Electrochimica Acta 84 (2012) 165173

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Electrochimica Acta
j our nal homepage: www. el sevi er . com/ l ocat e/ el ect act a
Review article
Electrochemical capacitors: Technical challenges and prognosis for future
markets
A.K. Shukla

, A. Banerjee, M.K. Ravikumar, A. Jalajakshi

Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, India
a r t i c l e i n f o
Article history:
Received 16 January 2012
Received in revised form13 March 2012
Accepted 14 March 2012
Available online 23 March 2012
Keywords:
Electrochemical capacitors
Electrical-double-layer capacitors
Pseudo-capacitors
Hybrid capacitors
Leadcarbon hybrid ultracapacitors
a b s t r a c t
Electrochemical capacitors are potential devices that could help bringing about major advances in future
energy storage. They are lightweight and their manufacture and disposal has no detrimental effects on
the environment. A comprehensive description of fundamental science of electrochemical capacitors is
presented. Similarities and differences between electrochemical capacitors and secondary batteries for
electrical energy storage are highlighted and various types of electrochemical capacitors are discussed
with special reference to leadcarbon hybrid ultracapacitors. Some envisaged applications of electro-
chemical capacitors are described along with the technical challenges and prognosis for future markets.
2012 Published by Elsevier Ltd.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
2. Types of electrochemical capacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
2.1. Electrical-double-layer capacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
2.2. Pseudocapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
2.3. Hybrid supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
3. Merits and demerits of supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
4. Applications of electrochemical capacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
4.1. Memory back-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
4.2. Electric and hybrid electric vehicles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
4.3. Power quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
4.4. Battery improvement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
4.5. Portable power supplies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
4.6. Renewable energy applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
4.7. Micro-scale energy scavenging systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
5. Capacitor-system sizing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
6. Technology challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
7. Market aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173

Corresponding author. Tel.: +91 80 22932795; fax: +91 80 23601310.

E-mail addresses: akshukla2006@gmail.com, shukla@sscu.iisc.ernet.in (A.K. Shukla).
0013-4686/$ see front matter 2012 Published by Elsevier Ltd.
doi:10.1016/j.electacta.2012.03.059
166 A.K. Shukla et al. / Electrochimica Acta 84 (2012) 165173
1. Introduction
A capacitor is a passive electronic component comprising a pair
of conducting plates separated by a dielectric. Capacitors store
electrical energy as electrostatic charge with equal quantities of
positive and negative charges on opposite faces of the conducting
plates resulting in a voltage difference between the faces. When
the two faces are connected by an external load, current ows
until complete charge balance is attained and the stored energy
is released. The capacitor can then be retrieved to its charged state
by applying voltage. Since the charge is stored physically without
any chemical or phase changes, the process is highly reversible and
the chargedischarge cycle can be repeated over and over again,
virtually without limit.
The quantity of charge (Q) stored in a capacitor is equal to the
device voltage (V) times proportionality constant (C) called capac-
itance, i.e.
Q = CV (1)
In Eq. (1), capacitance C is in Farad, charge Q is in Coulomb and the
voltage V is in Volt. In vacuum, the capacitance of such a capacitor
is proportional to the area (A) of the conductors divided by the
thickness (d) of the dielectric separating them as shown in Fig. 1,
i.e.
C =

0
A
d
(2)
In Eq. (2), proportionality constant
0
=8.910
12
F m
1
is the per-
mittivity of the free space or vacuum. Permittivity is the measure of
the resistance that is encountered whilst forming an electric eld
in a medium. In other words, permittivity is a measure of how an
electric eld affects, or is affected, by a dielectric medium. Per-
mittivity is determined by the ability of a material to polarize in
response to the eld that reduces the total eld inside the material.
Accordingly, permittivity relates to a materials ability to transmit
or permit an electric eld. The permittivity of a mediumdescribes
howmuch electric eld or more correctly electric ux is generated
per unit charge. Less electric ux exists in a medium with a high
permittivity per unit charge due to polarization effects. A dielectric
medium showing orientation of charged particles creating polar-
ization effects is represented in Fig. 2. Such a medium can have
a higher ratio of electric ux to charge (permittivity) than empty
space. When the region between the plates is lled with a dielec-
tric material of relativepermittivity(
r
), whichincreases theenergy
stored in the device, the capacitance (C) is then expressed as:
C =

r

0
A
d
(3)
Fig. 1. Schematic sketch of a parallel-plate capacitor.
Fig. 2. Adielectric mediumshowing orientation of charged particles creating polar-
ization effects.
On substituting Eq. (3) in Eq. (1), we get
Q =

