 37 (1978).
14. F. G. Will and C. A. Knorr, Zeit. f Elektrochem., 64, 258 (1960).
15. W. G. Pell, T.-C. Liu, and B. E. Conway, Electrochim. Acta, 42, 3541 (1997).
16. W. G. Pell, T.-C. Liu, and B. E. Conway, in Proc. Sixth IntI. Symposium on Electrochemical
Capacitors and Similar Energy Storage Devices, S. Wolsky and N. Marincic, eds., Florida
Educational Seminars, Boca Raton, Fla. (1996).
17. S. Trasatti and G. Buzzanca, 1. Electroanal. Chem., 29, App. 1 (1971).
18. D. Galizzioli, F. Tantardini, and S. Trasatti, 1. Appl. Electrochem., 4, 57 (1974).
19. S. Hadzi-Jordanov, H. A. Kozlowska, M. Vukovic, and B. E. Conway, 1. Electrochem. Soc.,
125, 1471 (1978).
20. S. Hadzi-Jordanov, H. A. Kozlowska, and B. E. Conway, 1. Electroanal. Chem., 60, 359
(1975).
21. J. P. Zheng and T. R. Jow, 1. Electrochem. Soc., 142, L6 (1995); 1. P. Zheng, P. J. Cygan, and
T. R. Jow, 1. Electrochem. Soc., 142,2699 (1995).
22. T. Arikado, C. Iwakura, and H. Tamura, Electrochim. Acta, 22, 513 (1977).
23. P. Siviglia, A. Daghetti, and S. Trasatti, Coli. Surfaces, 7, 15 (1983); see also 1. Electroanal.
Chem., 122,395 (1981).
24. M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, Nat!. Assoc.
Corrosion Engineers, Houston, Tex. (1974 reprint).
25. L. D. Burke and 1. F. Healy, 1. Electroanal. Chem., 124, 327 (1981).
26. L. D. Burke, M. E. Lyons, E. J. M. O'Sullivan, and D. P. Whelan, 1. Electroanal. Chem., 122,
403 (1981).
Chapter 19
19.1. INTRODUCTION'
*This section is based on material contributed by Dr. B. V. Tilak (Occidental Chemical Corp.),
Grand Island, N. Y. and Dr. S. Sarangapani, ICET Inc., Norwood, Mass., and edited for this volume
by the author.
597
598 Chapter 19
placed over a Toray H060 (Toray Marketing, New York) carbon paper (or the
Spectracorp equivalent) and gently rolled with a rolling pin between several lay-
ers of filter paper to remove excess water. The electrode is then sandwiched be-
tween several layers of dry filter paper and pressed in a hydraulic press at
100-400 psi for 1-2 min. At this stage, the microporous filter membrane can
be removed by gently peeling off the layer from the electrode. The electrode is
then placed between PEP Teflon films and pressed at 100°C at 100-400 psi for
1-2 min. The electrode is then dried at 100°C for 1 h, baked at 270°C, and sin-
tered at 340°C for 20 min.
The hydrophobic nature of such electrodes prevents the full realization of
the maximum available capacitance during the initial testing period. However,
these electrodes undergo a "break-in" phenomenon, during which period the
electrolyte seeps into the electrode and wets the internal finer pores. Vacuum
filling of the electrolyte is desirable to speed up the break-in process, and/or a
trace of surfactant can be added to the electrolyte.
A titanium foil is immersed in hot oxalic acid for 2-3 min; it is then ultra-
sonically cleaned in distilled water. A solution of the following composition is
prepared (South African Patent, 680,834):
. - - - - - - - Electrode 1
. - - - - - Separator
Electrode 2
Heater
Pad
~ '/4.1r-~1/4'
__ .1 ~
1/2" 1/2'
FIGURE 19.1. Sectional diagram of laboratory-scale electrochemical cell for testing capacitor
electrodes at various temperatures.
Preparation and Evaluation of Electrochemical Capacitors 601
glass fiber paper (Whatman) soaked with 6 M sulfuric acid electrolyte. Suitable
end plates made of resin-filled graphite (Carbone of America, JP1345 or equiva-
lent) can be used as current collectors. A simple framework that consists of two
stainless-steel end plates, with pedestals machined into them, serves as the cell
housing, as shown in Fig. 19.2. This arrangement is useful for laboratory screen-
ing of potential capacitor materials in successive series of tests. The cell assem-
bly is placed between the two end plates, which are clamped together with bolts
and wingnuts. Care should be taken to apply insulating sleeves on the bolts to-
gether with nylon washers to prevent shorting of the two electrodes. Sufficient
pressure can be applied to the cell by varying the thickness of the gaskets in the
cell andlor tightening the nuts. This design also permits cells with nonaqueous
electrolyte (assembled inside a glove box) to be tested under ambient condi-
tions. A spring-loaded cell construction suitable for the present application has
been described by Kronenberg, Stein, and Codd. 2 For the assembly and testing
of solid polymer electrolyte capacitors, the cell assembly shown in Fig. 19.2 can
be used (Sarangapani et a1. 3.4).
Gold Plated
Tab
Cell Assembly
~
Teflon Gasket
Insulated
Bolt
FIGURE 19.2. Cell assembly based on arrangement of electrodes illustrated in Fig. 19.1, but for
a solid polymer electrode.
602 Chapter 19
~ Electrode Holder
1 1 - - - Counter Electrode
DHE or HgS04
Reference
Electrode
Bridge
FIGURE 19.3. Electrochemical three-electrode cell (thermostated) for screening the behavior of
capacitor electrodes by means of cyclic voitammetry. DHE signifies dynamic hydrogen (reference)
electrode.
Noryl Base
Viton Pad
Gold Foil
~
Test E.lectrode
I
/ ~ Viton Washer
/ ~ Noryl
~ / ~;w
The charge, q, and energy, E, input and output to the capacitor can be cal-
culated through integration of the voltage time transients according to:
(19.1)
REFERENCES
Technology Development
20.1. INTRODUCTION
In very recent years, the following possibilities for new and expanded utili-
zation of such devices, including substantially scaled-up systems, both in actual
size and energy storage capacity, as well as in operating voltage, have been rec-
ognized:
20.4.1. Electrodes
The requirements for electrochemical capacitors are substantially different
from those for battery electrodes. The following aspects are ideal requirements.
In relation to the above ideal requirements, the active area, or active weight
or volume, is a common concept involved in descriptions or specifications of
battery electrodes. It refers to the active mass of electrode materials that can un-
dergo the required electrochemical redox reactions of the battery. A similar term
can be applied to electrochemical capacitors; in the case of double-layer-type
capacitors, it refers to the real area of electrode matrices that can undergo elec-
trostatic charge acceptance or charge depletion. In the case of redox-pseudoca-
pacitance devices, the terms have the same significance as for battery systems,
but the real accessible electrode area is also usually important because this de-
termines power performance.
The electrochemically significant active area in an electrochemical capaci-
tor device is usually significantly less than areas of carbon materials determined
by BET measurements in the dry state. As referred to earlier, this is due to prob-
lems of wetting and invasion by the electrolyte into the finer pores of the pore
distribution. A useful summary of the characteristics of various electrode mate-
rials is shown in Table 20.3.
Expectations Practical
(20.1)
i.e., the overall capacitance of n identical capacitor units in series is one nth of
the individual value, so charge (q) storage for a given overall interterminal volt-
age, V = II V j is nq/Cj , which is q/Cn from Eq. (20.1) since Vi = q/Ci. Corre-
spondingly, the energy stored is the same as that for an individual unit, as shown
below.
