ELECTROLYTES

Contents
Overview
Gel
Ionic Liquids
Non-Aqueous
Polymer
Solid: Mixed Ionic-Electronic Conductors
Solid: Oxygen Ions
Solid: Protons
Solid: Sodium Ions

Overview
M Salomon, MaxPower, Inc., Harleysville, PA, USA
& 2009 Elsevier B.V. All rights reserved.

Introduction where the E o values are standard potentials (in units of

The electrolyte solution is a major component of all
battery systems and as such will greatly influence energy
densities (thermodynamic properties such as Gibbs en-
ergy, enthalpy, and ionic activity) and power densities
(nonthermodynamic properties such as viscosity, con-
ductivity, and transference). The electrolyte solution
consists of a liquid or solid phase containing at least one
component, e.g., water, which is called the solvent, and an
ionizable substance, e.g., a salt or an acid, which is called
the electrolyte. The fundamental thermodynamic and
nonthermodynamic concepts that are of importance to
batteries are discussed below.
Thermodynamic Fundamentals
Standard Electrode Potentials
A battery is defined as a string of individual Galvanic cells,
and the basic cell consists of two electrodes (half-cells)
immersed in a solution containing an electrolyte com-
posed of ions reversible to each of the half-cells. The cell
reaction is
Li þ AgCl $ Liþ þ Cl þ Ag
volts) as indicated by the superscript and thus refer to
STP (standard temperature (298.15 K) and pressure
(101.33 kPa)), and the concentration or activity of the
electrolyte is unity. Under these conditions, the cell po-
tential (e.m.f.) for reaction [I] is written as
E o ¼ E o ðoxidationÞ þ E o ðreductionÞ
and using the half-cell e.m.f.’s given above, the e.m.f. of cell
[I] is E o ¼ 3.045 þ 0.2223 ¼ 3.267 V. For many half-cells,
standard e.m.f.’s, particularly for aqueous solutions, have
been tabulated in various text books on thermodynamics
and electrolytes. The value of 2.823 V is the standard e.m.f.
for cell [I], but in practice, the observed e.m.f. for this cell
will be dependent upon the concentration of the electro-
lyte in the electrolyte solution, or, more accurately, upon
the activity of the electrolyte in the electrolyte solution.
Provided the activities of all ionic species in solution are
known or can be calculated from theoretical expressions,
the e.m.f., E, of the Galvanic cell can be calculated from
the Nernst equation
 
RT
o Paproducts
E¼E  ln ½1
nF Pareactants
½I

In aqueous solution, the two half-cell reactions can be where R is the gas constant, T the absolute temperature, n
written in terms of standard potentials as the number of electrons involved in the electrochemical
reaction, and a the activities of initial reactants and final
Li$Liþ þ e ðoxidation e:m:f:Þ; E o ¼ þ3:045 V
products as indicated in eqn [I]. A discussion on activities
Liþ þ e $Li ðreduction e:m:f:Þ; E o ¼ 3:045 V and concentrations is given below.
There are numerous instances where tabulated e.m.f.
AgCl þ e $Cl þ Ag; E o ¼ þ0:2223 V values are not available, but it is still possible to calculate

