Electrochemical Supercapacitors for Energy Storage
and Conversion
Brian Kihun Kim1 , Serubbable Sy1 , Aiping Yu1 , and Jinjun Zhang2
1
University of Waterloo, Waterloo, Canada
2 National Research Council Canada, Vancouver, Canada
1 INTRODUCTION
With the increase in energy demand, developing clean,
sustainable, and efficient energy storage and conversion tech-
nologies has become one of the necessary approaches for
the world communities of science and technology. Among
different energy storage and conversion technologies, elec-
trochemical ones such as batteries, fuel cells, and electro-
chemical supercapacitors (ESs) have been recognized as
important. Particularly, the ES, also known as supercapac-
itor, ultracapacitor, or electrochemical double-layer capac-
itor, can store relatively higher energy density than that of
conventional capacitor. With several advantages, such as fast
charging, long charge–discharge cycles, and broad operating
temperature ranges, ESs have found wide applications in
hybrid or electric vehicles, electronics, aircrafts, and smart
grids. There are nevertheless still some challenges in ES
systems such as relatively low energy density and high manu-
facturing cost.
1.1 Conventional capacitors and electrochemical
supercapacitors
A conventional capacitor, also known as a condenser or an
electrostatic capacitor, is an energy storing device consisting
of two electrically conductive plates (sometimes called elec-
trodes), which are separated by a dielectric layer. The dielec-
tric materials are insulators such as ceramic, glass, paper,
Handbook of Clean Energy Systems, Online C 2015 John Wiley & Sons, Ltd.
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in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces112
plastic, and aluminum oxide (Al2 O3 ). The charging process
of capacitors is simple. When the two conductive plates are
connected to an external power source, which induces a
potential difference between the two plates, positive charges
accumulate on one plate and negative charges build up on the
other plate. The charges remain on their corresponding plates
even after the removal of the external power source; this is the
charged state of a capacitor. During discharge, the capacitor
releases the positive/negative charges to a connected resistive
load to deliver its stored energy. However, the applications
for these conventional capacitors are limited by their low
energy capacity. As a result, the search for a new mate-
rial led to a new type of capacitor called supercapacitors
or ECs. Unlike conventional capacitors, ES electrodes are
normally composed of high surface porous materials such
as carbon particle materials and the separator is either solid
or liquid, thus electrode/electrolyte interfaces are generated.
These interfaces, called electric double layer, have higher
surface area than dielectric capacitors and thus can store
more charges. It is recognized that the improved structure of
an ES allows better energy storage than conventional capaci-
tors. Regarding the detailed discussion about the fundamen-
tals of ES, a section is presented to take care of that. Before
diving into the ES principles, it would be beneficial to briefly
learn about the history of this energy storage device.
1.2 History
In antiquity, the phenomenon of rubbing amber with a
cloth was found to attract small particles. In 1745, this
unexplained phenomenon was used to develop the very
first known capacitor: the Leyden jar. At that time, the
2 Electrochemical Storage
Leyden jar comprised glass where its interior and exterior
surfaces were laminated with metal foils. The jar itself
served as a dielectric material, while the laminated surfaces
acted as conductive plates (Yu, Chabot, and Zhang, 2013).
Since then, capacitor technology rapidly evolved through
steady research. In 1957, the very first ES was patented by
Howard Becker of General Electric (GE) (Becker, 1957). He
pioneered a capacitor with a porous carbon electrode and
sulfuric acid as its electrolyte, forming an electric double-
layer system. However, GE did not pursue this develop-
ment. Meanwhile, in 1970, Standard Oil of Ohio (SOHIO)
patented an electrolytic capacitor based on carbon (Boos,
1970). Nippon Electric Company (NEC) licensed the patent
from SOHIO and marketed aqueous electrolyte capacitors as
ESs (Endo et al., 2001). Subsequently, NEC acquired the
first commercial success by promoting supercapacitors as
backup memory for electronics. In the late twentieth century,
numerous companies initiated the production of supercapac-
itors to compete in the market. Pinnacle Research Institute
(PRI) designed supercapacitors with low internal resistances
for high powered portable energy storage (Pandolfo and
Hollenkamp, 2006). In 1992, Maxwell Technologies took
over PRI’s development and manufactured their own super-
capacitors named “Boost Caps.” This continuous research
has led to today’s high performing commercially available
supercapacitors.
1.3 Importance of electrochemical
supercapacitors
ESs possess advantages that complement the many defi-
ciencies of other commercial energy storage devices,
which in return have aroused great interest academically
and commercially. ESs are capable of generating higher
power densities than fuel cells and batteries and greater
energy densities than conventional capacitors. Figure 1
shows a Ragone plot of specific power with respect to the
specific energy of significant energy storage and conversion
devices.
From the plot in Figure 1, it can be seen that superca-
pacitor technology can evidently bridge the gap between
batteries and capacitors in terms of both power and energy
densities. Furthermore, supercapacitors have longer cycle
life than batteries because the chemical phase changes
in the electrodes of a supercapacitor are much less than
that in a battery during continuous charging/discharging
(Yu, Davies, and Chen, 2012). These key attributes make
supercapacitors more attractive and versatile as high
powered energy storages. The US Department of Energy
(DOE) has spotlighted batteries and supercapacitors as
major future energy storage technologies (Goodenough,
2007).
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DOI: 10.1002/9781118991978.hces112
107
106
Capacitors
Power density (W kg−1)
105
104
Supercapacitors
103
102 Batteries
Fuel cells
101
100
0.01 0.1 1 10 100 1000 10,000
Energy density (Wh kg−1)
Figure 1. Ragone plot for significant energy storage and conver-
sion devices.
1.4 Application market and economy of
electrochemical supercapacitors
The earliest application of ESs was a backup power supply
for electronics. On one hand, supercapacitors, capable of
discharging large amounts of power in a matter of seconds,
are ideal for supplying instant and uninterruptable backup
power in response to energy surges or a shutdown. Batteries,
on the other hand, are less-than-ideal for this type of applica-
tion because they are more expensive and may induce uncon-
trollable temperature escalations (Yu, Chabot, and Zhang,
2013; Yu, Davies, and Chen, 2012).
Supercapacitors with its long cycle life and high power
delivery are applicable to both consumer and military
devices. Coleman’s portable cordless screwdrivers, which
are powered by supercapacitors, are currently listed on the
market for home usage. This power tool is fully charged
within 90 s for immediate use (Miller and Burke, 2008).
In military applications, supercapacitors are generally
implemented and used as alternative power for electronics
in armed vehicles, black boxes on helicopters, and so on
(Yu, Chabot, and Zhang, 2013).
Energy recovery in public transportations and hybrid
electric vehicle (HEV) has further reenergized interest in
supercapacitors. This is because the primary challenge
for public transportation was harnessing the regenerative
energy when braking for the frequent stops and reusing the
stored energy when accelerating to depart. Supercapacitors
are capable of storing instantaneous brake energy and
discharging upon demand, which improves fuel efficiency.
Moreover, current HEVs encounter temperature stability
challenges where the charging/discharging mechanisms
 Electrochemical Supercapacitors for Energy Storage and Conversion
in HEVs generate undesirable heat from resistances and
exothermic reactions. Possessing the ability to dissipate
heat effectively, supercapacitors can be implemented into
HEVs to manage the thermal issues, thus enabling them
easier entry into the HEV market (Miller and Burke,
2008).
1.5 Current research and development status
In spite of the rapid progression, supercapacitor technology
still faces the low energy density challenge. In order to over-
come this challenge, governments, industries, and academic
organizations around the world are making great efforts to
develop novel and high performing electrode and electrolyte
materials for supercapacitors. In addition, some efforts are
also putting on the system design and performance optimiza-
tion for some niche applications. For example, many research
groups have developed special carbon and polymer mate-
rials to fabricate flexible supercapacitors for applications in
electronic devices, as shown in Figure 2 (Yuan et al., 2012;
El-Kady et al., 2012; Davies et al., 2011; Meng et al., 2010).
In addition, some effort has also been given to the
hybridization of the electrode to increase the electrode’s
(a) (b)
1 cm
(c) (d)
Figure 2. (a) Carbon nanoparticles/MnO2 nanorods composed
all solid-state supercapacitors. Source: Reproduced with permis-
sion from C ACS Publications (Yuan et al., 2012). (b) Flex-
ible graphene/polyaniline nanofiber composite film. Source: Repro-
duced with permission from C ACS Publications (Wu et al., 2010a).
(c) Graphene-based flexible supercapacitors with electropolymer-
ized polypyrrole. Source: Reproduced with permission from C ACS
Publications (Davies et al., 2011). (d) Flexible all-solid-state paper-
like polymer supercapacitors. Source: Reproduced with permission
from C ACS Publications (Meng et al., 2010).
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DOI: 10.1002/9781118991978.hces112
3
capacitance. In this approach, battery and supercapac-
itor electrode materials are integrated together to yield
higher energy density hybrid supercapacitors. The results
showed that an improvement in energy density without
compromising its high power density, which is inherent in
supercapacitors, could be achieved with this kind of hybrid
supercapacitors (Wang and Xia, 2013; Lang et al., 2011).
However, these advantageous properties must always be
balanced against the decrease in cycle stability and loss in
power performance. Extensive research will continue to
overcome these challenges and evolve the supercapacitor
technology to be superior and eventually dominate the
energy storage market.
2 TYPES OF SUPERCAPACITORS
As discussed in the previous section, in the mid-1900s,
researchers pioneered electrostatic double-layer capacitors,
which are capable of accumulating exceptionally high
amounts of charge. These kinds of capacitors were later
called ESs because the charges stored inside the device reside
within the electric double layer at the electrode/electrolyte
interfaces. With rapid growths of mobile electronics and
hybrid vehicles, research in ES technology developed other
two additional variations: pseudocapacitors and asymmetric
supercapacitors. The following sections explain the energy
storage mechanisms behind conventional capacitors and
the three categories of ESs, such as electrostatic double-
layer supercapacitors, pseudocapacitors, and asymmetric
supercapacitors.
2.1 Conventional capacitors
Conventional capacitors, formerly referred to as condensers,
store energy electrostatically. Manifold forms of capacitors
exist commercially, but their fundamental design is similar.
Capacitors are generally composed of dielectric materials
such as glass, plastic, ceramic, and paper, which separates
two electrically conductive plates (electrodes).
Inducing a potential difference across the plates can
generate an electric field in the dielectric layer that accu-
mulates equal magnitudes of positive and negative charges,
as shown in Figure 3. Capacitance is the measure by
which capacitors store energy through this arrangement of
charges. Capacitance (C) is measured in farad (F) and can
be calculated by
A∗𝜖
C= , (1)
d
where A is the surface area of the plates, 𝜖 is the permittivity
of the dielectric material, which measures the resistance
4 Electrochemical Storage