For an individual unit, the energy stored at a potential difference of Vi is
(l/2)CiVr. For n such (identical) units in series, the overall interterminal volt-
age, V, is n Vi and the overall capacitance from Eq. (20.1) is Cn = C/n. The over-
all energy, E, stored is then
This is n times the energy stored in each unit of capacitance Cj , each charged to
a potential difference Vi' Thus, although n capacitors combined in series have
together lin of the individual unit capacitance value, the overall stored energy
is n times that for each unit, Eq. 20.2. Reflection will show that this result is a
necessity arising from the law of conservation of energy since the simple series
Technology Development 621
n
1 1 1 1 (20.3)
- = - + - + - + · .. etc.=I, lie;
en e, ez e3 ,
However, the potential differences across each unit are different but add up to
the total, V. Thus the potential differences are
(20.4)
(20.5)
Seals
//\
III f
Case
--"1HHHr--~~
Case
FIGURE 20.2. Schematic diagrams of bipolar electrode arrangements for an electrochemical ca-
pacitor showing a combination of capacitor units equivalent to a bipolar stack.
~ ___ Ieakage
I II I pathway
FIGURE 20.3. As in Fig. 20.2 but illustrating current leakage or shunt effect at a leaky seal in a
bipolar electrode array.
Technology Development 623
discharge. The effect is the same as that of putting the electrically joined cathode
and anode of two neighboring cells of a multicell battery into a common volume
of electrolyte; then short-circuit discharge between two such electrodes of
course rapidly occurs. The situation is closely analogous to the behavior of a
galvanic couple, e.g., Cu and Zn metals in contact, immersed in an electrolyte.
It must be understood that there is a double layer on each side of each bi-
polar electrode, but with a polarity opposite to that of the solution (Fig. 20.4).
Down the array of cells, from EI to E 2, there is a progressive series of potential
drops (Eq. 20.4) at each electrode interface along the cell stack. The bipolar ge-
ometry can be imagined to arise from bringing plates A and B in Fig. 20.4a di-
rectly into back-to-front contact corresponding to the bipolar plates AB in Fig.
20.4b. Electrolyte resides in the space between the end plate EI and the first
plate A and then between B and the next plate A, etc., to the end plate, E2 • The
configuration b requires the ends of each bipolar plate to be sealed to an outer
confining case so that each region is electrolytically separated from its neighbor.
Depending on the mode of construction of the bipolar assembly and the rigidity
of the plates, the bipolar configuration mayor may not require conducting sepa-
rators between E, A, B, and E2 , and between the repeated series of electrode
pairs, AB, AB, etc.
One of the practical developers of carbon-based bipolar electrochemical
capacitors in a major but exploratory way is Maxwell Laboratories (San Diego,
California). They were funded in 1992 under the DOE Ultracapacitor Develop-
ment Program, which aimed at units capable of providing at least 5 Wh kg -I and
power capability in the range of 500-1000 W kg-I. Another bipolar, carbon-
based capacitor, employing a nonaqueous electrolyte, and rated at 70 V, was
demonstrated by Redox, Inc. (Marincic, FES 1995).
(a) (b)
FIGURE 20.4. Change from a multi-unipolar stack to an equivalent bipolar electrode stack con-
figuration (schematic).
624 Chapter 20
some gas flow and water management arrangements can assist with the manage-
ment of heat produced from irreversibility of the cell reactions and PR heating
during power production (Section 20.8).
For large capacitor units for which there is no self-ventilation, heat man-
agement requires special design engineering and control. Continuing work in
this area is required for hybrid electric vehicle motive-power systems, espe-
cially those for high-power applications. Further details are discussed in Section
20.7.
Several of these problems also arise in well-known ways in larger scale battery
designs and in the technology of electroplating.
Scale-up factors for use of organic electrolyte electrochemical capacitors
in hybrid configurations with lead acid and zinc-bromine batteries were consid-
ered by Marincic (PES 1995) in some tests and modeling. A large bipolar plated
carbon-felt capacitor, rated at 70 V, was tested. Good plastic sealing of the edges
of the electrodes in the multiplate assembly was achieved, leading to virtually
zero shunt effects.
The energy density and the power density were shown plotted in a useful
comparative way against a common axis of capacitor weight fraction in the two
battery hybrid systems (Figs. 20.5 and 20.6). Capacitor power density increases,
as expected, relative to energy density of the hybrid combination because a
greater weig'lt fraction of the capacitor component is present. Note that the
crossover point arises at a higher capacitor fraction in the case of the Zn-Br2 than
for the lead acid hybrid system. These working diagrams provide a useful basis
for the design and optimization of performance of hybrid capacitor-battery
power systems for electric vehicles where scaleup becomes an important con-
626 Chapter 20
80 r-----------------------------------------------~600
LEAD-ACID HYBRID
101
x.
.s::
~ ~
"- 400 "-
>-
f-
>-
U) t:
Z 300 ~
W W
0 o
>- 200 a::
C)
a:: w
w ~
z o
w 100 c..
__ _ _ _ _L -_ _ _ _ _ _L __ _ _ _ _ _L __ _ _ _ _ _L __ _ __
0
~ ~ ~ ~ ~ ~ ~O
sideration for the high voltage and high energy, high power levels of operation
required for such applications.
With carbon-felt electrodes oflarge size in monopolar configurations that
do not need to be supported on a separate current collector matrix, scaleup can
lead to increasing voltage losses across the felt plate to the edge current collector
connections relative to those in a smaller scale electrode of the same, say rec-
tangular, geometry. These are the same factors that also apply in scaleup of the
size of battery electrodes. This ohmic scale-up factor depends on the specific re-
80 r-------------------------------------, 500
Zn/Br 2 HYBRID
'",""
.c:. 50
;:
"-
~
t:
rJ) 40
Z
W
Cl
>-
\!l
200 5
a: '!:
w 20 o
Z 100 Cl.
w
L-__L -_ _L-~__~~~--~~-L--~~~--~O
00 0.2 0.4 0.6 0.8 \
CAPACITOR WEIGHT FRACTION
FIGURE 20.6. As in Fig. 20.5 but for hybrid with a Zn-Br2 battery. (From Marincic, FES 1995.)
Technology Development 627
only a part of the stored energy is available (see Chapter 17); e.g., in discharging
from 400 to 200 V (or in general from Vinitial to (1I2)VinitiaI>, 75% of the stored
energy becomes available since stored energy is (1I2)CV 2 at any voltage, V. The
Maxwell sintered fused composite electrode structures are capable of meeting
these specifications with the stated energy-density requirement and are now fig-
uring prominently in electric vehicle power-train technology (see Section
20.13).
Deposition of other materials, such as the electroactive polymers, onto
carbon-fiber support material has also been employed, and was later investi-
gated in the author's own laboratory27 for the case of Ru02 in order to provide
more extended films.
Nishino and Yoshida (PES 1991) described the direct use of activated carb-
on fibers as the electrode material for a double-layer capacitor. The technology
involved plasma spraying aluminum directly onto the surface of a compacted fi-
ber matrix to provide good external circuit contract.
It has been emphasized in several chapters of this volume that for success-
ful design of double-layer capacitors, high-area carbon materials with accessi-
ble fine pore structures are required. Delnick, Ingersoll, and Firish (PES 1993)
have evaluated a variety of microcellular carbon foams (Fig. 20.1) derived by
controlled pyrolysis and carbonization of polymers such as polyacrylonitrile
(PAN), polymethacrylonitrile (PMAN), resorcinol-formaldehyde (RR),
divinylbenzene cross-linked methacrylonitrile (DVBPMAN), phenolics (furfu-
rylaicohol), and cellulose polymers such as rayon.
Further results of tests by Andrieu et al. (FES 1993, 1994) (Aicatel
Alsthom Recherche) on liquid organic electrolyte electrochemical capacitors of
D-size having a capacitance of 175 F (75 g) and operating voltage of 3.0-3.1 V
(internal resistance 25 mohms), and manifesting an energy density of 2.9 Wh
kg- 1 and power density of 1.20 kW kg- 1 are reported in PES (1994). The sepa-
rators used were 50-,um microporous polyolefin films, and the active surface
was ca. 600 cm2. The electrodes consisted of a thick coating of activated carbon
black on a perforated aluminum foil with a PTPE binder.