134

e.m.f.’s using Gibbs energies via the relation
DG ¼ nFE
or, if all components are at unit activity at STP,
DG o ¼ nFE o
where F is the Faraday constant. Values for DGo can be
calculated from Gibbs energies of formation by the fol-
lowing equation:
X X
DG o ¼ DGfo ðproductsÞ  DGfo ðreactantsÞ
DGfo values can also be found in many reference texts on
the thermodynamics of electrolyte solutions.
Specific Energy and Energy Density
In almost all textbooks and papers on electrochemical
cells and batteries, the energies of Galvanic cells are al-
most universally given in units of watt-hours per kg or
watt-hours per dm3 based on the molar mass or volume
of reactants only. Both the specific energy, SE (Wh kg1),
and energy density, ED (Wh L1 or Wh dm3), are
readily calculated from Eo and DGo values as shown
below.
Using reaction [I] as an example, DGo is calculated from
eqn [3] using the value of 96.487 kJ V1 (1 kJ ¼ 0.2778 Wh)
for F and 3.267 V for Eo yielding a value of 315.22 kJ mol1
(note that by convention, both the SE and ED are defined in
terms of  DGo). For 1 mol, the molar mass of reactants
Li þ AgCl is 0.1503 kg, and the volume of reactants calcu-
lated from densities is 0.038 78 dm3. Using the conversion
factor of 0.2778 Wh J1, the following can be arrived at. On
a gravimetric basis, the specific energy, SE, is
1
ð315:2 kJ mol Þð0:2778 Wh J Þ 1
SE ¼ ¼ 582:6 Wh kg1
0:1503 kg mol1
and the energy density, ED, is
1
ð315:2 kJ mol Þð0:2778 Wh J Þ 1
ED ¼ ¼ 2258 Wh dm3
0:03878 dm3 mol1
Concentrations, Activities, and Activity
Coefficients
In dealing with electrolytes used in Galvanic cells and
batteries, solutions are far from ideal. Deviations from
ideality arise, in part, from ion–ion interactions (e.g., ion
association), changes in the free solvent concentration
owing to different ions’ ability to strongly or weakly
coordinate to the solvent molecules, and changes in the
basic structure of the solvent itself owing to the influence
of the ions in enhancing or decreasing solvent structure.
One consequence of the last effect is a change in the
dielectric constant of the electrolyte solution as a
Electrolytes | Overview 135
function of electrolyte concentration. This subject is
discussed in detail in Overview and Electrolytes: Non-
½2
Aqueous of this encyclopedia.
For Galvanic cells, the relevant concentration scales
are the molality, m, which for solute 1 in solvent 2 is
½3
defined as m1 ¼ n1/n2M2, and the amount concentration
of solute 1, c1, in a solution of volume V defined as
c1 ¼ n1/V. Here, n represents the number of moles and M2
is the molecular mass of the solvent. For molality, the SI
unit mol kg1 is used, and for the amount concentration,
½4 the SI unit is mol dm3. The old terms molarity, molar,
and moles per unit volume are no longer used. In many
instances, data in the literature are reported in units of
mass fraction for substance 1, w1, or mass% 100w1 de-
fined as w1 ¼ g1/Sg , where g is g, kg, and so on. The
equivalent terms weight fraction, weight percent, and
g1/100 g solution are no longer used. To correct for
nonideality, an activity coefficient, g, is introduced, which
is defined as a number that when multiplied by molality
or amount concentration will yield the true chemical
activity of the solute (the product of the individual ions)
called the activity a. Because single-ion activities and
activity coefficients cannot be measured, corresponding
mean values are used, e.g., a7, which is defined as follows:
uþ u u
asolute ¼ a ¼ ðaþ Þða Þ ¼ a7 ½5
where n is the sum of number of cations, nþ, and number
u u
of anions, n. By noting that a7 ¼ ma7 on the molality
u
scale and c g7 on the amount concentration scale, the
Gibbs energy for the solute is given by
DG ¼ DG o þ RT lnðmgu7 Þ ¼ DG o þ uRT lnðmg7 Þ ½6
As an example of application of these relations, consider
reaction [I] operating in an aqueous lithium chloride
electrolyte solution (neglecting the time that metallic
lithium will react with water). By combining eqns [1], [2],
and [6], the e.m.f. of the cell is given by
 u 
RT m7
E ¼ Eo  ln ½7
nF aLi aAgCl
Because the activities of pure solids are assumed to equal
unity, the working relation to calculate the concentration
dependence of cell [I] takes the final form (note that
n ¼ 1 and n ¼ nþ þ n ¼ 2)
2RT  u 
E ¼ Eo  ln mg7 ½8
F
Mean activity coefficients for many, mostly aqueous,
electrolyte systems are available in the literature, but for
many systems, particularly for nonaqueous systems for
which data are scarce, mean activity coefficients can be
estimated from theoretical approaches such as the
Debye–Hückel and Pitzer equations.
The Debye–Hückel theory gives the relation for g7 in
terms of the ionic strength Im (molality basis) or Ic
136 Electrolytes | Overview

(concentration basis): conductivities, viscosities, ionic diffusion, and ionic

transference (transport) as discussed below.
1X 1X 2
Im ¼ mi z2i ; Ic ¼ ci zi ½9
2 i 2 i Ionic Conductivities