0
A
d

V (4)
The total charge stored in a capacitor is directly proportional to the
dielectric constant of the dielectric (
r
) and area of the electrode
(A), and inversely proportional to the thickness (d) of the dielec-
tric. Accordingly, to achieve a high energy density capacitor, the
dielectric should have high dielectric constant, large surface area
and thin dielectric medium. The electrical energy (E) stored in a
charged capacitor is:
E =

q
C
dq (5)
As the voltage of the capacitor increases from 0 to V, the charge
accumulatedonthe electrode increases from0toq andaccordingly,
the stored energy E is expressed as:
E =
1
2
Cq
2
=
1
2
CV
2
(6)
Taking the voltage V of the capacitor as 1V, the capacitor, according
to Eq. (6), can store a maximum energy of 14Wh kg
1
. But, in
practice, however, the useful available energyfromsucha capacitor
is only 3.5Wh kg
1
[1]. The maximum deliverable power by a
capacitor (P
max
) is
P
max
=
V
2
4R
ESR
(7)
In Eq. (7), R
ESR
is the equivalent series resistance (ESR) and is
simply the sum of all the resistive components within a capac-
itor. It is stated in ohms and referenced to specic frequencies.
It is noteworthy that lowering R
ESR
leads to high power. One of
the characteristics of a capacitor often mentioned in commercial
products is time constant (), i.e., the product RC. Capacitors with
small time constant are those delivering huge power in a relatively
short time whilst those with high time constants discharge over
relatively longer times. Ideally, energy pulses in the time range
10
2
s < <10
2
s are desired for most of the capacitor applications.
There are three types of capacitors, namely (i) electrostatic
capacitors, (ii) electrolytic capacitors, and (iii) electrochemical
capacitors.
Electrostatic capacitors, shownschematicallyinFig. 3(a), consist
of a pair of conductors separated with a dielectric such as air, mica,
polymer lm, ceramic, etc. These capacitors operate at gigahertz
(GHz) frequencies with charge times of 10
9
s. These capacitors
store the lowest energy of the three types.
A.K. Shukla et al. / Electrochimica Acta 84 (2012) 165173 167
Fig. 3. Schematic sketches for (a) electrostatic, (b) electrolytic and (c) electrochem-
ical capacitors.
Electrolytic capacitors, shown schematically in Fig. 3(b), use
a thinner and higher dielectric constant dielectric that is grown
on a strong metal surface such as etched aluminium. These can
store 10-times more energy thanthe electrostatic capacitors. These
capacitors can generally be used up to 20kHz.
It has long been accepted that an electrical double-layer exists
at the electrode/electrolyte interface that governs adsorption
phenomena andinuences chargetransfer reactionrates. As shown
in Fig. 3(c), the electrical double-layer stretches to about a few