The materials have been examined in some detail by Lipka (PES 1993);
they possess a high degree of crystalline anisotropy. Depending on processing
and important pretreatment conditions, a variety of specific properties, useful
for electrochemical capacitor fabrication, can be generated. In the work de-
scribed by Lipka (PES 1993), pitch-based carbon was used in as-received and
activated preparations, as well as some materials containing PAN-based carbon
fibers and epoxy matrices. The nominal fiber diameters were 10 ,urn. Capaci-
tance behavior was characterized by ac impedance and cyclic voltammetry.
An important relatively high-area carbon material, an alternative to high-
area carbon powders, is carbon fiber or felts of carbon fibers that give specific
Technology Development 629
capacitance values as listed in Table 20.5. These have the advantage of easier
handling and mechanical management.
The (proprietary) pretreatment conditions can give rise to specific differ-
ences in the morphology of the resulting modified carbon materials so that, to
some extent, tailormade structures of controllable morphology can be prepared
(Lipka, FES 1993). This offers important opportunities for advancing the tech-
nology in this field, leading to desirable materials properties of the basic carbon
structures required for double-layer-type, electrochemical capacitors.
Figures 20.7 and 20.8 show SEM micrographs of two carbon fiber materi-
als activated in two proprietary ways, "A" and "B." It can be seen that major
changes in the accessible inner area of the carbon fibers can be obtained, de-
pending on the mode of pretreatment.
Lipka and Zawacki (FES 1995) continued their earlier work (FES 1994)
by examining the cycling and other aspects (Tables 20.5 and 20.6) of the per-
formance of carbon fiber materials for electrochemical capacitors. Activated
carbon fibers of 10 11m diameter prepared from pitch were used in chopped
forms having a range of aspect ratios (length to diameter ratios). The activation
procedure (proprietary) leads to multiple splitting (see SEM photos, Figs. 20.7
and 20.8) of the fibers, producing an enhanced area. The initial fiber material
(so-called Type 1, short fiber), as received, had an area of 0.35 m2 g-1 while after
activation the specific area was increased to 0.73 m 2 g-I.
Parallel 167
Perpendicular 380
Random 371
Source: From Lipka (FES 1993).
aCapacitance per area of carbon fiber measured at 0.05 V vs. SCE.
630 Chapter 20
g
~
:s
o
0"
cc
'<
~
0"
'g
3
III
:s
-
FIGURE 20.7. Scanning electron micrographs of mesophase pitch carbon fibers and PAN fibers before and after activation treatments: (a) Mesophase pitch
carbon fiber A, as received (fiberlength). (b) Mesophase pitch carbon fiber A, as received (fiber end). (c) PAN carbon fiber A, as received (fiber end). (d) Meso-
phase pitch carbon fiber A, after activation process A (fiber end). PAN = polyacrylonitrile polymer precursor; Proprietary activation processes A and B are dis-
tinctively different, but proprietary, activation treatments. (SEM photos kindly provided by Professor S. Lipka of Aorida Atlantic University, FES 1993.)
Ol
W
.....
en
Co)
I\)
FIGURE 20.8. As in Fig. 20.7 but for two activated carbon fibers. (a) Mesophase pitch carbon fiber B, after activation process B (fiber length). (b) PAN carbon oJ
DI
fiber A, after activation process C (fiber length/end). (From Lipka, FES 1993.)
¥..
~
Technology Development 633
Io.1mA
FIGURE 20.9. Comparison of cyclic voltammograms for activated and unactivated carbon fiber
of Type I in 30 wt.% aqueous H2S04 taken ata sweep rate 0[200 mV s-l. (From Lipka, FES 1994.)
634 Chapter 20
.. + J
~
...... f
>- 200.- .. ............. ( 0)
!:: .... ......
... ".,
(/) -
zw
..........
,
o
100
a::
w
~
a.
-.
..........
O~------~--------~------~~"'e--
, 2 3
ENERGY DENSITY I Wh kg- 1
800
.,
r
'.
lOt ' ..... ,
~
... (b)
600 ... ...
.,
~
~
>-
I-
....
.... , ,
in 400
Z ,,
w
'.,
0 ..... ,
'.
a:: 200
w
3:
0 ...
a. ....
... I
0 2 1
3
ENERGY DENSITY I Wh kg- 1
FIGURE 20.11. Modeling of Ragone plots for a double-layer capacitor having a thin-film con-
figuration and electrolyte conductivity of 5 x 10-5 S cm -1, which is typical of most solid polymer
electrolytes. Capacitance value: 40 F g -I. (a) 1OO-,um electrodes, 50-,um electrolyte. (b) 50-,um elec-
trodes, 30-,um electrolyte. (From 8audry et aI., FES 1994.)
made from tantalum bearing a Ta20S barrier oxide film) coupled with a low-
voltage, high energy-density electrochemical redox pseudocapacitance elec-
trode (formed e.g., from RU02) serving as the cathode of the electrode pair.
Operating voltages of around 150-230 can be achieved with capacitances up to
100 mF. Capacitance values remain constant within about 2% over a voltage
range of 50 to 230 V. Complex-plane impedance plots are typical of a transition
638 Chapter 20
DIELECTRIC MMO
\\ /
I
p
E
o L
T C
E A
E A
C T
N N
T H
T 0 R
I D 0
0 D
A E
L E
L Y
T
E
+
-------
FIGURE 20.12. Voltage profile normal to the electrodes in an Evans Hybrid-type capacitor using
a mixed metal oxide cathode material (schematic).
Technology Development 639
where R; is the sum of the internal electrolyte and separator resistances. Nor-
mally such a capacitor is operated with recognition of its polarity, the high volt-
age being established over the thin oxide film of Al 30 3 or Ta205 at the anode
exhibiting capacitance Ca «<Co see above). The oxide film is the dielectric in
Ca and the pseudocapacitance of RU02 gives rise to Ce . At each oxide/electro-
lyte interface, double-layer charge separation also occurs, but the overall ca-
pacitance for such electrolytic capacitors does not arise primarily from the
capacitance of those double layers as it does in an electrochemical double-layer
capacitor.
In order to provide some examples, a selection of performance data for 50-,
28-, and 32-V units of the Evans "Hybrid" capacitor having capacitances of 18,
18.1, and 8 mF are listed in Table 20.7. Each unit has an attractive high operat-
ing voltage capability, but their capacitances are on the order of 1000 times
smaller per gram than those of currently developed regular carbon-based dou-
ble-layer or RU02 redox capacitors. However, the energy storage capability
must be considered: at 50 V, a 20-mF capacitor can ideally store (50)2 x (20/2)
X 10-3 joules, i.e., 25 J. An RU02 pseudocapacitor of, say, 10 F g-1 operating,
say, at 0.5 V (half of a I-V span between two similar electrodes) would store
only 1.25 J per gram. Thus the Evans high-voltage device would have better en-
ergy storage capability than a small (1 g) RU02 electrochemical redox pseudo-
capacitor. It also would have the advantage of substantially lower esr and
consequently higher pulse power capability, with a low RC time constant.
Weight, volume, and energy density of a hybrid Evans capacitor were
compared with these quantities for a corresponding aluminum electrolytic ca-
Capacitance Dimensions
No. of (120 esr (1 diameter X Anode
Hz) anodes Voltage kHz) height pellet No. of
Item (mF) (volts) (mohm) Weight (g) (mm) weight (g) anodes
18 50 20 56 36 x 12 12 3
2 18.1 28 10.2 30 36x 8 6 3
3 8 32 <50 20 36x7 12
Source: Prom Evans (PES 1993).
640 Chapter 20
FIGURE 20.13. Photo of an Evans Capattery capacitor capable of operation at selected voltages
of 15, 30, 60, or 120 V. (Photo provided by the Evans Co.)
>
.....