Electrodes

(ε ric
ct
+

le

)
−

ie
− +

D
+ − − + +
+ − Plates − + +
(A) − −
+ − + − + + −
−
+ + − − −
+
−
− +
+ − − + +
− +
+ − −
− + +
+ − Separator +
+ −
+ − − − − −
−− − −
+ − −
+ − − −−−
+ −+ + + + − + −
−
+ : Electrolyte
+ +
+ − +
+ + ++ + + − + −
+ −
− Ions
+ −− − −− −+ −
+ + + − − − − − −− : Interface
(d) + ++ − − −
++ − − −
+ − − − ++ −
+ − − − −− − − −
Figure 3. Arrangement of charges in a dielectric material during ++ − − −
++ + − −
the charged state of conventional capacitors.

Figure 4. A schematic of charged EDLCs.

of the material during the formation electric fields, and d

is the distance between the plates. Commercial capacitors
can store energy in the range between pico- and micro-
farads.
2.2 Electrostatic double-layer capacitor (EDLC)
EDLCs share a similar mechanism with conventional capac-
itors. However, instead of storing charges in the dielectric
layer, EDLCs utilize the interfaces between the electrode and
the electrolyte for their energy storage. As shown in Figure 4,
a potential difference across the EDLCs induces electrodes
with different polarity, leading to the migration of the elec-
trolyte ions to the micropores of the electrodes.
Unlike conventional capacitors, the capacitance is deter-
mined by the thickness of the separator (d in Equation 1).
EDLC’s capacitance is determined by the thickness of the
double layer at the electrode/electrolyte interface (Figure 4).
The thickness of the double layer is much smaller than
that of the separator, indicating that EDLC must have a
much higher capacitance than that of conventional capac-
itor according to Equation (1) (Zhang and Zhao, 2009). In
addition to shorter separation distance, significantly larger
area of electrode/electrolyte interface than that in conven-
tional capacitor can further give increased capacitance of
EDLC. In addition, excellent electrical conductivity of the
electrolyte in EDLC can reduce the internal resistance of
electrodes, while good wettability of the electrolyte will
facilitate increased mobility of ions into the pores of elec-
trodes to further enhance the capacitive performance of
EDLCs (Zhang and Zhao, 2009; Yu, Davies, and Chen,
2012). Normally, a specific type of abundant and inexpen-
sive carbon known as activated carbon (AC) is widely used
in commercial EDLCs. ACs can exhibit specific capaci-
tance values of 100–120 F/g in organic electrolyte (Simon
and Gogotsi, 2008). To further improve the capacitance of
AC material, further advances have engineered sophisti-
cated carbon structures, such as ordered mesoporous carbon,
carbon nanotubes (CNTs), and graphene. These materials are
generally more expensive than ACs; however, their capaci-
tive capabilities surpass that of ACs. For example, Zhu et al.
(2011) synthesized KOH-activated graphene that demon-
strates a superior specific capacitance of 166 F/g in organic
electrolyte.
2.3 Pseudocapacitor
In order to increase the capacitance of a supercapacitor,
some electrochemical active redox material can be compos-
ited with the carbon material such as AC to make elec-
trode materials for supercapacitor. In this way, the electron
storage at the electrode/electrolyte interface of EDLC is
not simply a physical process, some fast reversible oxida-
tion/reduction reaction(s) will occur to give 10–100 times
more capacitance than that of pure carbon-based EDLC
(Conway, 1991). This kind of ES is called pseudocapacitors.
One of the more thoroughly explored materials for pseu-
docapacitors is ruthenium oxide. This precious metal has
multiple redox phases [i.e., Ru(IV)/(III) and Ru(III)/Ru(II)]