A
and stores electrostatic energy like a capacitor. It is noteworthy
that the existence of the electrical double-layer has always been
inferred fromindirect observations of related properties and quan-
tities, but never directly probed. It was realized only recently that
the energy stored per unit surface area is signicant and becomes
technologically attractive with the introduction of materials with
high active-surface-areas, such as activated carbons.
In the electrical double-layer, solvated ions are attracted to
the solid surface by an equal but opposite charge in the solid as
shown in Fig. 4. These two parallel regions of charge form the
source of the term electrical double-layer where the charge sep-
aration as measured in molecular dimensions is less than 10
9
m
[2]. As the surface area of activated carbon is 1000m
2
g
1
of
material, this creates a capacitor cell with specic capacitance
of (68.910
12
10
6
)/10
9
, i.e. 10
5
F kg
1
and the possibil-
ity of realising devices rated at many thousands of Farad [38].
Owing to their appreciably high capacitance, these capacitors are
also referred to as supercapacitors or ultracapacitors. A com-
parison of size, mass and characteristic response time for 1MJ
energy storage systems with electrostatic, electrolytic and super-
capacitors are presented in Table 1. It is noteworthy that although
Fig. 4. Schematic sketch of an electrical double-layer capacitor.
supercapacitors are at least 10-fold lower in mass and volume,
they have much slower response times, typically 0.33s or even
greater. This precludes their use in alternating current ltering
applications, and this, in contrast to other type of capacitors, makes
super-capacitors effectively direct current devices. Accordingly,
electrical-double-layer capacitors cannot be used in applications
served by electrolytic or electrostatic capacitors.
Whilst the operation of electrical-double-layer capacitors
(EDLCs) is based on non-faradaic accumulation of electrostatic
charge at the electrolyte/carbon surface through reversible ion
adsorption on to the carbon surface of the electrodes, fast faradaic-
charge-transfer brought about by the charging of the electrical
double-layer at the electrode/electrolyte interface determines the
working of pseudocapacitors [1]. A combination of faradaic and
non-faradaic components would generate electrochemical capac-
itors that exhibit high capacitance for pulse power as well as
sustained energy; these electrochemical capacitors are referred to
as hybrid supercapacitors. A technically more appropriate termfor
all these capacitors is electrochemical capacitors.
In its essential structure, an electrochemical capacitor is akin
to an electrochemical cell as both are formed by two electrodes
separated by an electrolyte. The difference is that the latter oper-
ates on the basis of a faradaic process whilst the former operates
either by non-faradaic or fast faradaic charging of the electrical
double-layer. This difference is reected in the values of energy
and power density of the batteries and electrochemical capaci-
tors. Although power density values for a supercapacitor happen
to be much higher than batteries, the latter have energy densi-
ties much higher than the electrochemical capacitors. Accordingly,
electrochemical capacitors are categorized as power devices whilst
batteries are energy devices. Typically, energy density values for an
electrochemical capacitor are <10Wh kg
1
whilst energy densities
for batteries couldrange between30and200Wh kg
1
. The absence
of phase transformations and kinetic polarization limitations helps
electrochemical capacitors to have much longer cycle life, typically
Table 1
A comparison of size, mass and characteristic response time for 1MJ energy storage
systems with electrostatic, electrolytic and electrochemical capacitors.
Capacitor type Mass (kg) Volume (ml) Response time (s)
Electrostatic 200,000 14010
6
10
9
Electrolytic 10,000 2.210
6
10
4
Electrochemical 30100 0.020.110
6
1
168 A.K. Shukla et al. / Electrochimica Acta 84 (2012) 165173
Table 2
Taxonomy of electrochemical capacitors.
10
5
, than batteries, typically 5001000. But response times for
electrochemical capacitors are extremely fast in relation to bat-
teries (30s and more) where a 1s discharge time is equal to a
3600C-rate for a 1Ahbattery inbattery terms. Supercapacitors also
have lower operating voltages, limited by the breakdown potential
of the electrolyte, than other type of capacitors, typically between
13.5Vper cell. Inmany applications, this means that electrochem-
ical capacitors must be series connected, like batteries, to meet
voltage requirements.
In recent years, phenomenal progress has been made in the
development of electrochemical capacitors to combine themwith
the battery inanelectric vehicle, where the electrochemical capaci-
tors can provide the peak power needed for acceleration during hill
climbing whilst the main battery operates in a continuous lower-
power-regime. This combined action improves the reliability and
longevity of the electric vehicle power system whilst providing
improved performance. This article briey describes the types of
electrochemical capacitors, origin of their capacitances, their char-
acteristics vis--vis a battery, and their envisaged applications.
2. Types of electrochemical capacitors
Based on the current R&D trends, electrochemical capacitors
can be divided into three general classes, namely electrical-double-
layer capacitors, pseudocapacitors, and hybrid capacitors as shown
in Table 2. Each class is characterized by its unique mecha-
nism for storing charge. These are non-faradaic, faradaic, and
a combination of the two, respectively. Faradaic processes such
as oxidationreduction reactions, involve the transfer of charge
between electrode and electrolyte. By contrast, a non-faradaic pro-
cess does not use a chemical mechanism and charges are rather
distributed on surfaces by physical processes that do not involve
any making or breaking of chemical bonds.
2.1. Electrical-double-layer capacitors
These capacitors rely on carbon-based structures utilizing non-
faradaic electrostatic charging of the electrical double-layer formed
at the electrodeelectrolyte interface and are hence termed as
electrical-double-layer capacitors. Carbon is ideally suited for fab-
rication of EDLCs as it has a potential voltage range of almost ideal
polarizability with about 1V in aqueous solutions and up to 3.5V
in non-aqueous media. In an ideally polarizable electrode, changes
in potential due to ow of charge to or from the electrode cause
only changes in the charge density on the metal and conjugately
in the ion density on the solution side of the electrode interface
leading to the charging of the consequent electrical double-layer
withnocharges passingacross thedouble-layer interphasethrough
any faradaic process. Accordingly, at a given potential, the charged
electrical double-layer is at electrostatic equilibrium rather than
faradaically at a Nernstian equilibrium[3].
In the light of the foregoing, EDLCs store electrical energy at
the electrolyte/carbon interface through reversible ion adsorption
onto the carbon surface, thus charging the electrical double-layer
through a non-faradaic contribution between an electronic con-
ductor, namely the carbon, and a liquid ionic-conductor, namely
the electrolyte. The few nano-meter thick electrical double-layers
at the phase boundary between the electrode and electrolyte
can be referred to as a nano-dielectric akin to a parallel-plate
capacitor wherein the current collector of each electrode contacts
high-surface-area-conductive carbon impregnated with an elec-
trolyte. At the negative electrode, the negative charges received
during charge by an external source are balanced by the positive
charges of the electrolyte cations that accumulate on the surface
and within the pores of the carbon particles. The counter elec-
trode charges itself positively against the surrounding solution.
Because of the formation of the electrical double-layer at each
electrode/electrolyte interface, a complete cell is formed by two
capacitors in series and the overall capacitance (C
T
) is expressed
as:
1/C
T
= 1/C
+
+1C

(8)
In Eq. (8), C
+
is the capacitance of cathode/electrolyte interface and
C

is the capacitance of anode/electrolyte interface.