.J 3
<t
I-
Z
W 2
b
a..
o 2 3
Log [tim.e/h]
FIGURE 20.14. Self-discharge curves (log plots in time, cf. Chapter 18) for a commercial Pana-
sonic double-layer capacitor from four states of charge.•, 48 h; 0, 3 h; x,O.5 h; and D., 0.05 h. Volt-
age, 5-V, dc.
642 Chapter 20
24
-23°C
20 23°C
>
"-
0
...-
c 16
Q)
...-
0
a..
MAXWELL 24V
12
0 20 40 60 80
Time / h
FIGURE 20.15. INEEL self-discharge test at three temperatures on Maxwell 24-V unpackaged
capacitor. (From Murphy, Cole, and Davis, FES 1995.)
Technology Development 645
10.--------.--------.--------.--------r-------,
Q)
Cl
.s 7
o
>
300 A
4 L _______-L______ ~L_ ______ ~ ______ ~~ ______ ~
o 5 10 15 20 25
Discharge time (5)
FIGURE 20.16. Effect of temperature on discharge curves for a Panasonic 3-V, 1500-F double.
layer capacitor at 100 and 300 A discharge rates. (From INEEL test, Murphy, Cole, and Davis, FES
1995.)
120r---------------------------------------------------~
"0 M 50°C - __ _
~
Q) C 50°C ---
.~
---- ---
Qj
o
100
----------------
~
c
g
u
o 80
0.
8
'15
f
Q)
60
Q)
u
~
40~----------~~----------~~--------~~~--------~
0.00 0.25 0.50 0.75 1.00
Constant Current Discharge Load / A
FIGURE 20.17 Some comparative plots of the effect of discharge load and temperature on ca-
pacitance achieved for Maxcap (M) and Capattery (C) devices. Discharge voltage ranges: 5.5 V for
Capattery, 4.5 V for Maxcap. (From Moyer and Margalit, FES 1994.)
1.0 r---"~I.---------------t
~3Vt1500F
0.8 r- •~/3Vt500F -
~
W
.~
"-
W
0.6 f-
., -
0.4 .'----L.---L--'----'---J1L----L.-....I1---'----L-----I
o 500 1000
Power density I W kg-'
FIGURE 20.18. Constant power discharge characteristics of 3-V, lS00-F and 3-V, SOO-F Pana-
sonic capacitors shown as relative energy stored £/£100 vs. power density (INEEL tests, from Burke,
FES 1993).
Constant power charging or discharging is a third mode that has been em-
ployed, e.g., Fig. 20.18. Generally, for this procedure, the current must be de-
creased as the voltage increases so that I x V remains constant. This provides
better homeostasis of the conditions inside the packaged device.
been examined in testing programs, e.g., by Clark at Sandia (PES 1994). The
Pinnacle Research and the Evans types of capacitor devices were the subjects
ofthese tests, which were conducted (to some extent for military reliability pur-
poses) on systems used for computer memory backup.
The disposal of small, carbon-type capacitors probably involves fewer en-
vironmental pollution problems than those arising with domestic alkaline or Le-
clanche MnOrZn primary batteries, although some electrochemical capacitor
devices may contain Ni metal in the form of powder, filaments, or X-Met as cur-
rent collector. Such sources of Ni are now regarded as potentially carcinogenic,
though only after multiple exposures.
Finally, potential hazards arising in the transportation of appreciable quan-
tities of packaged electrochemical capacitors have to be recognized. Deliveries
of such materials are thus subject to various transportation regulations in some
states or across borders. However, in the discharged condition, capacitors are
much less hazardous in quantity than primary batteries or charged secondary
ones.
The safety, environmental, and health issues involved in the fabrication
and use of electrochemical capacitors, especially for advanced electric vehicle
applications, have recently been reviewed in a useful report from the National
Renewable Energy Laboratory (NREL) (Golden, Colorado) for the U.S. De-
partment of Energy.
y
R-N!0\-R1
3
R2
A1ky1-imidazolium ion
functional groups. The tubular structures are remarkably uniform and have ap-
preciable lengths. The morphologies of the carbon nanotubes are such that elec-
trodes can be fabricated having properties that are almost impossible to obtain
with other carbon materials. Capacitors constructed with these materials gave
excellent frequency response and a power density of 8 kW kg-I. Such capacitors
are capable of providing high pulse power at large repetition rates. The imped-
ance behavior was that of a porous electrode performing according to the clas-
sical transmission-line model. Remarkably, virtually all the available surface
area was accessible for charge acceptance. This is probably because the inter-
tube pore structure (visible under the TEM) is relatively open and quite different
than that of other porous carbon materials exhibiting a distribution of macro,
meso, and micro «1 nm) pores. This material can now be prepared in commer-
cially significant quantities (Hyperion Catalysis International Inc., Cambridge,
Massachusetts).
Molybdenum nitride has recently been proposed as an inorganic, high sur-
face-area material for use in electrochemical capacitors as an alternative to
Ru02 or Ir0 2. It obviously has the advantage of being relatively cheap, and can
be easily prepared by chemical vapor deposition (CVD) by reaction between
MoCl 5 and NH3 between 500 and 800°C, or by reactive conversion from Mo0 3
by a spray pyrolysis procedure. A procedure for its preparation has been given
by Jaggers (Ph.D. thesis, University of California, Berkeley, 1988; UMI order
No. 8916713).
Rather simple capacitor modules were fabricated by Finello (PES 1994)
for use with either a nitromethane plus KI electrolyte or an aqueous 32 wt. % sul-
furic acid solution. Relative to a comparable RuOz electrode, about 40 to 50%
of the capacity of the RuOz-based capacitor was realized. Few further details
have been published, but in the work by Jaggers it was observed that the cyclic
voltammogram obtained with molybdenum nitride was not reversible (i.e., it
had a nonmirror-image form for directions of charging and discharging) in the
way Ru02 is (see Fig. 11.2 in Chapter 11). It is therefore not, in that stage of
preparation, able to substitute Ru02 or conducting polymers (Chapter 12) as a
material approaching behavior of an ideal capacitor.
It has been suggested in a conference discussion (FES 1994) that the active
material of molybdenum nitride is actually Mo0 3 arising from hydrolysis in the
acid medium. For example, Conway31 found that an Mo0 3 film (Fig. 20.11 in
Ref. 31 and Fig. 11.12 in Chapter 11) gave good mirror-image cyclic voltam-
mograms (see Chapter 10) over ca. an 0.8-V range, such behavior being the re-
quirement for satisfactory capacitative behavior. Later work (1998) by Conway
in collaboration with Roberson (in press) showed that the CVD films of Mo 2N
and MoN on Ti could give reversible responses in cyclic voltammetry (Fig.
20.19), with almost constant capacitance as a function of potential, but only over
654 Chapter 20
0.2
N
E
0
<E 0.1
---
>.
VI 0.0
c:
Q)
C
.....c:
....
Q) -0.1 -
....
:::J
()
-0.2
FIGURE 20.19. Cyclic voltammogram for CVD preparation at 4()()OC of M02N showing behav-
ior like that of Ru02 but over a shorter operating voltage range. [From Liu, Conway, and Roberson,
J. Electrochem Soc., 145, 1882 (1998)].
ca. 0.7 V, beyond which film decomposition took place, with some of the film
spalling off.
During 1996, work at Pinnacle Research Institute (PES 1996) was ex-
tended to inorganic conducting solids, which are analogous to Ru02 but sub-
stantially cheaper. Good capacitative performance has been demonstrated, for
example, with nitrides ofMo (M02N, MoxN), Ti (TiN and TiON in KOH), and
Fe (Fe4N). These species provide materials much cheaper (5.8 to $1.8 kg-I) than
RuOrTa205 systems ($1000 kg-I!). y-M0 2N has, however, an operating volt-
age range of only 0.8 V, but Fe4N in aqueous KOH can reach 1.3 V with a ca-
pacitance density of about 32 F g-I. Other advances in this field reported by
Oesten (FES 1996) have involved investigations of stoichiometry changes in
perovskites, for example, by using some ruthenates that have good electronic
conductivity (e.g., SrRu03) and exhibit capacitative behavior like that of RU02'
depending on doping, e.g., with La3+.