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DOI: 10.1002/9781118991978.hces112
 Electrochemical Supercapacitors for Energy Storage and Conversion
in proton-rich environments [e.g., sulfuric acid (H2 SO4 )],
supplying more electron transfers for greater capacitance
(Zhang and Zhao, 2009; Conway, 1999). For example, Hu
et al. (2006) synthesized RuO2 nanotubes that gave around
1300 F/g in H2 SO4 electrolyte. Unfortunately, although this
RuO2 electrode material can give outstanding performance,
its toxicity, high cost, and scarcity limit its practical appli-
cation in supercapacitors. In this regard, research and devel-
opment have shifted their resources to less toxic and inex-
pensive alternatives: nonprecious transitional metal such as
cobalt oxide, nickel oxide, and conductive polymers. For
example, cobalt oxide nanowires displayed capacitance of
570–700 F/g (Gao et al., 2010) and nickel oxide nanoflowers
presented a capacitance range of 600–760 F/g, respectively
(Yuan et al., 2009; Kim, Chabot, and Yu, 2013). A conduc-
tive polymer, polypyrrole (PPY), produced by Zhang et al.
(2010) demonstrated capacitance values of 150–400 F/g.
Although these alternatives could exhibit promising perfor-
mances, their low conductivity (relative to carbonaceous
materials) and lack of long cycle stability seemed to inhibit
their application in pseudocapacitors. To address these draw-
backs, carbonaceous additives were explored to integrate into
the electrode for improved performance (Kim, Chabot, and
Yu, 2013).
2.4 Asymmetric supercapacitor
As the name implies, an asymmetric supercapacitor
is configured with dissimilar electrodes: a battery-like
Faradaic electrode and a capacitive carbonaceous elec-
trode. This unique design can adjust the operating voltage
window and increase the energy density due to the electro-
chemical redox process at the Faradaic electrode (Malak
et al., 2010). However, optimization of both electrodes
through careful design is mandatory. The prototype of
+ −
Load
Graphene/MnO2
e−
e−
e− e−
e−
e−
50 nm
Cation MnO2
Ni foam
Figure 5. Schematic of an asymmetric MnO2 -graphene/AC supercapacitor. Source: Reproduced with permission from C Wiley (Fan et al.,
2011).
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DOI: 10.1002/9781118991978.hces112
5
asymmetric supercapacitors was invented by Amatucci
et al. (2001) and it was further researched by many groups.
For example, Wu et al. (2010) assembled a high energy
density asymmetric supercapacitor from MnO2 nanowires
and graphene with an energy density of 30.4 Wh/kg. In
comparison with symmetrically configured supercapac-
itors composed of graphene/graphene (2.8 Wh/kg) and
MnO2 /MnO2 (5.2 Wh/kg), the asymmetric MnO2 /graphene
cell reported by Wu et al. displayed a significant superiority
in energy density. Fan et al. (2011) further improved the
energy density by incorporating MnO2 into graphene as an
electrode and complementing it to an AC nanofiber-based
electrode. Figure 5 illustrates the design of the MnO2
graphene/AC supercapacitor that possesses an outstanding
energy density of 51.1 Wh/kg.
Furthermore, Fuji Heavy Industry designed a commercial
lithium-ion-doped AC/AC asymmetric supercapacitor that
could supply an energy density up to 25 Wh/kg (Naoi
and Simon, 2008). It should be noted that although the
energy densities of asymmetric supercapacitors could
be increased when compared to those of symmetric
supercapacitors, implementing the Faradaic materials
into electrodes to fabricate asymmetric supercapacitors
may lead to the reduced cycle stability. Nevertheless,
asymmetric supercapacitors have great potential for
future energy storage devices in terms of energy density
improvement.
3 SUPERCAPACITOR COMPONENTS
AND MATERIALS
Optimizing supercapacitor design will typically enhance
performance. The optimization includes careful selection
of electrodes, electrolyte, conductive current collectors, and
ACN
e−
e
1 μm
Separator
6 Electrochemical Storage
sealants. Matured engineered designs should not be contin-
gent on performance but should also consider cost and safety.
3.1 Supercapacitor components and materials
As briefly mentioned in Section 2, depending on electrode
materials, supercapacitors can utilize two energy storage
mechanisms. EDLCs, which are primarily composed of
carbonaceous materials, statically deposit charges within the
porous structures of electrodes. Pseudocapacitive superca-
pacitors, which consist of transitional metal oxides/nitrides
and conducting polymers such as electrodes, accumulate
energy through fast, reversible electrochemical redox reac-
tions on the active surfaces of the electrodes. Both mecha-
nisms share common qualifications for selecting appropriate
materials in electrodes, which include the following:
1. Large surface area and porosity
2. Good surface wettability
3. High electrical conductivity
4. Long cycle stability (>105 cycles)
5. Facile manipulation of morphology (e.g., pore sizes,
pore distributions, particle dimensions/distributions)
6. Thermodynamic stability for a wide operational poten-
tial range
3.1.1 EDLC electrode materials
The widely accepted materials for EDLC electrodes are
carbon. Its low manufacturing cost, abundance, large surface
area, controllable morphology, and high electrical conduc-
tivity are ideal characteristics of EDLC electrodes. Further-
more, carbon materials can be post-treated to alter their
structures and chemical/mechanical properties for various
(a)
85 nm
Figure 6. (a) Transmission electron microscope (TEM) image of catalytically grown carbon nanotubes. Source: Reproduced with
permission from C AIP Publishing (Niu et al., 1997). (b) Scanning electron microscope (SEM) image of a carbon nanotube forest. Source:
Reproduced with permission from C ACS Publications (Lau et al., 2003).
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DOI: 10.1002/9781118991978.hces112
applications. Common classifications of modified carbon
include AC, CNT, and graphene.
3.1.1.1 Activated carbon (AC). In general, current
commercially available supercapacitors utilize AC as their
electrode material. AC is processed either via thermal or
chemical activation of carbonaceous precursors such as
petroleum pitches, coals, woods, and hard-shells. Potassium
hydroxide (KOH) activation is one of the most prevalent
techniques used to produce AC due to its low processing
cost. During the activation, sufficient energy is applied to
small hexagonal carbon rings, which are also known as
graphene sheets. This energy breaks the linkage between
these sheets, deforming the structure and creating pores
(Qu, 2002). The creation of pores increases the surface area,
which contributes to the high capacitive performance of AC.
AC can store specific capacitance between 100 and 200 F/g
in aqueous electrolytes and 50 and 150 F/g in organic elec-
trolytes (Frackowiak, 2007). Wang et al. (Wang, Wang, and
Liang, 2003) and Wen et al. (2009) achieved capacitances
of 160 and 225 F/g, respectively, with KOH-treated AC in
aqueous electrolytes.
3.1.1.2 Carbon nanotubes (CNTs). CNTs are engi-
neered carbon with superior properties compared to AC.
CNTs are composed of graphitic walls assembled in near-
one-dimensional (1-D) cylinders (Figure 6). The thickness of
the tubes divides CNTs into single-walled carbon nanotubes
(SWCNTs) and multi-walled carbon nanotubes (MWCNTs).
The long 1-D structure of CNTs offers excellent mechan-
ical properties and prevents the scattering of electrons,
exceeding the electrical conductivity of AC (Baughman,
Zakhidov, and De Heer, 2002). Highly ordered CNT
arrays have significant surface area, offering large porous
area for electron storage (Hu et al., 2009). Depending
(b)
1 μm
 Electrochemical Supercapacitors for Energy Storage and Conversion
on morphology and purity, the specific capacitance of
CNTs ranges between 15 and 200 F/g (Liu et al., 2010b).
Unfortunately, a major deterrent from the potential usage of
CNTs in commercial supercapacitors is its high production
cost. Carbon arc discharge and chemical vapor deposition
are currently implemented techniques in producing lab-scale
amounts of high purity CNTs (Ding et al., 2001). However,
these techniques require further research before scaling up
production and purification.
3.1.1.3 Graphene. Possessing high thermal/electrical
conductivity, mechanical strength, chemical stability, and
large surface area, graphene distinguishes itself from other
competitive carbon materials. Recently, it became the rising
advanced material for supercapacitor applications (Wang
et al., 2009b). Graphene is a flat 2-D honeycomb-shaped
monolayer sheet of carbon atoms that is the basic building
blocks of other carbon materials as illustrated in Figure 7
(Geim and Novoselov, 2007).
Graphene may possess a theoretical surface area of up to
2675 m2 /g and translates to 550 F/g if all of the theoretical
area is fully utilized (Liu et al., 2010a). However, as with all
nanostructures, especially graphene sheets, agglomeration
and restacking limit the specific capacitance of graphene
between 100 and 200 F/g. To reduce the restacking, Wang
et al. (2011) incorporated CNTs as a spacer between
2-D graphene sheet
Particle 1-D CNT 3-D graphite
Figure 7. Illustration of 2-D graphene sheet as the building blocks
for other carbon materials such as particle, 1-D CNT, and 3-D
graphite. Source: Reproduced with permission from C ACS Publi-
cations (Geim and Novoselov, 2007).
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DOI: 10.1002/9781118991978.hces112
7
graphene sheets (Figure 8a). This drastically improved
the capacitance to 318 F/g. Other techniques such as
KOH-activated graphene by Zhu et al. (2011) exceeded the
theoretical surface area of graphene, achieving 3100 m2 /g
through exposing hidden sheets and creating extra pores.
Hassan et al. (2013) doped the graphene planes with
nitrogen atoms (Figure 8b) to increase the electrical conduc-
tivities and promote graphene–ion interaction in electrolyte
solutions. The nitrogen-doped graphene demonstrated a
capacitance value of 194 F/g.
3.1.2 Pseudocapacitor electrode materials
Transition metal oxides and electrically conductive polymer
are commonly selected as the electrode materials for pseu-
docapacitors. Pseudocapacitor electrodes utilize redox reac-
tions on the surfaces of electroactive materials. The redox
reactions are electrode potential dependent and change with
charging and discharging. This mechanism provides supe-
rior capacitance and energy density compared to purely
carbon-based EDLCs. However, these advantageous proper-
ties are normally counterbalanced with poor life cycles. For
example, EDLCs can achieve up to half a million cycles,
whereas pseudocapacitors are compromised with cycling
issues. This is because the multiple cycles of chemical reac-
tions can damage the pseudocapacitive material and induce
undesirable changes to the morphology, leading to reduction
in performance as cycling progresses. In response, carbon
supports are often added to resolve the detriment.
3.1.2.1 Transition metal oxides. Common transition
metal oxides that are currently researched for pseudocapac-
itive electrodes are RuO2 (Zheng and Jow, 1995), Co3 O4
(Lin, Ritter, and Popov, 1998), MnO2 (Pang, Anderson, and
Chapman, 2000), NiO (Liu and Anderson, 1996), and V2 O5
(Reddy and Reddy, 2006). These metal oxides undergo
multiple oxidation states at specific potentials, leading to
increased capacitance. RuO2 is one of the most popular
pseudocapacitive materials because of its good reversibility,
three oxidation states within a potential range of 1.2 V,
and an acceptable life cycle (Simon and Gogotsi, 2008).
For example, Hu, Chen, and Chang (2004) maximized
the performance of hydrous RuO2 by annealing it at high
temperature achieving a capacitance of 1340 F/g. Unfortu-
nately, ruthenium metal is toxic and expensive due to scarce
availability. This shifted the attention of researchers toward
nonprecious metals that are more commercially available,
including cobalt, manganese, nickel, and vanadium oxides.
Table 1 lists the specific capacitances and the morphologies
of the previously mentioned metal oxides and Figure 9
illustrates each of their morphologies.
8 Electrochemical Storage

N
O O

N N
N
N

N N

N
N
N
N
(a) (b) O−

Figure 8. (a) Model of graphene sheets separated by CNTs. Source: Reproduced with permission from C ACS Publications (Wang et al.,
2011). (b) Nitrogen-doped graphene structure. Source: Reproduced with permission from C RSC Publications (Hassan et al., 2013).