In an ideal electrical-double-layer capacitor, only charge sep-
aration takes place at the electrode and there are no oxidation
or reduction reactions. Accordingly, charge (Q) stored in such a
capacitor is related to its capacitance (C) and voltage (V) as: Q=CV.
Consequently, the capacitance is voltage independent but does
depend on electrode surface area, the double-layer thickness and
dielectric constant of the electrolyte.
Traditionally, activated carbons have been used in EDLCs. But
conducting carbons withgraphitic structure alsoinclude templated
andcarbide-derivedcarbons, nanotubes, nanohorns, onions (multi-
shell fullerenes), polyhedral particles, scrolls, carbon blacks and
graphene [8,9]. It is noteworthy that each of these includes sev-
eral structural varieties. For example, nanotubes can be single-,
double- and multi-walled; they can have scroll or co-axial cylin-
der structure, be polygonized or have a disordered wall structure,
they can have various functional groups or be doped with nitrogen.
Accordingly, a variety of carbons substantially differing in struc-
ture, properties and cost are available for use in EDLCs. However,
one needs to select the carbon depending on the required device
performance or electrolyte used.
An ideal capacitor will retain charge forever. However, all
capacitors experience some self-discharge due to aw sites or
other transfer mechanisms through the dielectric medium. Self-
discharge can be measured by recording the potential difference
between the two terminals of a capacitor under open circuit as a
function of time following its charge or by applying a oat current
after charging the capacitor so as to maintainthe full-charge poten-
tial difference across the capacitor; the oat current matches the
self-discharge rate at that potential. Life tests have shown the elec-
trochemical capacitors to be very robust with cycle life of generally
10
6
. Most manufacturers rate the life of capacitors in terms of
cycle life where one cycle consists of full charge and full discharge
in an operating voltage window. This is in contrast to batteries,
which have limited cycle-life, generally less than 1500.
For any electrical energy source, there is always a trade-off
between the amount of power and energy that it can provide.
The faster one tries to pull energy from a device, the lesser is the
A.K. Shukla et al. / Electrochimica Acta 84 (2012) 165173 169
total energy output from it. Electrochemical capacitors have lim-
ited energy density but are known to exhibit high power densities.
Accordingly, electrochemical capacitors cannot replace batteries
but can complement themin many applications. Applications that
can benet fromelectrochemical capacitors include medical, such
as X-ray and MRI (magnetic-resonance imaging), spot and contact
welding, audio-line stiffening, actuators, large electric motor start-
ing, and power quality such as initial pulse power for UPS systems.
2.2. Pseudocapacitors
Pseudo-capacitive ultracapacitors are based on charge stor-
age brought about by the charging of the electrical double-layer
at electrodeelectrolyte interface from quick faradaic charge-
transfer reactions. In pseudocapacitors, electrical double-layer is
fast charged by charge transfer at the electrodes comprising metal
oxides such as RuO
x
or conducting polymers such as polyaniline.
The charge transferred in the redox reactions is voltage-dependent
and hence is the capacitance [39].
In the pseudocapacitor arena, noble metal oxides typically have
a highcapacitance of about 700F g
1
. However, cost andeconomics
limit the use of noble metal oxides and carbon-based graphene
or carbon nanotube related structures [310]. Therefore, there is
a need to explore alternative systems that have good electronic
conductivity, adequate surface area, and the ability to undergo
faradaic electrochemical redox reactions to store charge. Transi-
tion metal oxides and non-oxides are well known for their ability
to undergo faradaic electrochemical redox mechanism of charge
storage. Vanadiumnitride (VN) is one such transition-metal nitride
that has electronic conductivity comparable to carbon. Researchers
are attempting to generate high surface area transition metal non-
oxide and oxide superstructures with high capacitance, scan rate
response, and cyclability for sustained short- and long-termpulse
power. The goal is toimprove performance of EDLCs using activated
carbon or graphene, possibly in combination with transition metal
non-oxide materials.
Researchers are also focusing on high surface-area-carbons, to
achieve desirable power and energy densities along with VN and
other transition metal oxides and non-oxides to generate com-
posite structures for grid power storage. Experiments are being
conducted to increase the lifetime, rated voltage, range of oper-
ating temperatures, and combined power/energy density with the
target capacitance values of 1000F g
1
[11]. It is shown that syn-
thesized vanadiumnitride nanoparticles exhibit these capacitance
values due to the formation of a thin amorphous oxide/oxynitride