Russian developments in high power electrochemical capacitor technol-
ogy have been slow to appear in the Western literature, but an account of some
recent developments at Econd-Sojus was given at a conference by Ivanov, Poli-
ashov, and Radinov (PES 1993). The application is mainly to starter-assist for
Technology Development 655
has also provided a survey of the 1995 performance status of various develop-
ers' products. Some of his data are collected in Table 20.2. A brief but useful
survey of the historical aspects of capacitor development and perceived appli-
cations has been prepared by Barnett and Wolsky (FES 1994).
Table 20.10 contains a list of current uses and explorations of capacitor ap-
plications. Table 20.4 listed the energy storage expectations from carbon dou-
ble-layer capacitor devices. Table 20.11 categorizes capacitor types according
to their provision of general power requirements related to typical discharge
times and corresponding types of application. Table 20.12 summarizes qualita-
tively the performance requirements for several applications.
A capacitor-battery (sealed lead acid, 15 Ah) test configuration for simu-
lation of a hybrid power source for an electric vehicle was reported by Burke
(PES 1993) together with a FUDS test regime. The latter also enabled the cur-
rent splits between the battery and the capacitor at 79 W kg- 1 peak power to be
evaluated.
Another potential use in future years for electrochemical capacitors having
large energy (charge) storage capacity is in the storage of electrical energy gen-
erated from solar photo voltaic systems. Each unit of a photovoltaic device is es-
sentially a low-voltage system, which would therefore be compatible with
TABLE 20.14. Characterization Test (3 times repeated) for the Panasonic SOO-F,
3-V Capacitors
Step time(s) Voltage (V) Current (A) Approx. duration (sec)
Charge 0-3 25 60
Rest 3 0 20
Discharge 3-0 25 60
Rest 0 0 20
Charge 0-3 50 30
Rest 3 0 20
Discharge 3-0 50 30
Rest 0 0 20
Charge 0-3 50 30
Rest 0 0 20
Discharge 3-0 100 15
Rest 0 0 20
Source: Based on INEEL test data from Burke (FES 1993).
Technology Development 661
ducted with discharge currents as high as 400 A at power levels of23 kW. Self-
discharge power was below 1 W maximum. The power performance tests were
conducted by measurements using three types of loads: resistance, current sink,
and power sink. Figure 20.13 shows a photograph of this capacitor. The 13-inch
diameter end plates are separated by 6.5 inches. Electrically isolated tension
rods are connected to intermediate cell current collectors to allow operation at
tappings of 15, 30, 60, or 120 V. By this means, the Evans prototype EC can be
configured for 15-,30-,60-, or 120-V operation using external bus connections.
This original design of capacitor has attracted much attention, especially for
high-power applications. See photo in Fig. 20.13.
A five-element (cf. Miller's calculations cited in Chapter 17) equivalent
circuit of the transmission-line type was examined in simulation of the Evans
capacitor's impedance behavior in a series-connected, two-unit 1.5-F cell stack.
Other possible commercial sources of capacitors are Alcatel Alsthom
(SAFf) in France (1995) and later developments from NEC, who are producing
an aqueous sulfuric acid carbon double-layer capacitor in a series-stacked, 18-
cell unit that can provide an energy density of 1.3 Wh kg-I and a usable power
density of 500 W kg-I. Asahai Glass Co. in Japan is another supplier of low-
power capacitors that is moving to produce higher power and larger units of
3300 and 4300 F employing an organic electrolyte with carbon electrodes.
10,000
A
...
r"'"
lat
Oak Ridoe EV motorl
~
oen/electronics PULSE
_Flywheel
~
_Advanced ulfrocapocifor goal
"»
S·lpoar
I I d .
ea aCI
HEV PRIMARY
~ ',000
C
41
I{pulse power) USABC
'0 Motor/controller-1993 • • /---
.... ICE /tron;l..-....... -Flywheel
41
Neor-term . .......Bipolar lead ocid
~ ultrocopacltor • (primary storage)
Il.
L-I
goal / /
at
0 Monoblock nickel-cadmium-x
..1
Monoblock lead acid-x
100,
10 '00 500
Log [Energy density IWh kg-1]
FIGURE 20.20. Energy vs. power requirements for various energy storage technologies (1993).
(From Burke, FES 1993.)
Technology Development 663
These have an energy density on the order of 6-8 Wh kg- I and a power density
of 500 W kg-I. Figure 20.20 shows energy vs. power requirements for various
energy storage techniques as of 1993.
For the normal vehicle, the power and energy requirements are, of course,
usually only for SLI purposes. For the electric vehicle, competitive cost is ca.
$10 (U.S.) per kilowatt-hour for future commercial viability.
Double-layer capacitor design targets for electrically heated exhaust cata-
lysts (EHC), as well as projected electrically powered steering (EPS) and elec-
tric vehicle power trains, were evaluated as shown in the table.
The interface electronics systems required for energy-efficient hybridizing
between electrochemical capacitors and batteries form a very important compo-
nent of the overall power train for electric vehicles. Developments have been re-
viewed by Dorcker at INEL (cf. Burke, FES 1994), but any detailed description
or discussion of this aspect of power-train technology is outside the scope of this
monograph. It is essentially hardware electrical engineering.
A useful comparison of energy vs. power requirements (Ragone-type dia-
gram, Chapter 15) for various energy storage systems was also given by Burke
(FES 1993) (Fig. 20.17) and a record of interface electronic development
(Solectria Corp., Wilmington, Massachusetts) was published by Burke, together
with a schematic diagram of an electronics circuit for an electric vehicle drive
control. A single point is given for the near-term (1993) electrochemical capaci-
tor goal and this is presumably for the fully charged condition. However, as dis-
Interface
Electronics
75kW
50
(Wh)cap = 500
Battery
Power (kW) 25
25
Capacitor
Power (kW) 0
FIGURE 20.22. Effect of introduction of a load· leveling electrochemical capacitor (500 Wh) in
hybrid combination with a battery for the motive power of an electric vehicle as determined in a
Federal Urban Driving Cycle. (From Burke, FES 1993, 1994.)
at that date were tabulated by Farahmandi (FES 1993). More demanding speci-
fications now exist.
held (e.g., the FES series) over the past 8 to 10 years or so. More attention, how-
ever, is desirable (Anderson, FES 1995) on such aspects as mass-production
techniques and "real-world" applications.
Market shares for various types of capacitors as perceived in 1996 (Zogbi,
FES 1996), are estimated to be as follows: ceramic $4.2 billion; AI(oxide elec-
trolytic) $3.0 billion; dc film $1.5 billion; ac film $.0.9 billion and electrochemi-
cal $0.08 billion (anticipated to increase to $0.225 billion by the year 2000). The
latter remains a small market fraction, but for most envisaged applications, elec-
trochemical capacitors do not suffer competition from the types listed here since
they have specialized applications.
soker Associates) in 1994 under the title "The International Technology and
Market Study of Electrochemical Capacitors" (see Ref. 34). This is a very thor-
ough assembly, not only of information on the patent history of the development
of technology in this field, but also of specifications, performance data, and ap-
plications of Japanese patents, which are not easy to trace otherwise. They are
listed in this publication together with the North American and European litera-
ture. Market study information is also included in various forms. Based on the
patent overview,34 a figure of 78.8% has been estimated for the extent to which
Japanese patents dominated the technology development in 1994, compared
with only ca. 8.6% in the United States and less than 1% in Canada.