A form of the Debye–Hückel equation that accounts for
the finite size of ions, di, is
pffiffiffi
jz þ z  jA I
log g7 ¼ pffiffiffi
1 þ Bd I
where di is in angstrom (Å) units and, on the concen-
tration scale, Debye–Hückel parameters are
1:8246  106
A¼ mol1 dm0:5 K1:5
ðT eÞ1:5
and
50:29  108
B¼ cm1 mol0:5 dm0:5 K0:5
ðT eÞ0:5
where e is the relative permittivity (dielectric constant)
for the given solvent or solvent mixture. For g7 on the
basis of molality, the following relations are used (sub-
scripts m and c refer to molal and concentration bases,
and the subscript 7 in g7 is omitted for convenience,
and do is the density of the pure solvent or solvent
mixture):
cgc ¼ do mgm
pffiffiffiffiffi pffiffiffiffiffi
Am ¼ Ac do and Bm ¼ Bc do
The Debye–Hückel equation [10] is applicable to rela-
tively dilute solutions, generally for concentrations
r0.1 mol dm3. The literature cited below does review
extended models of the Debye–Hückel equation for
higher concentrations, and a more accurate treatment for
g7 is given by the Pitzer equations. Derived parameters
for the Pitzer equations are available for many aqueous
solutions, but for nonaqueous solutions commonly used
for high-energy lithium batteries, Pitzer-derived pa-
rameters are extremely rare.
Transport Fundamentals
Although the thermodynamic concepts discussed above
permit the determination of the maximum (theoretical)
energies obtainable from Galvanic cells as a guide, they
do not fully relate to the properties of electrolyte solu-
tions, which significantly limit both energies and power
capabilities of practical (i.e., commercial) battery systems.
For these concepts, one must address nonthermodynamic
transport properties of electrolyte solutions. These
properties are all interrelated and are based on ionic
The conductivities of electrolyte solutions relate to the
maximum rate at which a Galvanic cell can be dis-
charged. Because a volume-based quantity is dealt with
here, i.e., resistance as a function of concentration, for
½10 theoretical interpretation, experimental conductivities
are based on mol dm3 units. Experimentally, one de-
termines the resistance of an electrolyte solution between
two inert electrodes by alternating current (a.c.) methods
and, from the voltage drop and current, computes the
experimental resistance, R, from the standard relation of
½11
R ¼ V/i, where V is the experimental voltage drop and i is
the experimental current. To convert this measurement
into resistivity with units of O1 cm1 or its reciprocal
conductance, s, in S cm1 for SI units, the resistance is
converted to a specific resistance, Rsp, using the rela-
½12
tionship of Rsp ¼ t/AR, where A is the area of the inert
electrodes and t is the distance (thickness) between the
two inert electrodes. For theoretical treatment and ana-
lyses, the specific conductivity is converted to molar
conductivity, L, defined on a mol dm3 basis using the
relation L ¼ 1000s/c, which yields a quantity with units
of S cm2 mol1. The first important theoretical treatment
of molar conductivity data is known as the Onsager
equation,
pffiffi
L ¼ Lo  S c ½13
where S is a precisely defined constant that takes into
account electrophoretic and relaxation effects, dielectric
constant, and temperature, and Lo is the molar con-
ductivity extrapolated to infinite dilution where the
electrolyte is assumed to be completely ionized. The
electrophoretic effect relates to the central ion (Liþ when
considering lithium batteries), which, under an applied
electric field, moves toward the negative electrode,
whereas its ionic atmosphere of negative ions and solvent
molecules moves in an opposite direction. The relaxation
effect refers to retardation of the motion of the central
ion toward the negative electrode owing to the electro-
static force imposed on it from the motion of the ionic
atmosphere of negative ions and solvent molecules
moving in the opposite direction. This first major ad-
vance in the theoretical treatment of conductivity data
was later improved by adding terms accounting for
additional effects relating to solvent properties and
electrolyte charge (the E term) and the distance of closest
approach of oppositely charged ions (the J terms) ac-
cording to the expanded relation
pffiffi
L ¼ Lo  S c þ Ec ln c þ J1 c þ J2 c 1:5 þ ? ½14