layer on the surface of the nitride.
2.3. Hybrid supercapacitors
Most supercapacitors rely on carbon-based structures utiliz-
ing electrochemical double-layer capacitance effect. By contrast,
a pseudocapacitor relies on charge stored due to faradaic charge-
transfer process with surface atoms. A combination of faradaic
andnon-faradaic components wouldgenerate supercapacitors that
exhibit high capacitance for pulse power as well as sustained
energy. These supercapacitors are referred to as hybrid superca-
pacitors.
Conventional rechargeable batteries store higher energy than
supercapacitors. The energy densities of rechargeable batteries are
in the range of 30200Wh kg
1
. However, their charge/discharge
rates are slow, typically C/10 and C/5. They also have limited
cycle-life. By contrast, energy densities of supercapacitors range
between 3 and 10Wh kg
1
. But supercapacitors can be charged
and discharged quickly. Supercapacitors also have higher cycle-
life in relation to batteries. The combination of the two storage
devices, namely the battery and the supercapacitor, could be a
Fig. 5. Simplied equivalent circuit of double-layer capacitor including EPR.
good alternative. Supercapacitors comprising one carbon double-
layer electrode and a battery-like electrode are also referred to as
hybrid supercapacitors. These capacitors overarch the energy den-
sity advantage of the batteries and have the benet of high power
density of electrochemical double-layer capacitors.
Researchers are nowfocusing on other nano structured battery
materials, such as Ni(OH)
2
, MnO
2
, PbO
2
, etc., to develop nano-
hybrid capacitors [1222]. Among these, PbO
2
-based leadcarbon
supercapacitors are at fairly advanced stage of development.
Recently, a 12V/200F leadcarbon hybrid supercapacitor employ-
ing substrate-integrated PbO
2
positive electrodes and activated
carbon anodes with silica-gel sulphuric acid electrolyte has been
developed and performance tested [23].
The equivalent circuits in Fig. 5 comprise three components:
the capacitance, equivalent series resistance (ESR), and equivalent
parallel resistance (EPR). ESR is a loss termthat results in internal
heating in the capacitor and is therefore of importance during its
charge and discharge. It also will reduce terminal voltage during
discharge due to the resistive divider-effect. EPR is related to leak-
age current that impacts long-term energy storage performance
of the capacitor. The details on the evaluation of the capacitance,
ESR, and EPR for the 12V leadcarbon hybrid supercapacitors or
ultracapacitors as a case study are discussed below. Capacitance is
determined from the constant-current charging and discharging
characteristics of the capacitor. For each constant-current dis-
charge of the capacitor, its capacitance is determined from the
relation
C =
It
V
1
V
2
(9)
In Eq. (9), I is charge/discharge current, t is charge/discharge
time, and V
1
and V
2
are initial and end capacitor voltages. Fig. 6
shows the capacitance for the 12V leadcarbon hybrid ultracapac-
itor at varying discharge currents [23]. ESR could be determined by
two methods. Firstly, from constant-current discharge where the
current (I) is interrupted or abruptly changed at the beginning and
Fig. 6. Discharge data for the 12V leadcarbon hybrid ultracapacitor at varying
discharge rates.
170 A.K. Shukla et al. / Electrochimica Acta 84 (2012) 165173
Fig. 7. ESR data for the 12V leadcarbon hybrid ultracapacitor at varying voltages.
end of the charge/discharge of the cycle. In this procedure, ESR is
calculated fromthe IR (ohmic) step at the beginning of charge and
discharge of the capacitor fromEq. (10).
ESR =
V
IRStep
I
(10)
Alternatively, impedance spectra are used to determine capac-
itance and ESR. ESR data for the 12V leadcarbon hybrid
ultracapacitor as obtained fromimpedance measurements at vary-
ingvoltages are showninFig. 7[23]. It is noteworthythat duringthe
discharge of a capacitor, capacitive component represents the volt-
age change due to the change in energy within the electrochemical
capacitor. The resistive component represents the voltage change
due to ESR of the electrochemical capacitor. Equivalent parallel
resistance or internal parallel resistance relates to leakage effects
and reects on the long-term energy storage performance of the
capacitor. To estimate EPR of the capacitor, it is slowly charged to
aninitial voltage V
1
. Subsequently, it is left inopencircuit condition
for 24h. At the end of 24h, the terminal voltage (V
2
) is measured
and recorded. Assuming rated capacitance, EPR is calculated using
Eq. (11).
EPR =
86400
ln(V
2
/V
1
)C
(11)
In Eq. (11), V
1
is initial capacitor voltage and V
2
is terminal voltage
of the capacitor at the end of 24h [24]. Alternatively, the capacitor
is charged to its working voltage and maintained at that voltage for
24handthe residual current is measuredafter 24h. EPRis obtained
fromthe ratio of the working voltage and the current [25].
Fig. 8 shows EPR values as obtained from the self-discharge
data for the 12V leadcarbon hybrid ultracapacitor at (a) 28