The early patents of Becker (1957) and of Sohio, noted in the text else-
where, should be specially recognized here. There are also the European and Ca-
nadian patent claims of D. R. Craig 38 for the first Ru02 pseudocapacitor
technology developed in collaboration with the present author, beginning in
1975 at the University of Ottawa under contract with Continental Group, Inc.
devices overcome one of the problems of stacking units of low voltage electro-
chemical capacitors to achieve high operating voltages, e.g., for electric vehicle
power systems. Dielectric constants of various polymer film formulations were
investigated and values from 3 to 16 were realized. Good performance was re-
tained over a temperature range of -50 to +125°C, with a capacitance change
of about ± 25%.
These somewhat new capacitor variants serve to bridge the gap between
conventional capacitors, including electrolytics, and the developing family of
electrochemical capacitors. The main and advantageous difference is the high
operating voltages that are offered by this new family of electrostatic thin-film
capacitors. Large-scale, high-power applications are envisaged using materials
of excellent structural strength. The possibility of operating voltages being as
high as 500 V offers a good energy storage opportunity on account of the quad-
ratic dependence, E = (l/2)CV2, of energy density on voltage across the capaci-
tor plates, a situation that is achievable with electrochemical capacitors only by
multiple unit series stacking.
Maxwell's technologies have extended to developments in high-voltage,
energy storage and pulsed discharge electrostatic capacitors and have been re-
viewed by Ennis, Haskell, and Sevigny.36 These high energy-density pulse ca-
pacitors are contributing to the introduction of new military, industrial and
commercial systems of original kinds. The advances are based largely on new
dielectric materials and dielectric systems, but not of the electrochemical ca-
pacitor kind.
A paper by Laghari and Sarjeant37 discussed the technology for pulsed
power and energy storage by regular dielectric capacitors rather than those of
the double-layer type, so the material covered in that paper is mainly outside the
scope of this volume. However, some ceramic materials (e.g., barium titanate)
having dielectric constants between 500 and 6000, with quoted breakdown volt-
ages of some 50 V per mil, are of interest for the development of solid-state de-
vices. For example, for a dielectric constant of 1000 and a thickness of 10 mil,
the achieved energy storage density at 500 V would be about 1.2 x 10-3 J cm-2
or 1.2 x 10- 1 J cm-3, but this is a rather small value compared with the double-
layer capacitor energy storage densities that have been achieved, but at much
lower voltages.
years with applications of small devices for computer memory backup and low-
frequency filtering being recognized, while substantially bigger devices have
been developed for possible larger-scale uses in the future for capacitor-battery
hybrid power systems for electric vehicle drive trains and for low-temperature
power assists for starting diesel engines. Another projected larger-scale appli-
cation is for back-up power in the electrical grid system when short-period
power outages occur.
Substantial research and development of technology has been achieved by
companies such as Panasonic-Mitsushita, Maxwell, Evans, Pinnacle Research,
and others referred to earlier in this chapter. Notably, important advances have
been made in the fabrication and pretreatment of high specific-area carbon ma-
terials for double-layer capacitors, especially in preparation of carbon fibers,
carbon felts, and carbon aerogels, as well as some glassy carbon materials.
In addition to this work and that involving Ru02' important advances of a
different kind have been made using conducting polymers such as polyaniline,
polypyrrole, and especially poly thiophene derivatives as electrochemical ca-
pacitor materials, sometimes supported on high-area carbon fiber substrates, as
in the work and publications by the Los Alamos group (Gottesfeld et al.) and that
at the University of Texas at Austin (Bard et al.). Conducting oxide and nitride ma-
terials are also under examination as less expensive alternatives to Ru02.
From a fundamental point of view, as discussed in several earlier chapters,
there are opposing effects that arise between the requirements of high energy
density (scaling with high specific-surface area for double-layer capacitors) and
high power density, necessitating low internal resistance (esr). This is a central
problem with the use of high specific-area porous electrodes as discussed in
Chapters 14 and 15. It has led to much interesting work on characterization of
the impedance and pulse-response behavior of such systems and to new levels
in understanding of the relation of pore-size distribution to real specific-area
values, their connection to electrolyte accessibility (wetting) of pores, and the
specific capacity values obtained.
The remaining problems in the technology of electrochemical capacitors
are connected to the engineering of high-rate production lines for fabrication of
very well-matched units for stacking in multicell, high-voltage devices; the pro-
duction of reliably sealed, low esr, bipolar, stacked devices; and the broader
general problem of the appreciable self-discharge rates that most electrochemi-
cal capacitors suffer, especially at elevated temperatures.
over the past 7 years or so, apart from a multitude of patent claims, some of
which are summarized in the next chapter. Other information has been provided
to the author in private communications.
In the foregoing pages, material has been selectively abstracted from pa-
pers presented at seminar conferences. Mainly, topics of technological interest
in the developing field are referred to, especially those organized by Florida
Educational Seminars, Inc. and designated as PES in the text. The author wishes
to thank Drs. S. P. Wolsky and N. Marincic for permission to use information
from the seminar preprint books and reproduce various diagrams. These semi-
nars were held in Florida in the years 1991-1996 and have continued.
In this chapter, these symposia have been referred to for brevity by PES 1,
2,3,4,5,6, and 7, respectively, which took place annually (and continue) in the
period 1991-1997. For these publications, available from Florida Educational
Seminars, Inc., 2300 Glades Road, Suite 307E, Boca Raton, Florida 33431,
there are no volume or page numbers; hence only the author attributions and the
above designations are given in the references.
Papers on electrochemical capacitors have also been presented at confer-
ences held by the Institute of Electrical and Electronics Engineers (IEEE) and
at the bi-annual Brighton (UK) Power Sources Conferences, published in pro-
ceedings volumes of those meetings (now in J. Power Sources).
One of the first IEEE power-sources conferences at which a section was
specifically devoted to electrochemical capacitors was the Thirty-fourth Inter-
national Power Sources Symposium held in June 1990, and sponsored by the In-
dustry Applications Society of the IEEE (proceedings available as catalog No.
90 CH 2863-9) and by the U.S. Army Laboratory Command. Seven papers were
presented on pulse power batteries and electrochemical capacitors; three were
devoted to capacitor electrochemistry. The present author opened the session
with a general comparative examination of batteries and capacitors in a paper
on the transition from supercapacitor to battery behavior in electrochemical en-
ergy storage. The subject matter of this contribution has been dealt with in
Chapters 2 and 10 in this volume and in Ref. 39. At this conference, Burke de-
livered one of the earliest papers specifically addressed to the application of so-
called ultracapacitors to electric vehicle propulsion systems.
Besides the Florida Educational Seminars proceedings, other principal
symposium proceedings that contain information on electrochemical capaci-
tors, are as follows:
Proc. 34th IntI. Power Sources Symposium, IEEE, catalog No. 90-CH-
2863-9.
Proc. Electrochemical Society Symposium on Electrochemical Capaci-
tors, vol. 95-29, F. Delnick and M. Tomkiewicz, eds., The Electro-
chemical Society, Pennington, N.J. (1995).
Technology Development 673
REFERENCES
1. T. C. Murphy and P. B. Davis, in Proc. Electrochemical Society Symposium on
Electrochemical Capacitors, no. 95-29, p. 269, The Electrochemical Society, Pennington, N.J.
(1996); see also T. C. Murphy, O. H. Cole, and P. B. Davis, FES (1995).
2. S. Sarangapani, B. V. Tilak, and C. P. Chen, in Electrochemical Society Proceedings on
Electrochemical Capacitors, F. Delnick and M. Tomkiewicz, eds., vol. 95-29, The
Electrochemical Society, Pennington, N.J. (1995).
3. 1. D. LeMay, R. W. Hopper, L. W. Hrubesh, and R. W. Pekala, Materials Research Society
Bull., December, 19,43 (1990).
4. 1. H. Aubert and A. P. Sylwester, Chemtech, 21, 234-290 (1990).
