Supercapacitors

In our quest to improve energy storage, a new device-Supercapcaitor comes into picture, with
characteristics intermediate between a battery and capacitor; and also with inherent similarities to
both. At the Thin Film Physics laboratory, Shivaji University, Kolhapur, under the guidance and
supervision of my mentor, Prof. C.D. Lokhande, I had the opportunity to delve deeper into this topic
and see real Supercapacitors being made and tested for. It was an exciting venture into the
theoretical aspects of electrochemistry at work and I could only marvel at the potent ideas this
technology could create. In the following pages, I would like to explain the theory of Supercapacitors
and its research, as best as my comprehension permits.
A supercapacitor or an ultra-capacitor, in a more general sense, is known as the electrochemical
capacitor based on the electrochemical mechanism of charge storage. But the name supercapacitor
is used more often because of the very high capacitance (of a few hundred farads) compared to the
conventional capacitors that it can exhibit.
From the study of batteries and capacitors it can be summarised that batteries have a higher energy
density whereas capacitors have a higher power density but Supercapacitors bridge this gap with
moderate values for both parameters and show interesting results on various modifications.

Capacitance of Supercapacitors
The capacitance of Supercapacitors cannot be simply attributed to geometric construction as in Eq. 2
of previous chapter. It depends on two storage mechanisms that simultaneously exist in varying
proportions based on electrode materials and electrolytes.
The two storage principles are:
Electrical Double Layer Capacitance: This is the electrostatic storage of charge in a double layer of
charge at the interface of electrode and electrolyte.
Pseudocapacitance: This is the electrochemical storage of charge and energy in the form of faradaic
chemical reactions.
Now there might be a high ratio of one principle over another and that gives us: a double layer
capacitor with charge storage using the first mechanism prevailing over the second or vice-versa, a
pseudocapacitor. Or yet another possibility suggests the complementary presence of both
capacitances, i.e. a hybrid capacitor.
A supercapacitor essentially has two electrodes and an electrolyte in between. The electrode is a
combination of a current collector and an electrode material deposited over it-which can be any of
the following: carbonaceous substances like activated carbon, carbon nanotubes, etc or metal oxide
or even a conducting polymer.


Electrical Double Layer Capacitor (EDLC) and Capacitance
It is found that, at the interface of electrode-electrolyte, a Helmholtz double layer similar to one
present on colloidal particles exists and this separation of charges is a seat of potential difference
that stores energy electrostatically.
Helmholtz visualized the double layer as two thin parallel layers of opposite charges separated at a
distance of a few nanometres like a nano-scale version of a parallel plate capacitor with the thin
layer of solvent molecules acting as dielectric. The inverse dependence of capacitance on distance
increases the capacitance manifold. Though this theory accounted for higher capacitance, it failed to
take into consideration the thermal energy of ions in solution. Gouy and Chapman, independently,
considered the layer on the solution side to be made of diffuse layers and Stern made corrections as
to the finite size of the ions, thus rejecting the point charge approach and finally, the so-called
Electric Double Layer was born. This finite size placed a limit on the closeness of the double layer,
and thus an upper limit on the capacitance that can be generated on decreasing distance.







Some other modifications in the basic theory give rise to further structural clarification. As shown in
the figure above,