Table 1. Morphology and performance of currently researched

metal oxides for pseudocapacitor applications. (a) (b)

Compound Morphology Specific Reference

Capacitance (F/g)
Co3 O4 Brush-like 1525 Rakhi et al. (2012)
nanowires
MnO2 Nanowires ∼800 Chin, Pang, and
Anderson (2010) 100 nm
NiO Nanopetals 710 Lee et al. (2011)
V2 O5 Nanoporous 316 Saravanakumar, 50 μm
network Purushothaman, (c) (d)
and Muralidharan
(2012)

Nonetheless, metal oxides generally suffer performance

loss for possessing lower electrical conductivity than carbon
materials. Additions of carbon scaffolds can normally
resolve this issue. For example, Li and Zhitomirsky (2009)
incorporated MnO2 into MWCNTs to enhance the capacitive
performance. Kim, Chabot, and Yu (2013) investigated the
effect of adding different carbon supports on nickel oxides.
For example, addition of SWCNT could significantly
increase the capacitive performances from 474 to 810 F/g at
rapid charge/discharge rates.
3.1.2.2 Conducting polymer. Besides transition metal
oxides, electrically conductive polymers [e.g., PPY, polyani-
line (PANI)] are also explored due to their inexpensive
and facile synthesis. Electrochemical deposition and chem-
ical oxidation are the main techniques in synthesizing
these materials. Tailoring the synthesis conditions could
result in different morphologies. During the charging and
discharging periods, conducting polymers switch between
two doping states (p-doping/n-doping) where electrolyte
2 μm
1 μm 10 29 SEI
Figure 9. SEM images illustrating the detailed morphologies of (a)
brush-like Co3 O4 nanowire. Source: Reproduced with permission
from C ACS Publications (Rakhi et al., 2012). (b) MnO2 nanowire.
Source: Reproduced with permission from C Elsevier (Chin, Pang,
and Anderson, 2010). (c) NiO nanopetals. Source: Reproduced with
permission from C Elsevier (Lee et al., 2011). (d) V2 O5 nanoporous
network. Source: Reproduced with permission from C ACS Publi-
cations (Saravanakumar, Purushothaman, and Muralidharan, 2012).
ions are inserted/extracted from the polymers’ backbones
(Figure 10) (Rudge et al., 1994).
Unlike metal oxides, entire polymer structures are exposed
to the doping of ions, which grants high capacitance. For
example, PANI synthesized by Zhou et al. (2005) exhibited
a capacitance of 609 F/g. However, the fast charge/discharge
nature of supercapacitors can damage the polymer structure

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 Electrochemical Supercapacitors for Energy Storage and Conversion 9

Polymer
backbone
+ −
− + + +
− P-doping − + −
+ − +
+ −
e− −
− −+
+ −+ +
−
+ P-dedoping + − +− −
− + +
− +−
+
Current − + Current − + −
collector Undoped Solution collector P-doped Solution
plate conducting + Cations plate conducting
polymer − Anions polymer film
(a) film

− + +
+ −
− N-doping −
+ + −
+ + −
− +
e− − +
− + −
− + −
+ N-dedoping − −
+ − − + +
+ +−
− + −
Current Current
collector Undoped Solution collector N-doped Solution
plate conducting + Cations plate conducting
polymer − Anions polymer
(b) film film

Figure 10. Illustration of conducting polymer’s charging/discharging mechanism with two doping states: (a) p-doping and (b) n-doping.
Source: Reproduced with permission from C Elsevier (Rudge et al., 1994).

through swelling and cracking, which shortens the poly-
mers’ overall life cycle. To improve the life cycle, conduc-
tive polymers and carbon supports are combined. Wang
et al. (2009a) demonstrated the improved capacitance by
comparing PANI only (216 F/g) to graphene oxide (GO)-
doped PANI (531 F/g). Figure 11 displays PANI arrays on
GO sheet and PPY on graphene by Xu et al. (2010) and
Davies et al. (2011).
3.2 Electrolyte
Apart from electrodes, electrolytes also play a key role
in supercapacitor performance. Electrolytes directly affect
the cell’s operational voltage window and its resistance.
Energy density is proportional to the square of the voltage
window, while the ionic resistivity is inversely proportional
to the cell’s power capability (Burke, 2007). Therefore,
careful selection of the most fitting electrolyte is crucial in
constructing high performing supercapacitors. Three types
of electrolytes are currently available for supercapacitors:
aqueous, organic, and ionic liquids (ILs). Table 2 lists the
density, ionic resistivity, and voltage window for various
electrolytes and Figure 12 visually illustrates the effects
of the different electrolytes on energy density and specific
capacitance. The following sections discuss each electrolyte
type in detail.
3.2.1 Aqueous electrolyte
Aqueous electrolytes are primarily adopted in research stages
for their low cost and abundance. H2 SO4 , KOH, and potas-
sium chloride (KCl) are the common aqueous electrolytes
bearing the merits of easy handling in an open environment
and low ionic resistivity. The diverse variety between acid,
base, and neutral electrolytes offer researchers many solu-
tions for enhancing performance. For example, switching
from H2 SO4 to KOH for nickel oxide electrodes could
increase the specific capacitance from 16 to 155 F/g because
nickel oxide will undergo a Faradaic reaction in OH− ion-
rich environment (Srinivasan and Weidner, 2000). Unfortu-
nately, aqueous electrolytes’ commercial success was stinted
due to their narrow voltage window (only 1.2 V). Increasing
the voltage window evokes water decomposition, that is,
oxygen/hydrogen evolution, and builds pressure within the
system, which would ultimately result in rupturing the cell.
Moreover, strong pH acid–base can induce corrosion on
metals (e.g., nickel and aluminum). Chloride ions from KCl
can also tamper with these metals.

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10 Electrochemical Storage

(a) (b)

300 nm
1 μm

Figure 11. SEM images of (a) PANI arrays on GO sheet. Source: Reproduced with permission from C ACS Publications (Xu et al., 2010).
(b) PPY deposited on graphene. Source: Reproduced with permission from C ACS Publications (Davies et al., 2011).

Table 2. Density, ionic resistivity, and voltage window for various Ionic
electrolytes. 140 liquids
Organic
Electrolyte Density Resistivity Cell Voltage electrolytes
4V
(g/cm3 ) (Ω cm) (V) 120 3V
KOH 1.29 1.9 1 Graphene-based Aqueous
100
Sulfuric acid 1.2 1.35 1 electrodes electrolytes
E* (Wh/kg)

Propylene carbonate 1.2 52 2.5–3 Other 2V

Acetonitrile 0.78 18 2.5–3 80 RuO2
carbonaceous
Ionic liquids 1.3–1.5 125 (25◦ C) 28 (100◦ C) 4 3.25 materials
60
Source: Reproduced with permission from C Elsevier (Burke, 2007).
40 MnO2
hybrids
1V
3.2.2 Organic electrolyte 20
Carbonaceous
materials
Commercially available supercapacitors employ organic 0
200 400 600 800 1000
electrolytes such as acetonitrile and propylene carbonate CG (F/g)
(PC) because of their wide operating voltage windows (0
to 2.2–2.7 V). The broad voltage range definitely raises Figure 12. Energy density of a two-electrode cell as a function of
the energy density to the standard of commercial demand. voltage window and specific capacitance of various electrolytes.
Acetonitrile is more favorable than PC because it only bears Source: Reproduced with permission from C ECS Publications
one third of PC’s ionic resistivity. However, acetonitrile’s (Pope et al., 2013).
toxicity and flammability are an issue for safety. Overall,
aging (i.e., degradation) of carbon electrodes are observed
when exposed to organic electrolytes. The decomposition
of organic electrolyte blocks the pores of the electrodes, However, the major drawback of ILs is the inadequate
reducing the capacitive performance and cyclic stability ionic conductivity compared to the other two types of
(Azais et al., 2007). electrolytes. The conductivity can be improved by heating
ILs to 125◦ C, but this raises other design challenges.
El-Kady et al. (2012) prepared laser-scribed graphene
3.2.3 Ionic liquids (ILs)
(LSG) supercapacitors and characterized the products
ILs are composed of solvent-free molten salts in liquid with aqueous, organic, and IL electrolytes. Figure 13
form at room temperature, which is due to their low melting summarizes the results, where IL-based LSG superca-
temperatures. This type of electrolyte is nontoxic and pacitors surpass both organic- and aqueous-based devices
nonflammable and provides the widest voltage window (0 to with respect to both energy density and power density.
3–5 V), without thermal or chemical instability (Galinski, Although the performance of ILs is promising, several
Lewandowski, and Stepniak, 2006). ILs can also be heated challenges, including high costs, lie ahead for commercial
up to 300◦ C without any vaporization (Burke, 2007). applications.