5. C. L. Renschler and A. P. Sylwester, Materials Sci. Forum, 52-53, 301 (1989).
6. H. Hatori, Y. Yamada, and M. Shiraishi, Carbon, 30, 303 (1991).
7. C. Arnold, 1. H. Aubert, R. L. Clough, P. B. Rand, and A. P. Sylwester, U.S. Patent 4,832,881
(May 23, 1989).
8. R. L. Clough and A. P. Sylwester, U.S. Patent 4,832,870 (May 23, 1989).
9. R. R. Lagasse, P. K. Leslie, K. R. Thompson, and R. 1. Weagley, Advances in Preparing and
Characterizing Low-Density PAM-Carbon Microcellular Foam, SAND 93-0172, Sandia
National Laboratories, Albuquerque, NM (1993).
10. R. R. Lagasse, in Extended Abstracts, 21st Bienniel Con! on Carbon, vol. 158, American
Chemical Society, Washington, D.C. (1993).
11. D. Barby and Z. Haq, European Patent No. 0-060- \38 (Sept. 3, 1982).
12. C. 1. C. Edwards, D. A. Hitchen, and M. Sharples, U.S. Patent 4,775,655 (Oct. 4, 1988).
13. R. W. Pekala, U.S. Patents 4,873,218 (Oct 10, 1989) and 4,997,804 (March 5, 1991).
14. R. W. Pekala, C. T. Alviso, and 1. D. leMay, 1. Noncryst. Solids, 125,67 (1990).
15. R. W. Pekala and R. W. Hopper, 1. Mater. Sci., 22,1840 (1989).
16. R. de Levie in Advances in Electrochemistry and Electrochemical Engineering, P. Delahay,
ed., vol. 6, Interscience Publishers, New York (1967).
17. F. M. Delnick, C. D. leager, and S. Levy, Chem. Eng. Commun., 35, 231 (1985).
18. F. M. Delnick, in Proc. Symp. on the Science of Advanced Batteries, No. 8-9, D. Scherson,
ed., Case Western Univ. for The Electrochemical Society, Pennington, N.l.(l995).
19. N. Nawa, T. Nogami, and H. Mikawa, 1. Electrochem. Soc., 113 (6), 1457 (1984).
20. D. Kohler,1. Zabasajja, and B. Tartarchuk, 1. Electrochem. Soc., 137 (I), 136 (1990).
21. D. Kohler, 1. Zabasajja, F. Rose, and B. Tartarchuk, 1. Electrochem. Soc., 137 (6), 1750
(1990).
22. S. T. Mayer, 1. Kaschmitter and R. W. Pekala, Abstract No. 500, in Extended Abstracts of the
186th Electrochemical Society Meeting, vol. 94-2, The Electrochemical Society, Pennington,
N.J. (1994).
674 Chapter 20
23. T. P. Hoar and J. N. Agar, Disc. Faraday Soc., 1, 291 and 297, (1947).
24. J. Newman, Electrochemical Systems, Prentice-Hall, Engelwood Cliffs, N.J. (1991).
25. S. Sekido, Y. Yoshina, T. Muranaka, and M. Mori, Denki Kagaku, 48, 40 (1980).
26. N. Marincic, private communication (1996).
27. W. Pell, T. C. Liu, and B. E. Conway, Electrochim. Acta, 42, 3541 (1997).
28. 1. E. Oxley, in Extended Abstracts, J4Ist Electrochemical Society Meeting, Houston, Texas
(1972).
29. S. Sarangapani, P. Lessner, J. Forchione, A. Griffith, and A .. B. LaConti, in Proc. 25th
Intersociety Energy Conversion Conference, vo!. 3, p. 137; see also S. Sarangapani, 1. A.
Kosek, and A. B. La Conti, in Handbook of Solid-State Batteries and Capacitors, M. Z. A.
Munshi, ed., p. 601, World Scientific Pub!. Co., Singapore (1995).
30. 1. Robinson and R. A. Osteryoung, J. Am. Chem. Soc., 101, 323 (1979); see also J.
Electrochem. Soc., 130, 1968 (1983).
31. B. E. Conway, in Proc. of the Symposium on Electrochemical Capacitors, F. M. Delnick and
M. Tomkiewicz, eds., vo!. 95-29, p.15, The Electrochem. Society, Pennington, N.J. (1995).
32. R. W. Pekala, in Ultrastructure Processing of Advanced Materials, D. R. Uhlmann and D. R.
Ulrich, eds., pp. 711-717, Wiley, New York (1992).
33. 1. R. Miller, in Proc. 11 th IntI. Seminar on Primary and Secondary Battery Technologies and
Applications, S. P. Wolsky and N. Marincic, eds.; Horida Educational Seminars, Boca Raton,
Ha. (1994).
34. S. P. Wolsky and R. S. Wissoker, The International Technology and Market Study of
Electrochemical Capacitors, Horida Educational Seminars, Inc., Boca Raton, Ha. (1994).
35. T. R. Jow, P. J. Cygan, J. Carter, S. Guilman, and L. Krzastek, in Extended Abstracts, I83rd
Electrochemical Society Meeting, The Electrochemical Society, Pennington, N.J. (1993).
36. 1. B. Ennis, D. K. Haskell, and 1. A. Sevigny, in Proc. 34th Inti. Power Sources Symposium,
p. 392, C. Berger, ed., Inst. Electrical and Electronic Engineers, Piscataway, N.J. (1990).
37. J. R. Laghati and W. J. Sarjeant, in Proc. 34th Inti. Power Sources Symposium, p. 380, C.
Berger, ed., Inst. Electrical and Electronic Engineer, Piscataway, N.J. (1990).
38. D. R. Craig, Canadian patent 1,196,683, (1985) and Electrochemical Energy Storage Devices,
European Patent Application, 82,\09,061,0 submitted September 30, 1982, pub!, no.
0,078,404, May 11th (1983).
39. B. E. Conway, in Proc. 34th IntI. Power Sources Symposium, p. 319, C. Berger, ed., Industry
Applications Soc. ofinst. of Electrical and Electronics Engineers, Piscataway, N.J. (1990).
1. Power Sources, 15 and 16, Proc. 19th and 20th Inti. Power Sources Symposia (Brighton), A.
Attewell and T. Keily, eds., Elsevier (1995 and 1997).
2. K. Kinoshita, Carbon: electrochemical and physicochemical properties, Wiley-Interscience
(1988), especially chapters 2, 3, and 6.
3. Proc. Electrochemical Society Symposium on Electrochemical Capacitors, vo!. 95-29, F.
Delnick and M. Tomkiewicz, eds., The Electrochemical Society, Pennington, N.J. (1995).
4. E. Gileadi, Electrode Kinetics for Chemists, Chemical Engineers and Materials Scientists,
VCH pub!" New York (1993).
5. A. E. Burke and J. R. Miller, Idaho National Engineering Laboratory Report,
DOFlED-l 049 I , October (1994).
6. Novel Forms of Carbon, Materials Research Society Proc., C. L. Renschler, J. J. Pouch, and
D. M. Cox, eds., 270, 3 (1992).
Chapter 21
Patent Survey
675
676 Chapter 21
°
group of V, Zr, Hf, Ti, Nb, Sc, and combinations thereof.
= oxygen
X = modifier element, F, CI, Br, I.
= =
a = 0.1 to 3, b 1 to 7, and c 0 to 5
Y 01.68 Clo.68 mixed with super P carbon and Teflon binder in
a wt.% ratio of 85:10:5 showed anodic and cathodic charge
of 0.06 C/cm 2 at a sweep rate of 200 mVIs in 31 % KOH.
6. 5,388,025 (217/95) Rechargeable energy storage device with electrodes made of
organometallic compound selected from the group
consisting of metaUocenes, metal porphyrins, metal acetyl
acetonates, organometallic polymers, and metal bipyridines
blended with or coated with one or more metals such as
Ag, AI, Au, Co, Cr, Cu, Fe, Ir, Mg, Mn, Mo, Ni, Pd, Ru,
Pt, Zn, and alloys thereof. Cobalt acetate-based electrodes
showed a voltage of 0.725 V after charging.