This double layer that exists at the electrode/electrolyte boundary involves adsorption of ions and
counter-ions and so forth forming a diffuse layer. Since this phenomena does not have any phase
changes or chemical changes which might induce irreversibility to the entire system, i.e. the
processes are non faradaic in nature, the cyclability improves tremendously. This point
differentiates it from the batteries which can undergo only several thousand cycles owing to the
chemical interconversions that take place. On the other hand, an ordinary capacitor, which only
charges and discharges reversibly can undergo millions of cycles.
However, unlike the ordinary capacitors whose capacitance is only determined by the bulk
properties of the dielectric medium, the double layer capacitance is affected by the microscopic
properties of dielectric at molecular level because the distance of separation here is of the order of
nano meters or angstroms comparable to the size of ions and is under intense electric field. As a
result the capacitance is a function of the solvent used, the nature of ions present, the hydrated and
bare radii, etc. Varying the use of solvents can greatly alter the capacitance and this leads to more
active research as to attain the best suitable electrolyte. In this interest, replacing aqueous
electrolytes with non-aqueous electrolyte (like propylene carbonate) which has a higher solution
decomposition potential, thus increasing the total energy that it can store. This is explained by the
dependence of the energy on the voltage squared term in Eq.3. This increases the theoretical energy
density 10-16 times as high and the power density 3-4 times (Source: book). But non-aqueous
solutions with higher resistivities increase the equivalent series resistance of the circuit which is
undesirable as it dissipates power. Another aspect that controls power density is the dissociation of
electrolytes which affects conductance and depends on electrolyte concentration to a large extent.
Thus it is a subtle interplay of resistivity of electrolyte and its decomposition potential that could
optimize the energy density as well as power density.
So far, we have only been discussing the effect of distance and dielectric constant of solution but
another factor that may affect the capacitance drastically is the specific area of the electrode
material which can be increased by means of using porous electrodes. This is where carbon steps in.
As we already know, Carbon has several allotropic forms-some of which happen to be graphite,
diamond and fullerenes. Graphite is electronically conducting because of the sp² hybridisation which
leaves one electron free to move between layers of carbon stacked over one another. Similarly many
powdered carbons have high specific surface area and carbon fibres can be synthesised having high
mechanical integrity and good electric conductivity. Moreover these electrode materials are
subjected to activation pre-treatment to improve surface area and optimize pore accessibility.
For EDLCs, electrode materials are various carbon allotropes like activated carbons, carbon aerogels
and carbon nanotubes. Let’s discuss these in brief:
Activated carbon (ACs): Activated Carbon was the first material to be used in EDLC capacitors and
is cost-effective in accordance with the current development of supercapacitors. It has a high
specific surface area of a few thousands of m² per gram. This powdered amorphous form of carbon
can be easily produced from carbonization of peat, husk, coconut shells, charcoal, etc.
Carbon Aerogels: Carbon aerogels are highly porous with uniform pore structure and ultra-light
materials with better conductivity (i.e. better power density) and chemical stability. They can be
synthesised from resorcinol-formaldehyde condensation products.
Carbon nanotubes (CNTs): These are recently developed allotropes of the structural fullerene
family that has a nanostructured cylindrical design. They have exceptional properties like thermal
conductivity, semi-conducting nature and mechanical sturdiness. And have been already put to use
in supercapacitors owing to their large specific surface area (about 3 times as large as those of ACs)
but remain commercially elusive due to their expensive synthesis.
Graphene: Graphene is nothing but a one-atom thick layer of graphite that has better conductivity
as well as higher specific area than activated carbons. They can theoretically have energy density
comparable to a NiMH battery and power density hundred-fold. But the only shortcoming as of now
is that it can only be produced in labs and that too, meeting a high cost requirement.
Now researchers at UCLA have used a standard LightScribe DVD optical drive to produce
such electrodes. The electrodes are composed of an expanded network of graphene — a one-
atom-thick layer of graphitic carbon — that shows excellent mechanical and electrical
properties as well as exceptionally high surface area.

Source: http://phys.org/news/2012-03-graphene-supercapacitor-portable-electronics.html#jCp


From this analysis, it is clear that the EDLC is more similar to the regular capacitor than a battery. It
seems to have taken the concept of capacitors to nano-scale and rendered it possible to make
microscopic changes in the capacitive system to optimize energy storage.
But, seldom can we ignore the pseudo-capacitance even in carbon based EDLCs and so it becomes
necessary to study this other capacitive phenomena in detail so that a fuller understanding of
Supercapacitors is made.