C
and (b) 50

C using Eq. (11). Generally, ultracapacitors perform

under a wide range of climatic conditions, typically from+70

C to
40

C. Interestingly, leadcarbon hybrid ultracapacitors can cycle

for 10
5
times with little decay in their performance as shown in
Fig. 9. The energy storage inanelectrochemical capacitor is a highly
reversible process. The process will move charge and ions only, and
does not make or break chemical bonds like a battery. This pro-
cess allows for hundreds of thousands of charge/discharge cycles
with minimal changes in performance over the product life cycle.
Besides, leadcarbonhybridultracapacitors exhibit acceptable per-
formance both at low and high temperatures as shown in Fig. 10.
Thepower densityfor the12V-gel hybridultracapacitors as derived
fromits energy density of 1.4Wh kg
1
, which is obtained fromits
Fig. 8. Self-discharge data for the 12Vleadcarbonhybridultracapacitor at (a) 28

C
and (b) 50

C.
25W constant-power discharge [23], and response-time of 4.82s
[23] is 1.46Wh kg
1
/4.8s =1046Wkg
1
[26].
In principle, by packing multiple cells in a module, any volt-
age requirement is attainable in a way that is lightweight and
efcient. An increase in specic energy of an asymmetrical ultra-
capacitor could be achieved by rstly identifying the cell voltage
limiting electrode, and then adjusting the capacitance ratio of
the electrodes [27]. Leadcarbon hybrid ultracapacitors are cost-
effective and the resources for their manufacturing are practically
Fig. 9. Pulsed chargedischarge cycle life data for a 12V leadcarbon hybrid ultra-
capacitor.
A.K. Shukla et al. / Electrochimica Acta 84 (2012) 165173 171
Fig. 10. Effect of temperature on the capacitance of the 12V leadcarbon hybrid
ultracapacitor.
unlimited since almost 95% of the materials used are recyclable.
Recently, Axion Power International was awarded a purchase order
for leadcarbon ultracapacitors from SilTek for participation in a
Zero-Energy Building in Washington DC Naval Yard. Axion is also
providing its leadcarbon ultracapacitors to Penn State University
for testing in conjunction with the US Army Tank & Automobile
Command (TACOM).
Li-ion hybrid supercapacitors are also promising since the oper-
ating voltage for these supercapacitors could be as high as 3.5V.
These supercapacitors use a non-aqueous solvent and a suitable
lithiumsalt as the electrolyte. The high voltage-output of superca-
pacitors provides higher specic energydensityandpower density
values to Li-based hybrid supercapacitors. There are various types
of lithium-based hybrid supercapacitors but most attractive are
those with Li
4
Ti
5
O
12
anode and activated carbon as cathode;
lithiumintercalated metal oxides, such as MnO
2
, V
2
O
5
, etc., are also
important cathode materials for lithium-based supercapacitors. In
recent years, hybrid capacitors with such intercalation electrodes
are being explored for non-aqueous hybrid capacitors. However,
these battery electrodes have the problem of poor Li diffusion
co-efcient and poor electronic conductivity. In order to over-
come these difculties researchers have adopted nanomaterials
technology. Such supercapacitors are called nanohybrid capacitors.
Since the nanostructured materials, such as nanotubes, nanorods,
nanoparticles of carbon, metal oxides and transition metal non-
oxides, etc., offer high surface-area, supercapacitors employing
these materials are certain to achieve higher energy and power
density. Recently, nanohybrid capacitors based on nano-crystalline
Li
4
Ti
5
O
12
attached onto carbon nanobres have been reported [6].
In a recent study, dendritic conducting polymer based on
bithiophenetriarylamine is shown to give a peak specic capac-
itance of more than 990F g
1
[28]. Problems of swelling and
contractionleadingtomechanical degradationandfailureas well as
chemical degradation over repeated cycling must be addressed to
make conducting polymer-based supercapacitors attractive. Use of
nanoscopic materials suchas CNTs canmitigatedegradationcaused
by volume changes by reducing diffusion lengths [29]. For exam-
ple, aPANI/CNTcompositeelectrode[30] withahierarchical porous
nanostructure gave a specic capacitance of 1030F g
1
. Advantages
that accrue fromthe use of such nanostructures based on CNTs are
a conducting network that facilitates efcient charge transport, a
high specic surface area and nanometric sizes that ensure high
utilization of electrode materials, a hierarchically porous structure
that can enhance ionic conductivity, and improved mechanical
properties of the support that can reduce electrode degradation
caused by volume changes [31].
Because a higher specic surface area can expose more of the
active centres, it is clear that an effective way to improve specic
capacitance is to increase the specic surface area. For example, a
nanotubular array electrode incorporated with hydrous ruthenium
oxide yielded a specic capacitance of 1300F g
1
[32]. Similarly,
introducing RuO
2
into nanostructures can effectively increase its
surface area as well as provide increased paths for diffusion, which
should translate into high capacitance values. Nanostructuring the
metal oxide can also lead to improved results by virtue of higher
specic surface area and short diffusion paths as compared to bulk
counterparts [3335]. Deng and Chen [36] reported that -MnO
2
nanowires with a diameter of 3040nm and mean pore diam-
eter of 3.1nm yields a specic capacitance of 466F g
1
and high
cycling efciency. Use of aligned CNTs instead of disordered CNTs
can provide advantages such as low contact resistance, large sur-
face area, and fast electron transfer. In fact, capacitances as high
as of 642F g
1