Details on these theoretical refinements can be found in
the references cited in Further Reading, and for the
present discussion, the Onsager equation, eqn [13], will
be used to demonstrate the importance of interpreting
conductivity data.
One important concept relating to molar conductivity
data for any given electrolyte is the division of L values
into individual cation and anion contributions, i.e.,
L ¼ lþ þ l, and this will be discussed below. Another
important concept relates to the ability to use conduc-
tivity data, a nonthermodynamic property, to determine
ion association equilibrium constants, which is a ther-
modynamic property. Almost all studies on conductivities
show a significant deviation from eqns [13] and [14]
owing to the formation of noncharged ion pairs, which
results in a decrease of ionic conductivity compared with
the assumption that all electrolytes are fully ionized,
which is not true for many electrolyte solutions, par-
ticularly where dielectric constants are small, e.g., o70.
Because ion pairs are neutral species and do not con-
tribute to conductivity, their existence can be accounted
for in the following manner. Consider a symmetrical
electrolyte (1:1) MA at concentration c, which ionizes
into ions Mþ and A followed by partial association of
ions into ion pairs according to
sln $ MAsln
þ
Msln þ A
ac ac ð1aÞc
Denoting the amount concentration of MAsln (the ion
pairs), which forms as the fraction a of the initial (total)
electrolyte concentration c, the concentration of the free
ions will be ac and the concentration of the non-
conducting ion pairs, MAsln, will be c(1  a). Thus, the
thermodynamic ion association constant, Kao , for reaction
[15] can be written as
1a
Kao ¼ ; i:e:; a ¼ 1  a2 Kao g27
a2 cg27
where the activity coefficient for the ion pair is assumed
to equal unity. In terms of conductivity data, the fraction
of ionization a can also be defined as the ratio of the
experimental molar conductivity at a given concentration
to the infinite dilution value, i.e., a ¼ L/Lo. From this
relation, L ¼ aLo, and substitution into eqn [13] results
in the following:
pffiffiffiffiffi
L ¼ Lo  S ac  Kao Lg27 ðacÞ
Thus if Kao values obtained from conductivity data and
activity coefficients obtained from experiments or a
Debye–Hückel or Pitzer equation are known, then Ka
values for solutions of almost any practical concentration
can be computed.
Electrolytes | Overview 137
Viscosity, Ionic Transference Numbers, and
Diffusion
These quantities are interrelated and have a significant
effect on ion conductivities and the overall performance
of all Galvanic cells and batteries. Solution viscosities
influence the transport properties such as conductivity
and diffusion, which can be related to the diffusion co-
efficient Di and the ionic transference (or transport)
number ti. It is Di and ti that influence the magnitude of
the concentration gradients that arise during the dis-
charge of electrochemical cells, and the greater the
concentration gradient, the greater the overpotential
owing to concentration polarization.
The transference number of an ion is the fraction of
the total current that is carried by an ion crossing a
reference plane during the passage of 1 F of electricity
through solution. Because of the differences in size and
solvation of anions and cations, different ions carry dif-
ferent fractions of the current because different ions
move at different speeds under the same potential gra-
dient, i.e., a cation and an anion differ in the amount of
current they can carry during the discharge of a battery,
and by definition, the sum of cation and anion transfer-
ence numbers is unity, i.e.,
tþ þ t ¼ 1 ½18
½15
In determining which electrolyte and which solvent
system is best for a given Galvanic cell, it is important to
maximize the transference numbers of the ionic species
involved in the cell reaction because a low value will
result in large concentration gradients, which can sig-
nificantly decrease the power capability of the cell. For
example, in a lithium–manganese dioxide cell, the cell
reaction is Li þ MnO2-LiMnO2 (Eo ¼ 3.5 V) in which
only the transfer of Liþ ions in solution is involved in this
discharge reaction. To minimize polarization owing to
concentration gradients, clearly the transference number
½16
tþ for Liþ should be maximized and ideally the goal will
be tþ ¼ 1. Experimentally, tþ and t values for concen-
trated liquid electrolyte solutions of interest to batteries
are not readily available in the literature. In addition,
because of solvation effects, ion–ion interactions, and ion
association, transference numbers are concentration and
solvent dependent, and the values reported in the lit-
erature are often infinite dilution values, e.g., tþo or to
values determined experimentally in dilute solutions
from conductivity data or from direct measurements
½17 based on Hittorf, moving boundary, direct current (d.c.)
polarization, and e.m.f. methods. Still, even to values are