Pseudocapacitance
As already mentioned, the faradaic reactions taking place at the electrode/electrolyte contributes to
another type of capacitance called Pseudocapacitance. Of course, this differs greatly from the
conventional capacitor or EDLC where charge is stored electrostatically and non-faradaically. This so-
called Pseudocapacitance has origins in electrosorption and redox reactions at electrode surfaces or
oxide films and in this manner it can be said to be similar to a battery where energy is stored
electrochemically.
Here there is a passage of charge across the double layer and this charge storage mechanism
contributed to overall capacitance as follows: the thermodynamic relation between the extents of a
charge acceptance, say an infinitesimally small charge dQ over a similar change in potential
difference, dV i.e. dQ/dV is equivalent to capacitance. This capacitance is called Pseudocapacitance
(as pseudo- means apparent or false) because it originates in its own unique way radically different
from the electrostatic manner.
Research has shown that the electrode processes in a Pseudocapacitor can be Redox, intercalation
or electrosorption or more than one occurring simultaneously. In a redox, the electrode material
undergoes a number of changes of oxidation states and often many of them have overlapping
potentials. In intercalation, as previously mentioned, a molecule or ion gets reversibly inserted into a
layered structure and there may be charge transfer. Charge transfer complexes are formed when an
electron donor bonds with an electron acceptor which maybe one atom or a part of a molecule or
large structure (like an electrode surface). These are not strong chemical bonds but rather
electrostatic attractions.
As for Electrosorption, I quote from two references:
We define here “electrosorption” as the reversible adsorption or the reversible retention of
ions , molecules , or particles from a liquid phase on or near an electronic conducting
surface as a function of electric potential difference between the surface and the liquid.
Adsorption: Science and Technology
NATO ASI Series Volume 158, 1989, pp 193-221

A third [principle type of Pseudocapacitance] is electrosorbed H at the Pt metals, but this is not
feasible for commercial development
Source: Electrochemical Supercapacitors-Scientific Fundamentals and Technological Applications by
B.E. Conway


Metal Oxides
Delving deeper into the redox mechanism, we see that most of the transition metal oxides
electrodes like RuO₂ (ruthenium dioxide), MnO₂ (Manganese dioxide), IrO₂ (Iridium dioxide),NiO
(Nickel Oxide),etc have a lattice that facilitates the intercalation of protons into/ deintercalation out
of them. And being transition metals they have a number of oxidation states that are inter-
convertible quite reversibly. The chemical reactions themselves are quite complex but have been
observed to involve the RuO₂/Ru₂O₃ couple and O²¯/OH¯ couple, in case of ruthenium oxide
electrode. During charging H⁺ is intercalated into and during discharging, it is de-intercalated as
shown in the above figure.
Though this might be mildly reminiscent of an alkaline battery if we consider MnO₂, a point of
difference in the redox reactions of batteries and of supercapacitors is that in the latter, the
reactions are a comparatively faster sequence of reversible chemical changes accompanied by
charge transfer without phase changes. They don’t involve strong covalent bonds and so
irreversibility is mostly reduced due to which they are more stable over time. Due to this excellent
reversibility, they have a high cyclability, around several hundreds of thousands.

Conducting Polymers
Several Conducting Polymers like polyaniline, polythiophene, polypyrrole and their derivatives are
used as electrode materials. They have several characteristic behaviours like high conductivity
because of the π-orbital conjugation and electrochemically oxidised or reduced by withdrawal or
injection of electrons and are often compared to doping of p-type (oxidised/positively charged) and
n-type (reduced/negatively charged) semiconductors. This type of electrochemical redox takes place
in the entire bulk and is fast as it does not involve any irreversible chemical changes and phase
changes. They have a substantial amount of Pseudocapacitance and are cheaper than the expensive
transition metal oxides. But being organic in origin, the do not have much stability and neither do
they have long cyclability (only a few thousand cycles). They are also known to swell and contract on
charge and discharge respectively.