are demonstrated with a nanostructured composite
electrodemadeof denseandverticallyalignedCNTs anda thinlayer
of MnO
2
[18].
3. Merits and demerits of supercapacitors
The vivid merits of supercapacitors are fast charging, long cycle-
life, high power, little maintenance, wide temperature-range and
limited heat-dissipation. The demerits of the supercapacitors are
high equivalent series resistance, low energy, high rate of self-
discharge, high leakage-current and high cost.
4. Applications of electrochemical capacitors
Applications of electrochemical capacitors are discussed in a
recent book by Miller [37]. The major applications of electrochem-
ical capacitors appear to be in high-pulse power and short-term
power hold. Some applications of electrochemical capacitors are
discussed below.
4.1. Memory back-up
Many appliances now incorporate digital components with
memory where even a very brief interruption in the power supply
could cause the loss of stored information. In such applications, the
capacitor canact as a back-upsupply for short periods. Batteries are
the alternative to the capacitors for these applications but batteries
have a limited lifetime, and therefore need to be replaced regularly.
Electrochemical capacitors are a preferredchoice as back-uppower
supply due to their long lifetime.
4.2. Electric and hybrid electric vehicles
Battery-powered electric vehicles have the limitations of low
power-density, limited charge/discharge cycles, high-temperature
dependence, and long charging-time. Electrochemical capacitors
are bereft of these limitations albeit they are faced with other
limitations such as low energy-density and high costs. Peak-load
requirements that result from accelerating or climbing up-hills
could be met by the high-power device, namely the electrochem-
ical capacitors bank. Utilization of electrochemical capacitors also
facilitates harvesting energy fromregenerative braking.
An electrochemical capacitor is presently the power supply in
hybrid cars for start/stop application. When a hybrid vehicle stops,
its internal combustion engine (ICE) shuts down which is restarted
by the electrical system powered by an electrochemical capacitor
172 A.K. Shukla et al. / Electrochimica Acta 84 (2012) 165173
that is recharged when the ICE resumes powering the vehicle. This
helps reducing fuel consumption. Electrochemical capacitors are
ideally suited for city-transit buses with stop-and-go driving, in
trash trucks that can experience as many as a thousand start/stop
cycles during a day, and in delivery vans that operate on similar
drive cycles. The primary challenges for any energy storage unit
used in heavy duty hybrid vehicles are the long cycle-life and the
needtodissipatetheheat generatedduetocharge/dischargelosses.
Electrochemical capacitors are highly efcient and have limited
heat dissipation owing to their low-energy content.
4.3. Power quality
Static-synchronous-compensator system injects or absorbs
power froma distribution line to compensate for any voltage uc-
tuations. Sucha systemrequires a DCenergy storage device of some
sort fromwhich energy could be drawn or stored. Since the major-
ity of voltage perturbations on the distribution bus are short-lived,
usually not lasting more than 10 cycles, electrochemical capacitors
are an attractive option for energy storage and delivery to improve
the power quality [38].
4.4. Battery improvement
Batteries are being used widely in the portable power appli-
ances, such as UPS, laptops, and mobile phones. Many such devices
draw high-power pulsed currents which result in the reduction
of battery performance. Batteries in parallel with electrochemical
capacitors could be an effective alternative for these applications
[39].
4.5. Portable power supplies
Most devices presently using battery power supplies have long
recharge time and need to be charged overnight. These need to be
replaced with the electrochemical capacitors that can be quickly
charged and discharged. Indeed, for any portable electronic equip-
ment with moderate energy demands, electrochemical capacitors
are ideally suited as rechargeable stand-alone power sources.
4.6. Renewable energy applications
In solar photovoltaic applications, batteries need to be replaced
every 13 years because of continuous cycling that has a detri-
mental effect on batteries [40]. But electrochemical capacitors can
be charged and discharged quickly for large number of cycles,
and need to be replaced every 20 years only, which is similar
to the life-span of the photovoltaic panels. Life-cycle costs are
therefore reduced by eliminating frequent maintenance require-
ments. Energy efciency is always of primary concern in renewable
power generation. In this regard electrochemical capacitors are
attractive as they exhibit much higher charging efciency than
batteries.
The pitch of wind turbine three-rotor blades can be adjusted
to respond to current conditions. Pitch adjustments allow wind
turbines to maximize energy generation. In order to adjust the
blades, turbines need power. To date, wind turbine manufactur-
ers have relied on battery-driven energy storage systems for that
power. In a wind turbine, pitch control of each of the blades
ensures optimum positioning for efcient use of wind speed for
both performance and safety. Though wind turbine blades are
long and awkward to reposition, it is vital to adjust them quickly
to grab useful winds. It is even more vital to quickly get blades
turn out of potentially damaging winds. Engineers accomplish
the pitch control either mechanically or electrically, but electrical
control systems are more reliable. However, when electrical con-
trol systems rely on battery-based back-up systems, the potential