Rechargeability demonstrated with manganese
acetylacetonate and nickel pthalocyanine
tetrasulfonate-based electrodes.
7. 5,383,089 (1117195) Electrode material is a mixed valence complex (e.g., platinum
blues, platinum reds, cis-diamine platinum a-pyridone
blue, tetracyano platinate complexes with stacked anions)
containing at least two metal atoms and at least one ligand
attached to the metal atoms, the metals existing in multiple
oxidation states. Excellent rechargeability claimed.
(continued)
Patent Survey 6n
TABLE 21.3. Authors, Date, and Assignee for Patents in Tables 21.1 and 21.2
u.s. Patent No. (Date) Authors Assignee
ELECTRODE MATERIALS
5,442,197 (8/15/95) x. Andrieu and L. Kerreneur Alcatel Alsthom Compagnie
Generale D'Electricite, Paris
France
5,430,606 (7/4/95) K. Adachi, T. Kurosaki, and Y. Takeda Chern. Industries, Ltd,
Iwashima Osaka, Japan
5,429,893 (7/4/95) G. Thomas Motorola, Inc., Shaumburg, Ill.,
U.S.
5,420,168 (5/30/95) S. T. Macer, J. L. Kaschmitter, Regents of the University of
and R. W. Pekala California, Oakland, Calif.,
U.S.
5,260,855 (1119/93) 1. L. Kaschmitter, S. T. Macer, Authors
and R. W. Pekala
5,392,191 (2121195) G. Thomas, S. Prasad, and J. E. Motorola, Inc., Schaumburg, Ill.,
Nerz U.S.
5,388,025 (2127/95) 1. L. Davis, 1. K. Arledge, T. 1. Ibid.
Swirbel, and M. Williams
5,383,089 (1117/95) M. Williams and 1. L. Davis Ibid.
5,369,546 (11129/94) T. Saito, Y. Shimizu, and 1. NEC Corp., Tokyo, Japan
Tabuchi
5,351,164 (9/27/94) I. I. Grigortchak, K. D. Tovstjuk, T. N. Frontsevich Institute for
Z. D. Kovalyuk, I. D. Kozmik, Problems in Materials Science,
and B. P. Bahmatyuk Kiev, Russia
5,319,518 (6/7/94) R. A. Blood J. Cole, Naalehu, Hawaii, U.S.
5,245,512 (9/14/93) R. S. Rounds Colgate-Palmolive Co., New
York, N.Y., U.S.
5,212,622 (5/18/93) D. R. MacFarlane, 1. R. Tetaz, Specialized Conductives Pty.,
and M. Forsyth Ltd., Neerim, Australia
5,172,307 (12115/92) 1. Tabuchi, T. Saito, A. Chi, and NEC Corp., Japan
Y. Shimizu
5,168,433 (1211192) H. Mukouyama, M. Mmaesaka, Murata Manufacturing Co., Ltd.,
K. Watanabe, and M. End Kyoto, Japan
5,161,094 (11/3/92) J. F. Bruder and L. N. Swink Quadri Electronics Corp.,
Chandler, Ariz., U.S.
5,136,478 (8/4/92) Ibid. Ibid.
5,047,899 (9/10/91) J. F. Bruder Ibid.
5,428,501 (6/27/95) 1. F. Bruder Marine Mechanical Corp.,
Cleveland, Ohio, U.S.
5,151,848 (9/29/92) D. Finello The United States of America by
the Secretary of the Air Force,
Washington, D.C., U.S.
5,150,283 (9/22192) A. Yoshida and K. Imoto Matsushita Electrical Industrial
Co., Ltd., Kadoma, Japan
5,144,537 (9/1/92) Y. Tsuchiya, K. Kurabayashi, and Isuzu Motors, Ltd., Tokyo, Japan
Y. Niida
5,136,474 (8/4/92) S. Sarangapani, P. M. Lessner, Giner, Inc., Waltham, Mass., U.S.
and A. B. Laconti
5,136,473 (8/4/92) Y. Tsuchiya, K. Kurabayashi, and Isuzu Motors, Ltd., Tokyo, Japan
H. Moroboshi
5,136,472 (8/4/92) Y. Tsuchiya and K. Kurabayashi Ibid.
(continued)
682 Chapter 21
685
686 Index
Nonaqueous Polarization
media, double-layer in, 170 cooperative, 96
solutions, outlook for use of, 180 dielectric, illustrated, 93
solvents in dielectrics, 91
acceptor numbers for, 359 and dielectric constant, 97
classification of, 174 electronic of atoms and molecules, 78
donor numbers for, 340 and field, 97
Nyquist plots, 484 orientation, 96
of power source, 430
Ohmic potential, in porous electrode, 398 of solvent, in double-layer, 81
Orientable dipoles, dielectric polarization of, 99 relations for power source, 432
Orientation polarization, 96 Polarography, A.C, 508
Ottawa group, capacitor project, 6 Polyaniline film growth, EQCM results, 331
OverpotentiaL 44 Polyaniline films, ellipsometry applied to, 324,
current-density relations, for porous electrode, 235,330
399 Polyelectrolyte ionization, 302
current relation for fuel-cell electrode, 431 Polymers, conducting, 299
distribution, for fuel-cell electrode, 398 Pore
Oxidation accessibility, impedance behavior, 411
of carbon, 196 current distribution in, 396
states in ruthenium and iridium oxide elec- element of equivalent circuit, 390
trodes,277 equivalent circuit of, element, 383
Oxide films, model with equivalent circuit, 348
conductive, general reading references, 297, 298 penetration depth into, 395
various, exhibiting redox capacitance, 286 of signal, 387
Oxygen contents, and heats of immersion of of a porous electrode, electrically represented, 381
charcoals, 214 size, 407
Oxygen, interaction with carbon surfaces, 212 sizes, classitlcation of, 408
structure, complex in porous electrode, 399
Parsons' treatlnent surface areas, for carbon fibers, 410
of volcano relation, 40 illustrated, 409
of double-layer, water clusters in, 143 Pores, distribution of charging rates in, 388
Particle size effects in capacitance, 469 Porous electrode, 545
Patent literature, for technology, 667 behavior, simulation ot: 547
Patent survey complex plane impedance diagram, 402
authors dates and assignees for patents, 681 complex plane plot for, 545
electrolytes, 679 complex structure in, illustrated, 400
Pauling ionic radii, I 13 cumulative pore area, 165
Penetration depth current distribution in, 396, 397
de Levie calculation, 387 double-layer in, 402
of signal in pore, 387 double-layer overlap in, 403
of signal in pore, tabulated, 395 equations for, 383
Permanent dipole, in a field, 79 and ESR, 545
Permittivity fractal surfaces of, 404
relative, 89 impedance, and ESR, 545
of space, 69 overpotential-current density relations, 399
value of, 70 pore width related to pore area, 165
pH response function in time, 386
and heats of immersion, 216 Porous electrodes
and work function differences of carbons, 215 of carbon, 376
Phase-angle complex structure in, 399
plots for Faradaic pseudocapacitance, 553 de Levie model, 382
in porous electrode, frequency spectrum 393 de Levie's treatment, 382
related to diffusion, 388 electrochemical behavior at, 376
Phase relations, between current and Voltage, 487 electrochemistry at, 555
Phase-sensitive detection, 504 high area, 376
Poisson's equation, 75, 76 internal electrolyte conductivity, 360
Polarity induction, model of, 94 real areas of, 410
Index 695
USABC advanced battery technology X-ray plots for thermally formed ruthenium oxide,
criteria, 656 274
secondary criteria, 656 XPS spectra, of carbon fibers, 192
Usage bases of capacitors, 655
Uses, of capacitors, 610 Zinc--bromine hybrid system, 626