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 Electrochemical Supercapacitors for Energy Storage and Conversion 11

10−2 3.4 Current collectors

4 V/500 μAh
Energy density (Wh/cm3)

LSG-EC, lonic liquid

10−3
Li thin-film battery The majority of energy storage devices require current
2.75 V/44 mF
collectors that complement performance because of the
commercial AC-EC LSG-EC, TEA-BF4/CH3CN active materials’ inadequate conductivity. Normally found
10−4 Organic electrolyte
LSG-EC
within the cell, a current collectors’ role is to transport
LSG-EC Aqueous electrolyte current from electrodes to external loads. Therefore, they
−5 Gelled electrolyte
10 must be electronically conductive and resilient in the cell
3 V/300 μF
Al electrolytic capacitor environment withstanding chemical abuse from electrolytes.
10−6 With these caveats, aluminum, steel, and iron are popular
current collectors. Moreover, coating active materials
10−3 10−2 10−1 100 101 102
directly onto current collectors can provide firm molecular
Power density (W/cm3)
contact, which amplifies the performance by minimizing
the interfacial resistance between active layers and current
Figure 13. Illustration of energy density of two electrode cell as
a function of voltage window and specific capacitance of various collectors (Wu et al., 2009). Unfortunately, owing to the
electrolytes. Source: Reproduced with permission from C AAAS extensive cycling of the supercapacitors and the physical
Publications (El-Kady et al., 2012). disorientation of the active materials, a determination
between the active material and the collector may occur,
leading to high resistance. To address this, polymeric
3.3 Separators binding agents (i.e., NafionR and polytetrafluoroethy-
lene) are supplemented to inhibit the dislocation of active
While many advances have been established in improving materials from the current collectors. In addition, it is also
performance of supercapacitor electrodes, little research important for current collectors to dissipate heat generated
has been initiated in developing well-engineered separators. within the cell. As such, aluminum is commonly used.
Separators can negatively influence the performance of
supercapacitors because poorly designed separators can
induce additional resistances in the cell. This can, in 3.5 Sealants
the worst case, short circuit the cell. Considerations in
selecting adequate separators for supercapacitors include Proper sealing in cell assembly is vital to avoid performance
the following: loss of supercapacitors. A sealants’ function is to prevent
foreign contaminants (i.e., water and air) from entering the
1. Nonconductive (prevent electron transport between elec- cell. The impurities can provoke electrolyte degradation and
trodes) surface oxidation on electrodes, resulting in loss of life
2. Electrolyte ion permeable with minimum ionic resis- cycles. For commercial applications, multiple supercapaci-
tance tors are linked in series to supply a high voltage window,
3. Chemical resistance to electrolytes and electrode mate- but this connection requires sophisticated sealing. Improper
rials sealing of cells in series can cause shunt resistances between
4. Mechanical resistance to pressure and volume changes neighboring cells. Shunt resistances can reduce the overall
such as swelling efficiency of the device by providing alternative current
5. Easily wetted by electrolytes paths (Kotz and Carlen, 2000). For sealants, polymer mate-
rials are generally selected for their dimensional flexibility,
Natural materials, such as glass, cellulose paper, and mechanical stability, moisture resistance, and electrical insu-
ceramics, were originally used as separators in the infantile lation.
stages of supercapacitor development. Nevertheless, evolu-
tion of polymer-based separators dominated the separator
markets because of their low cost, amazing flexibility, and 4 SUPERCAPACITOR PERFORMANCE,
high porosity. Polymer separators can be classified into two TESTING, AND DIAGNOSIS
categories: fibrous structure and monolithic network with
defined pores. Figure 14 illustrates the two separator struc- Performance evaluation of supercapacitor components and
tures. It is worth pointing out that Shulga et al. (2014) the full cell/stack is vital in optimizing the technology. The
successfully utilized GO films as separators for supercapac- major parameters used to quantitatively evaluate the super-
itor applications. capacitor’s performance are capacitance, energy and power

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12 Electrochemical Storage
(a)
S370 2.00 kV 10.2 mm x 500 ESED 20 Pa 9/19/2011
Figure 14. SEM images of (a) Millipore JVWP separator with fibrous structure and (b) GE Osmotics K50CP01300 separator with
monolithic/defined pores. Source: Reproduced with permission from C ECS Publications (Cameron, 2012).
density, internal resistance, and cycle stability. All methods
used to obtain these parameters are electrochemical ones, as
described.
4.1 Electrochemical cell design for performance
testing
For characterization of supercapacitors, testing apparatus
are classified into two configurations: three-electrode and
two-electrode systems. The former configuration focuses on
the evaluation of electrode materials by screening electrode
materials with minimal amounts of the active material. The
latter system, resembling the structure of fully assembled
supercapacitors, evaluates the performance of a cell under
less-than-ideal conditions.
4.1.1 Three-electrode system
The three-electrode system consists of a working elec-
trode, reference electrode, and counter electrode, which
are all connected to a potentiostat. This potentiostat is
used to control the electrode potential while recording
the change in electrode current with potential, or control-
ling the current passing through the electrode and then
recoding the change in electrode potential with current.
Figure 15 illustrates the three operating components: (a)
working electrode, (b) reference electrode, and (c) counter
electrode.
In Figure 15, the working electrode is normally prepared
by coating the active material onto the surface of a stable
electrode, that is, glassy carbon or platinum metal. The
active material is dispersed in a selected solvent (e.g., water,
ethanol, or isopropanol) until an ink with a uniform disper-
sion is acquired. Carbon supplements are integrated into
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(b)
100 um
Potentiostat
Reference electrode
V I (Ag/AgCl)
Working electrode (recycled
carbon fibre sheet)
Counter electrode
(platinum rod)
Electrolyte
(a) (b) (c)
Figure 15. Schematic drawing of a three-electrode system: (a)
working electrode, (b) reference electrode, and (c) counter elec-
trode. Source: Reproduced with permission from C Elsevier (Pang
et al., 2012).
this ink if the active material is conductively deficient. A
desired amount of ink is then pipetted onto the surface of
prepolished electrodes. Often, a small amount of polymeric
binder (e.g., Nafion) is incorporated following the ink depo-
sition to prevent the ink from diffusing away into the elec-
trolyte. A reference electrode establishes a base potential
in the three-electrode system by acquiring a fixed poten-
tial. There are many different types of reference electrodes
with discrete fixed potentials. Normal hydrogen electrode
(NHE), silver chloride electrode (Ag/AgCl), and saturated
calomel electrode (SCE) are a few common reference elec-
trodes. Lastly, a counter electrode, also known as an auxil-
lary electrode, balances the reaction that is occurring in
the working electrode by adjusting its potential. For this
 Electrochemical Supercapacitors for Energy Storage and Conversion 13

purpose, highly conductive yet inert materials such as plat- techniques, cyclic voltammetry (CV) and galvanos-
inum meshes or graphitic rods are employed as the reference tatic charge–discharge (GCD), are used to evaluate the
electrodes. capacitance of materials.

4.1.2 Two-electrode system 4.2.1 Cyclic voltammetry

Figure 16 illustrates a two-electrode system designed by
Tsay, Zhang, and Zhang (2012). In a two-electrode system of
Figure 16, two active electrodes are included: a cathode and
an anode. A separator is placed between these electrodes to
avoid short circuits. Metal plates as current collectors adjoin
the two electrodes and their separator. Lastly, a metal casing
with three screws applying pressure evenly encloses the cell.
Before testing, the cell is submerged in a vessel filled with
electrolyte, and then, it is dried in a vacuum oven to remove
any trapped air. The anode and cathode are synthesized by
creating inks/pastes from the active material(s). The inks
are subsequently pasted or sprayed onto the stable electrode
sheets (e.g., carbon papers or carbon fibers) and trimmed to
specified dimensions. To measure the potential of individual
electrodes, a reference electrode can be installed in the cell;
however, this may give extra design challenges.
CV assesses quantitative and qualitative data relating to the
electrochemical phenomena occurring in the active materials
of the working electrode. This technique applies a potential
to the working electrode, with respect to the reference elec-
trode’s fixed potential, which linearly sweeps back and forth
between the two predefined potentials. The potential range
is limited by the electrolyte’s operating stability. Scanning
the potential range yields a time-dependent current and plot-
ting this current (I) against the scanned potential (E) graphs a
cyclic voltammogram (CV) curve for capacitance diagnosis
(Figure 17).
(c)
(b)

4.2 Capacitance (C) I (mA)

Capacitance (C), which was briefly introduced in Section

2, is one of the key performance parameters evaluated
(a)
during the analysis of supercapacitors. It is measured
in (SI unit) farads (F). Specific capacitance (Cs ), which E (V)
is the capacitance normalized by the mass of the active
material, is calculated to compare the performance between Figure 17. Cyclic voltammogram curves of (a) ideal capacitor, (b)
electrodes with different masses. Two electrochemical EDLC, and (c) pseudocapacitive materials.