maintenance advantage over hydraulic systems is not necessar-
ily realized. Electrochemical capacitors are becoming the power
source of choice in wind turbine nacelles to power blade-pitch-
control.
4.7. Micro-scale energy scavenging systems
Products and systems can be designed around supercapacitor
technology for efcient energy storage and its retrieval later. The
concept is to generate electrical energy at anytime from see-saw,
swing, health-club equipment, exercising equipment, etc., with lit-
tle effort and its retrieval on demand.
5. Capacitor-systemsizing
It is noteworthy that capacitor-systemsizing is critical for each
of the aforesaid applications. At lower voltages, a constant power
requires higher current as the voltage decreases. This is often over-
looked during the initial analysis, and can result in under-sizing
a solution. During the sizing calculations if the total voltage drop
(dV
total
=I R
esr
+I dt/C) happens to be greater than the applica-
tion specication limit then one will either need to move to the
next size-up cell or to place two series stacks in parallel.
6. Technology challenges
For many applications, relatively higher cost of electrochem-
ical capacitors is currently the primary reason for not being the
energy storage technology of choice. Despite their high-level of
performance, electrochemical capacitors are simply too expen-
sive to compete against the other available approaches. For some
applications, potential users nd electrochemical capacitors to be
attractivebut ndtheir energydensitytobetoolow. Henceincreas-
ing energy density and lowering cost are the primary challenges
facing electrochemical capacitor developers. This must be achieved
without sacricing the high cycle-life and exceptional high-rate
performance that sets electrochemical capacitors apart from bat-
teries. It is desirable to generate high surface-area transition
metal non-oxide and oxide superstructures with high capacitance,
scan rate response, and cyclability for sustained short- and long-
term pulse power. The goal will be to improve the double-layer
capacitancebyusingactivatedcarbonor graphene, possiblyincom-
bination with transition metal non-oxide materials. Increasing the
voltage windowthrough which the electrochemical capacitors can
operate reliably is highly desirable owing to the V
2
term in the
stored energy for increasing the energy density of electrochemi-
cal capacitors. This would also increase the power performance,
whichis againproportional to V
2
. Ahigher operating voltage would
attract the usage of electrochemical capacitors in several differ-
ent ways. Besides, higher cell voltage would require fewer cells in
series for the specied systemvoltage. The problems that remainin
the technology of electrochemical capacitors are: (a) engineering
of high-rate production lines for fabrication of well-matched units
for stacking multi-cell high-voltage devices, (b) production of reli-
ably sealed, low ESR, bipolar, stacked devices, and (c) reduction in
self-discharge rates.
7. Market aspects
At present, electrochemical capacitor devices of various types
occupy only a limited niche market. But the special properties of
electrochemical capacitors, namely their high capacitance per unit
weight or volume and their capability for highpower-density oper-
ationondischargeor recharge, makethemsuperior toconventional
A.K. Shukla et al. / Electrochimica Acta 84 (2012) 165173 173
capacitors. Electrochemical capacitors are making and will con-
tinue to make new market and technology for themselves. This is
already apparent in the areas of power back-up and on a larger
scale in the development of hybrid-capacitor battery systems for
electric vehicle power requirements. Various other applications,
in addition to those referred earlier, that are being proposed are
cold-cranking assistance and exhaust-catalyst pre-heating, hand-
held power tools, fork-lift operations, emergency-door opening
in air-crafts, trains, etc. Although the market for electrochemical
capacitors is currentlylimitedbut it is projectedtotouch$40Billion
by 2015. Concomitantly, the cost per Farad for the ultracapacitors
is decreasing, for example the 3kF ultracapacitor that was available
for $5000 a decade ago is nowpegged at only $50.
8. Conclusions
Various types of electrochemical capacitors are discussed
with special emphasis on leadcarbon supercapacitors. Capaci-
tor measurements, namely capacitance, ESR and EPR, pertaining
to leadcarbon supercapacitors are briey discussed. The mer-
its and demerits of electrochemical capacitors are compared with
storage batteries. Electrochemical capacitors are ideally suited for
transportation, renewable power, industrial equipments and other
commercial applications. Electrochemical capacitors are designed
with low equivalent series resistance, and can deliver and absorb
a high current. They are quickly charged, making themperfect for
regenerative braking, i.e., capturing the energy of a train or other
quick charge and quick release scenarios. Various plausible appli-
cations of electrochemical capacitors are discussed. As anemerging
technology in the area of energy storage, electrochemical capaci-
tors are a promising device for certainniche applications at present.
But the global market share of supercapacitors is projected to reach
$40 billion by 2015.
Acknowledgements
Financial support from Department of Science & Technology,
Govt. of India, NewDelhi and Indian Institute of Science, Bangalore
under its Energy Storage Systems Initiative is gratefully acknowl-
edged. A.B. thanks Council of Scientic & Industrial Research, New
Delhi for a Senior Research Fellowship.
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