of interest because they serve as a guide in selecting
solvents to be used in new battery technologies, par-
ticularly for lithium-based batteries. Methods of esti-
mating to values and their relation to viscosity and
diffusion are reviewed below.
138 Electrolytes | Overview
The transport properties are all interrelated, and
starting with transference numbers and individual
molar conductivities for individual ions, l7 (note
L ¼ lþ þ l), the relation between the two parameters
for the cation is
loþ loþ
tþo ¼ ¼
loþ þ lo Lo
½19
and a similar relation exists for to for the anion. Note that
eqn [19] applies to symmetrical electrolytes (equal cation
and anion ionic charges where zþ ¼ z, e.g., 1:1, 2:2
electrolytes, and so on) at infinite dilution and in the
o
absence of ion association. Thus, in principle, t7 values
o
can be determined if l7 values are known and vice versa.
Although t7 values are concentration dependent, which
can be determined in dilute solutions (co0.5 mol dm3)
where ion association can be neglected, in the absence of
experimental literature data for t7 in electrolyte solu-
o
tions of interest, values of t7 are still very useful guides
in which solvent system and electrolyte will maximize
the transference number for the ion of interest for the
specific cell reaction of interest.
Ionic mobility can be related to solution viscosity by
the use of Stokes’ law, which relates the hydrodynamic
velocity of a sphere of radius r moving through a liquid of
viscosity Z. For an ion moving under the influence of a
potential gradient, Stokes’ law takes the form
z2i F 2 0:8204z2i
loi Z ¼ ¼ ½20
6pNA rs rs
where zi is the ion charge, F the Faraday constant, NA the
Avogadro number, and rs the Stokes radius (Å units used
in eqn [20]), and the units for Z are poise. If it is assumed
that the Stokes radius for a given ion is similar in several
solvents, e.g., solvents 1 and 2, then it follows from eqn
[20] that
ðloi ZÞsolvent 1 ¼ constant ¼ ðloi ZÞsolvent 2 ½21
Equation [21], originally known as the empirical Wal-
den’s rule, is valid for large ions, which have similar
hydrodynamic radii, but often is a very approximate re-
lation for small ions, which have different solvent co-
ordination spheres and thus have differing rs values. Still,
eqn [21] represents a method to use viscosity data to
estimate lo7 in one solvent if the corresponding lo7
values are known in another solvent.
Ionic diffusion coefficients, Di in units of cm2 s1, are
related to molar conductivities through the Nernst–
Einstein relation, which, for a univalent ion at infinite
dilution, can be used to determine transference numbers
using the equation
o
Dþ lo lo
tþo ¼ 1  to ¼ o o
¼ o þ o ¼ þo ½22
Dþ þ D lþ þ l L
The effect of solvent on transference numbers and dif-
fusion coefficients can be significant as shown by the
values for lithium perchlorate in water and propylene
carbonate determined from literature t7 o
, lo7 , and Do
values:
For lithium perchlorate in water at 298 K: tþo ¼ 0:365
and Dþo
¼ 4:65  106 cm2 s1.
For lithium perchlorate in propylene carbonate at
298 K: tþo ¼ 0:29 and Dþo
¼ 7:12  107 cm2 s1.
Concluding Remarks
This article reviews a number of basic concepts that
serve as a guide in the understanding of the concepts
used to explain, analyze, and predict the properties of
Galvanic cell, which are dependent upon the nature of
the electrolyte solution. Simplifications have been used to
illustrate how both thermodynamic and transport prop-
erties are important to determine the performance of
existing batteries and concepts needed in developing new
battery systems where limited literature data exist. The
simplification used in this article relates to examples
based on simple symmetrical electrolytes (1:1, 2:2, and so
on) with and without ion association, but the literature
cited provides numerous examples where advanced
concepts for unsymmetrical electrolytes (1:2, 2:1, and so
on) can be obtained.
The first part of this article deals with thermodynamic
properties, which, based on Gibbs energies and the
Nernst equation, demonstrate how to determine theo-
retical reversible potentials and then determine the
maximum specific energies and energy densities of
Galvanic cells and battery systems.
To determine the practical performance of Galvanic
cells and thus of batteries, mass transport of ions to and
from electrode surfaces is discussed. In a practical cell or
battery, mass transport of ions is a complex function of
the potential gradients at electrodes and concentration
gradients relating to concentration polarization and
conductivity relating to power capability. To demonstrate
the importance of these properties for practical cell and
battery systems, a review on basic concepts relating to
conductivities, transference (transport) numbers, and
diffusion coefficients is provided.
Nomenclature
Symbols and Units
a activity
A electrode area
A, B Debye–Hückel parameters
c amount concentration
d density or distance parameter
do density of the pure solvent
 Electrolytes | Overview 139