Reference electrode

Current collectors
End plate (metal)

Separator
Cell plate (Teflon)

Pressure coin

Cell plate (Teflon) Electrodes

End plate (metal)

Figure 16. Illustration of a two-electrode system. Source: Reproduced with permission from C Elsevier (Tsay, Zhang, and Zhang, 2012).

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14 Electrochemical Storage

Theoretically, a rectangular CV, shown in Figure 17a
resembles an ideal capacitor; however, EDLC materials do
not behave ideally, resulting in a deformed rectangular shape
as displayed in Figure 17b. Faradaic reactions from pseudo-
capacitors output redox peaks as seen in Figure 17c. From
these curves, capacitance can be appraised. Capacitance can
be calculated as (Kim, Chabot, and Yu, 2013)
idV
∫ responsive potential with respect to time. Generally, the
C= , (2)
2Vs ΔV
where ∫ idV is the integrated area under the CV curve, Vs
the potential scan rate, and ΔV the potential range. Dividing
the capacitance by the mass of the active materials gives the
specific capacitance (Cs ) as
C
Cs = , (3)
m
where C is the calculated capacitance from Equation (2)
and m the mass of the active material. Moreover, potential
scan rates have significant effects on measured capacitances.
At lower rates (e.g., 0.005 mV/s), CV curves exhibit near
ideal capacitive behavior with a rectangular shaped curve, as
shown in Figure 18.
However, increasing scan rates distort the ideal rectangular
CV curve. At extreme scan rates, the electrochemical kinetics
cannot contend with the rapid change in potential. Consid-
ering the sluggish transportation of ions and the underutilized
micropores in active materials, a decline in performance is to
be expected. This consequence is commonly observed with
pseudocapacitive materials due to their slow Faradic reac-
tions in the mid of fast scan rates.
4.2.2 Galvanostatic charge–discharge (GCD)
In addition to CV, GCD is an alternative method to measure
the capacitance of the material. The GCD technique applies
a constant current density (e.g., A/g) and measures the
working electrode is charged to a preset potential and the
discharge process is then monitored to assess the capaci-
tance. Figure 19 illustrates GCD plots for EDLC and pseu-
docapacitive materials.
From Figure 19, it can be seen that similar to CV plots,
the two materials demonstrate dissimilar responses. EDLC
materials charge and discharge linearly, while the nonlin-
earity of pseudocapacitive materials is due to the redox reac-
tions. Because of this discrepancy, each type of material has
its unique equation to calculate its capacitance. For EDLC,
the slope of the discharging section is utilized, which gives
(Stoller and Ruoff, 2010)
I
C= , (4)
dV∕dt
where C is the capacitance of the material, I the applied
current, and dV/dt the slope of the discharging GCD curve.
For pseudocapacitive material, an altered form of the
equation without the slope is employed (Kim, Chabot, and
Yu, 2013), which gives

(Δt)(I)
C= , (5)
ΔV
4
where Δt is the total discharge time, I the applied current,
and ΔV the potential difference at the discharging phase.
Specific current (A/g)

0
Charging
(a)
−2 Discharging
E (V)

50 mv/s (b)
−4 20 mv/s
5 mv/s
−6
−0.3 −0.2 −0.1 0.0 0.1 0.2 0.3
Potential vs (H+|H2) (V)
t (s)
Figure 18. Cyclic voltammograms (CVs) of ordered graphitic
mesoporous carbon at different scan rates. Source: Reproduced with Figure 19. Galvanostatic charge–discharge plots of (a) EDLC and
permission from C Elsevier (Zhang et al., 2009). (b) pseudocapacitive material.

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 Electrochemical Supercapacitors for Energy Storage and Conversion 15

To compute the specific capacitance, Equation (3) can again
be used. Similar to the dependence on scan rates, current
density also affects capacitance. A high current density leads
to a rapid discharge where the utilization of the materials’
properties is hindered and the electrochemical kinetics is
limited. On the other hand, an extremely low current density
induces leakage current and self-discharge that is discussed
in detail in Section 4.6.
an increased RESR , which can reduce the overall power
performance. The maximum power can be averaged by
applying a lucid relationship between specific energy density
and average specific power density, which gives
ED
PDaverage = , (8)
Δt
where Δt is the rate of discharge of the cell.

4.3 Energy and power densities 4.3.3 Ragone plot

Assessing the energy and power densities of a supercapacitor
is imperative in diagnosing its deliverable performance for
real-life applications. Both CV and GCD techniques can
determine both energy and power densities.
4.3.1 Energy density
Specific energy density (watt hour per kilogram) is expressed
by
1 1C
ED = Cs (ΔV)2 = (ΔV)2 , (6)
2 2m
where Cs is the specific capacitance from CV or GCD
techniques and ΔV the operating potential range. The latter
part of the equation correlates specific energy density to
the capacitance and mass of active materials. The squared
potential range indicates that the operating voltage window
significantly dictates the energy density. As discussed in
Section 3.2, the electrolyte determines the operating poten-
tial range. Research is continuing to direct its resources
toward organic electrolytes and ILs to widen the potential
window and ultimately resolve the supercapacitors’ lack of
a high energy density. However, moving toward electrolytes
that possess a wider voltage window will give a net reduction
in power density.
Plotting the specific power density against its specific energy
density generates a Ragone plot (as shown in Figure 1),
which provides an overview of the performance in terms
of energy and power. Actually, Figure 1 illustrates Ragone
plots of several well-known electrochemical energy storage
devices, including supercapacitors. A trend of diminishing
power density with increasing energy density is evident with
all of the devices. Similarly, supercapacitors also conform
to this trend and encounter a challenge where increase
in the maximum energy density lowers its maximum
power density. Figure 20 shows that for supercapacitors,
maximum energy density can be improved using organic
electrolytes with a wider operating voltage; nonetheless,
organic electrolyte-based supercapacitors will yield lower
maximum power densities than aqueous electrolyte-based
supercapacitors. This inverse relationship between the
two densities emphasizes that optimization of cell design,
including the electrolyte, is necessary in improving both
power and energy of storage devices.
107
1 μm
10 μm
106 Aqueous
Maximum power density (W/I)

𝜎 = 0.8 S/cm

105
4.3.2 Power density Organic 100 μm
𝜎 = 0.016 S/cm

Specific power density (Watt per kilogram) defines how 104

quickly a device can deliver energy under a constant current
density to external loads. Maximum specific power density 103
is calculated as
(ΔV)2 1000 μm
PDmax = , (7) 100
4mRESR

where ΔV is the potential range, m the mass of the active 10

materials, and RESR the equivalent series resistance (ESR) 0.01 0.1 1 10 100
within the cell. The ESR includes ohmic resistance of the Maximum energy density (Wh/I)
electrolytes, resistances from the cell design, and other resis-
Figure 20. Calculated maximum achievable power density and
tances. This parameter is explained in a later section. Using
energy density of two capacitors in aqueous and organic elec-
organic or ILs as electrolytes can widen the voltage window; trolytes. Source: Reproduced with permission from C Elsevier
however, their inferior ionic conductivities contribute to (Kotz and Carlen, 2000).

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16 Electrochemical Storage

4.4 Internal resistances 4.4.2 Electrochemical impedance spectroscopy (EIS)

Most supercapacitors do not exhibit ideal capacitive EIS can also be used to measure and compute the ESR. More-
behavior due to internal resistances. Comprehending the over, EIS also provides further insight about other electrical
internal resistances of supercapacitors offers in-depth characteristics. In this method, an alternating current (AC)
knowledge about their power performance. The principal with small magnitude is supplied to supercapacitors over a
resistance is the ESR, which involves resistances of cell frequency range 0.01 Hz to 1 MHz. The response is charted
components, for example, electrolyte resistance and contact on a Nyquist plot, which plots imaginary resistance (Z′′ )
resistance between current collectors and electrodes (Zhao against real resistance (Z). From the Nyquist plot, the inter-
et al., 2010; Conway, 1999). ESR directly affects the section of the impedance curve at the x-axis corresponds
power delivery of a cell, as shown in Equation (7). It to the ESR. Figure 22 shows that both (a) ideal capacitors
restricts the rate at which supercapacitors can be charged and (b) supercapacitors possess the same ESR. However, a
and discharged, leading to power reduction and energy supercapacitor’s impedance response deviates from the ideal
capacitor at low frequencies. This deviation is caused by the
dissipation. Two methods, which can determine ESR,
equivalent distributed resistance (EDR), which accounts for
include GCD and electrochemical impedance spectroscopy
the ionic resistance of electrolyte within the pores of the elec-
(EIS).
trodes (Kotz and Carlen, 2000; Conway, 1999). Therefore,
increasing the number of pores in an active electrode will
4.4.1 Galvanostatic charge–discharge (GCD) induce an elevated EDR.

As mentioned in a previous section, the GCD technique

monitors the response in potential with respect to time during
4.5 Cycle stability
charging and discharging. At the initial discharge, a sudden
Another important property of supercapacitors is their cycle
drop in potential is observed that is referred as the IR drop,
stability. Commercial supercapacitors are well recognized
as shown in Figure 21.
for possessing a merit of long life cycles in which they would
Calculating the ESR requires dividing the IR drop (e.g., the
operate at full capacity, even after half a million cycles.
change in potential at initial discharge) by twice the current
At lab-scale testing, 1000 to 10,000 cycles are generally
applied. This method can be employed for three-electrode
systems as well as for two-electrode systems, including fully
assembled supercapacitors.
Frequency
High → Low

(a) (b)
1.4
Charging-discharging voltage (V)

1.2
V˚
−Z imaginary resistance

1.0 2IRESR

0.8 V ˚ − IRESR

0.6
Charging Discharging
0.4
𝛿
0.2

0.0
−1.0 1.0 3.0 5.0 7.0 9.0 11.0
ESR EDR
Charging-discharging time (s)
𝜑

Figure 21. Charge–discharge curves recorded using a symmetric Z real resistance

supercapacitor cell with a geometric area of 4.0 cm2 for each elec-
trode in 0.5 M Na2 SO4 aqueous solution at ambient conditions. The Figure 22. Schematic representation of the Nyquist plot of (a) an
IR drop is highlighted in blue box. Source: Reproduced with permis- ideal capacitor and (b) a supercapacitor. Source: Reproduced with
sion from C Elsevier (Ban et al., 2013). permission from C Elsevier (Kotz and Carlen, 2000).

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This article is C 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces112

100
100
80
Capacity retention (%)
80
Capacity retention (%)
60 CNT-sponge at 10 V/s
60
40 min MnO2-CNT-sponge at A/g
40 40
20
20
0 2000 4000 6000
Cycle number
0
0 20 000 40 000 60 000
Cycle number
Figure 23. Performance retention versus cycle number for CNT-
sponge and MnO2 -CNT-sponge. Source: Reproduced with permis-
sion from C ACS Publications (Chen et al., 2011).
conducted for investigating the cell’s cycle durability. One
cycle would equal to one charge/discharge cycle at a constant
current density. As charging and discharging are required
for the test, GCD method is employed. Extensive cycling
degrades the electrodes and induces corrosion in the cell’s
components, resulting in capacitance reduction and rise in
ESR. Therefore, comparing the initial and the final perfor-
mance from the cycle testing provides a foresight on how
the material will perform in real applications where it will be
utilized to extreme amounts of cycles. In addition, the type of
material impacts the cycle durability. EDLC materials with
static storing mechanism tend to have finer stability than
pseudocapacitive materials. For example, when compared to
a CNT-sponge’s cycle stability, Chen et al. (2011) illustrated
higher rates of degradation of pseudocapacitive MnO2 -
deposited CNT-sponge as cycling advanced. Figure 23
shows that a 2% drop in performance retention is visible
from the CNT-sponge over the course of 100,000 cycles,
whereas a 4% reduction in capacitance is evident from
MnO2 -CNT-sponge from a mere 10,000 cycles. If the MnO2
composite sponge was subjected to 100,000 cycles, severe
reduction in performance would be apparent.
4.6 Self-discharge
All capacitors, including supercapacitors, suffer from capac-
itance loss because of self-discharge. This phenomenon
involves the gradual decaying of voltage in a fully charged
cell due to a constant (leakage) current in an open-circuit
cell. The self-discharge reduces the deliverable power and
energy from supercapacitors; thus, it is considered a major
Handbook of Clean Energy Systems, Online C 2015 John Wiley & Sons, Ltd.
This article is C 2015 John Wiley & Sons, Ltd.
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DOI: 10.1002/9781118991978.hces112
Electrochemical Supercapacitors for Energy Storage and Conversion 17
2.5
2.0
Voltage across capacitor
1.5
1.0
Charged to 2.4 V
Charged to 2 V
8000 10 000 0.5 Charged to 1.55 V
80 000 10 0000
0
0 200 400 600 800 1000
Minutes
Figure 24. Self-discharge of carbon-based supercapacitors in
organic electrolyte at different charged voltages. Source: Repro-
duced with permission from C Elsevier (Ricketts and Ton-That,
2000).
issue for commercial applications. One reason behind self-
discharge is the thermodynamic instability in the charged
state, implying that the charged potential may surpass the
thermodynamic limitation of the electrolyte, resulting in a
Faradaic decomposition of the solution. Another reason for
the self-discharge is that the ions redistribute themselves
within the pores of the electrodes. Alternatively, fast charging
behavior of the supercapacitor does not allow sufficient time
for the entirety of pores to be thoroughly saturated with ions.
Once charging is completed, the excess ions in the pores will
be allocated to adjacent vacant pores, uniformly distributed
across the electrode. This redistribution results in voltage
decay. In order to investigate self-discharge, supercapacitors
are first fully charged, then idled to endure self-discharge.
The voltage drop is monitored and calculated. The measure-
ment duration can take between a few minutes to a couple
of weeks. Figure 24 is an example of self-discharge in a
carbon-based supercapacitor. Using organic electrolytes and
assembling cells in moisture-free environment can eliminate
the possibility of self-discharge originating from Faradaic
reactions (Zhang et al., 2011).
5 ASSEMBLY AND MANUFACTURING
OF SUPERCAPACITORS
Electrodes and electrolytes are the largest contributors to
the performance of supercapacitors. The fabrication of each
18 Electrochemical Storage

component is diverse due to the large variety of materials
made available. Different supercapacitor designs allow more
options for manufacturing and assembling of the devices.
5.1 Supercapacitor designs
Coin cells, cylindrical cells, and pouch cells are the three
prevalent supercapacitor designs used commercially. Coin
cell design as illustrated in Figure 25a is suitable for
supplying energy to small devices.
In the assembly of coin cell, two electrodes and
electrolyte-saturated separators are assembled in a conduc-
tive metal casing. An insulating polymer, such as Teflon,
is added between the casings to prevent electrolyte from
leaking and the cell from shorting. When the assembly is
completed, the metal casing can be crimped under high
pressure to seal the cell. However, excessive pressure
may induce a short circuit within the cell. The coin cell
design requires thin electrodes with low active material
mass; hence, alternative designs are preferable for bulkier
supercapacitors.
The cylindrical cell design is widely employed in
commercial supercapacitors. As shown in Figure 25b,
the design consists of rolled layers of electrode sheets
with separator sheets. Then, these layered sheets are fitted
into a cylindrical metal casing to reinforce its mechanical
durability. Subsequently, current collector tabs are soldered
onto the rolled sheets. Finally, electrolyte is injected in the
cell followed by sealing of the metal casing. As a safety
precaution, a one-way safety vent must be installed in
each device to release any pressure accumulation within
the cell.
Figure 25c shows an alternative design that also utilizes
layer-by-layer sheets of electrodes and separators, called a
pouch cell. The pouch cell design is effective in stacking
multiple electrodes provided that each soldered current
collector tab is correctly connected to the proper corre-
sponding terminals in the cell. These components are
assembled within polymer bags, which are flexible in
accommodating undesired volume expansions. Moreover,
this simple design minimizes the number of components
required in the cell, resulting in thin devices with low ESR
and excellent performance. The flexibility and slim design

Positive electrode
Stainless steel cap Separator
Negative electrode
MWNT buckypaper

Teflon ring

Nomex separators
with electrolyte Polymer-based cell case

MWNT buckypaper

Stainless steel cap

(a) (c)

Separator

Positive electrode
Separator
Negative electrode

(b)

Figure 25. Schematic of (a) coin cell design. Source: Reproduced with permission from CACS Publications (Hu et al., 2010). (b) Cylin-
drical cell design. (c) Pouch cell design.