Di diffusion coefficient of ion i r conductance

E electrode potential n total number of ions
E1 standard electrode potential Abbreviations and Acronyms
F Faraday constant a.c. alternating current
i electric current d.c. direct current
I ionic strength ED energy density
Ic ionic strength (concentration basis) SE specific energy
Im ionic strength (molality basis) STP standard temperature and pressure
J coefficient in the conductivity equation
Koa thermodynamic ion association
constant
m molality See also: Electrolytes: Non-Aqueous.
M2 molecular mass of the solvent
t
m7 mean molality for u ions
n number of moles Further Reading
NA Avogadro constant, 6.022  1023
mol  1 Bard AJ, Parsons R, and Jordan J (eds.) (1985) Standard Potentials in
R gas constant, resistance Aqueous Solution. New York, USA: Marcel Dekker.
Barthel JMG, Krienke H, and Kunz W (1998) Physical Chemistry of
Rsp specific resistance Electrolyte Solutions. Darmstadt, DE: Springer.
rs Stokes radius Bockris JO’M and Reddy AKN (1970) Modern Electrochemistry, vol. 1.
S Onsager parameter New York, USA: Plenum Press.
Fuoss RM (1980) Conductimetric determination of thermodynamic
ti transference number of ion i pairing constants for symmetrical electrolytes. Proceedings of the
T absolute temperature National Academy of Sciences of the United States of America 77:
v+, v– number of cations, anions 34--38.
Hammer WJ and Wu Y-C (1972) Osmotic coefficients and mean activity
w1 mass fraction for substance 1 coefficients of univalent electrolytes in water. Journal of Physical and
z ionic charge Chemical Reference Data 4: 1047--1099.
a degree of ion association Kay RL (1973) Transference number measurements. In: Yeager E and
Salkind AJ (eds.) Techniques of Electrochemistry, vol. 2, pp. 61--116.
DG change in Gibbs energy New York, USA: John Wiley.
DG1 standard Gibbs energy Krumgalz B (1983) Separation of limiting equivalent conductances into
DGfo standard Gibbs energy of formation ionic contributions in nonaqueous solutions by indirect methods.
Journal of the Chemical Society, Faraday Transactions I 79:
e dielectric constant 571--587.
g viscosity Marcus Y (1983) Ionic radii in aqueous solutions. Journal of Solution
c activity coefficient Chemistry 12: 271--275.
Pitzer KS (1973) Thermodynamics of electrolytes 1: Theoretical basis
ct7 mean activity for u ions and general equations. The Journal of Physical Chemistry 77:
ki molar conductivity of ion i 268--277.
K molar conductivity Pitzer KS (1991) Activity Coefficients in Electrolyte Solutions. Boca
Raton, USA: CRC Press.
Ko molar conductivity at infinite dilution Robinson RA and Stokes RH (1965) Electrolyte Solutions. Oxford, UK:
Paproducts product of activities of reaction producs Butterworths.
Pareactions product of activities of reaction Spiro M (1973) Conductance and transference numbers. In: Covington
AK and Dickinson T (eds.) Physical Chemistry of Organic Solvent
reactants Systems, ch. 5, Parts 2 and 3, pp. 615--680. London: Plenum Press.