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This article is C 2015 John Wiley & Sons, Ltd.
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DOI: 10.1002/9781118991978.hces112
 Electrochemical Supercapacitors for Energy Storage and Conversion 19

grant pouch-cell supercapacitors more spatial freedom than 5.3 Stacking of supercapacitors and stack
coin cells and cylindrical cells. performance

5.2 Component fabrication Stacking of supercapacitors allows multiple cells to operate

collectively, and thus exceed the limits of a single cell.
The fabrication techniques of commercial supercapacitors When individual cells are connected in series, the pack can
are normally trade secrets that manufacturers base their supply operating voltage up to 60 V. Supercapacitor packs are
sole success on. On the other hand, laboratory techniques often assembled in metal casings (i.e., modules) that provide
for fabricating electrodes, electrolytes, membranes, and sturdiness at the cost of additional weight and volume. To
current collectors are well established and made public. quantify its performance, capacitance in series is expressed
These processes may resemble some of the commercial as
techniques. 1 1 1 1 ∑n
1
= + + ···= , (9)
Electrode fabrication requires preparing a paste from Cstack C1 C2 C3 i
C i
mixing active materials (e.g., AC) and binding agents (e.g.,
polyvinylidene fluoride) in solvents (e.g., isopropanol). If identical cells are assumed, then Equation (9) can be
Additional sonication homogenizes the paste. For the simplified to
C
fabrication of electrodes, the prepared mixture can then be CStack = i , (10)
processed via one of two methods. The paste can be spread n
onto a plate, hot pressed, and then dried into thin sheets or where n is the number of cells. Voltage in a stacked series
the paste can be diluted into a slurry with more solvent and can be expressed similarly as
sprayed onto current collectors.
Compared to the electrode fabrication, electrolyte prepa- ∑
n

ration is fairly simple. However, special conditions need Vstack = V1 + V2 + V3 · · · = Vi , (11)

to be met depending on the electrolyte type. With safe
handling of strong acids/bases and neutral salts, aqueous
electrolytes (e.g., H2 SO4 and KOH) can be simply prepared
at ambient conditions. Conversely, organic electrolyte (e.g.,
acetonitrile and polycarbonate) and ILs [e.g., 1-ethyl-3-
methyl imidazolium tetrafluoroborate (EMIMBF4 )] must
be formulated in a moisture-free environment (e.g., glove
box) to avoid water-based contamination of the electrolyte.
Presence of water molecules in organic and ILs stimu-
lates gas evolutions at high operating voltages, which leads
to an increase in cell pressure and, consequently, safety
concerns.
In terms of separators, a wide range of materials from
filtration papers to polymer membranes are used. Electrolyte
ions must be permeated through separators, yet the separators
should be electrically insulating. Ideally, separators should
be saturated with electrolyte before the assembly of the
cell. For better contact, polymer separators are sandwiched
between the electrodes, hot-pressed, cooled down, and then
soaked with electrolyte.
Nonprecious metal foils (e.g., aluminum and stainless
steel) that are chemically resistant and mechanically durable
are extensively used in commercial current collectors. These
foils are etched by acids to eliminate any impurities and to
increase the surface area. As mentioned earlier, electrode
pastes can be directly applied to current collectors. However,
poorly adhered active materials on current collectors will
suffer from high resistances and, as a result, performance
losses.
i
with identical cells assumption:
VStack = nVi , (12)
Lastly, the energy density of a pack can be expressed as
1 1
EStack = C (V )2 = CStack n(Vi )2 , (13)
2 Stack Stack 2
This equation states that the energy density of a stacked cell
is equivalent to the energy density of a single cell multiplied
by the number of cells. Stacking the cell increases the perfor-
mance, and it also creates complications that are not present
in a single cell. Although cooling systems are built within
modules, nonuniform heat distribution in the stack may
impair physical properties and reduce cycle durability. More-
over, despite the fixed stack voltage of modules, the potential
difference across each cell can differ. The discrepancy
between each capacitor can actually overcharge/discharge
individual cells, leading to electrode degradation, elec-
trolyte decomposition, and gas evolution within the packs.
Charging the cells in parallel and discharging in series can
be implemented as a potential solution; however, tailoring
such configuration would be a challenge.
5.3.1 Bipolar electrode configuration
An alternative stacking design involves a bipolar electrode
configuration, as shown in Figure 26. The bipolar electrode

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This article is C 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces112
20 Electrochemical Storage

Casing can be operational within minutes of charging. Furthermore,

E1 E2
− +
A B A B has recently been replaced with smaller supercapacitors.
+ − + − The controller can now be charged instantly. Addition-
: Bipolar electrodes
: Electrolyte
Figure 26. A schematic of bipolar electrode configuration.
arrangement effectively minimizes the volume of the stack
and circumvents additional connections between cells,
lowering the internal resistance. Electrodes are coated on
both sides of each plate, serving as bipolar electrodes.
The plates are spaced out in the assembly, whereas the
gap between each electrode is filled with electrolyte. The
bipolar plates must prohibit the transfer of electrolyte ions;
otherwise, the lack of electrolyte insulation will trigger
short circuits. Sealants are often applied to ensure the
isolation of electrolytes. The primary drawback of the
bipolar arrangement is inadequate heat distribution within
the cells. Therefore, implementation of a cooling system is
necessary.
6 APPLICATIONS
For decades, rechargeable lithium ion batteries have
dominated the energy storage market. However, with
the increasing demand of improved energy storage for
manifold applications from portable electronics to HEVs,
supercapacitors are recognized for their high power density,
rapid charge/discharge capability, and long life cycle. New
technologies are being developed to optimize the perfor-
mance and simultaneously reduce the cost of production.
The steady advance in supercapacitor research has opened
opportunities for real-world applications. This section
discusses the existing markets for supercapacitors and
prospective applications.
users can disconnect the screwdriver at any time while it is
charging without damaging its components (Conner, 2007).
In addition to household tools, Maxwell Technologies, a
supercapacitor manufacturer, collaborated with Celadon to
develop supercapacitor-powered remote controllers. The
controller originally operated with two AAA batteries but
ally, the life span of the supercapacitors can outlast the
remote controllers (Wald, 2013). Recently, Sam Beck from
Blueshift constructed portable speakers equipped with
supercapacitors. The speaker is fully charged within 5 min
and operates up to 6 h of playback at full volume (Denison,
2013). Figure 27 illustrates the speaker, which is currently
available for purchase.
6.2 Industrial application
For industrial applications, supercapacitors are generally
employed as an emergency backup power source because
of their instant discharging capability. In the event of a
power failure in computer components, hospitals, and facto-
ries, supercapacitors can assure a supply of uninterrupt-
able energy to prevent catastrophic failures until the power
is restored. For example, implementing supercapacitors in
solid-state drives can prevent the deletion of data due to
power disruption (Cellergy, 2012). Also, supercapacitors are
implemented as an emergency power source in airplanes.
An array of supercapacitors is installed in the Airbus A380
to immediately power the emergency doors in any circum-
stance (Simon and Gogotsi, 2008). Unlike batteries, inert

6.1 Consumer application

One of the first consumer products was the cordless screw

driver solely powered by supercapacitors. This tool from Figure 27. An image of a supercapacitor-powered speaker with
Coleman Company Inc. cannot supply the same capacity charging time of 5 min and playback time of 6 h. Source: Repro-
as lithium-ion battery-based screw drivers; nonetheless, it duced with permission from CBlueshift (Beck, 2013).

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DOI: 10.1002/9781118991978.hces112
 Electrochemical Supercapacitors for Energy Storage and Conversion
carbon-based supercapacitors are stable in extreme condi-
tions. This advantageous property created an opportunity for
FastCAP systems to develop supercapacitor-powered drills
for oil, petroleum, and geothermal exploration. The drill was
fully functional at 150◦ C without accompanying overcharge
(FastCAP, 2013). Furthermore, Ioxus developed a tech-
nology that conjoins supercapacitor and battery together to
harness the advantages from each energy storage technology.
The hybrid system can supply more energy than superca-
pacitors and more power than batteries. Lastly, a Japanese
company, JSR Micro, constructed these hybrid devices to
serve as a backup power source for medical imaging equip-
ment (Patel, 2010).
6.3 Public sector application
As a clean and alternative energy source, the wind energy
market is constantly expanding, presenting more opportu-
nities for supercapacitors. Pitch control in wind turbines
adjusts the blades to current conditions in order to maxi-
mize generation. Batteries have been the dominant energy
source to power the pitch control; however, setbacks, such
as insufficient power output and low life cycle, have redi-
rected wind turbine operators to more reliable supercapac-
itors. Supercapacitors are capable of responding instantly
to unpredictable weather conditions, supplying short bursts
of power to operate the turbines (Andrews, 2011). Addi-
tionally, the low maintenance cost and long cycle life of
supercapacitors are suitable to be installed in unmanned
wind turbines. Another application of supercapacitors can be
found with the Emirates Airline cable cars. Each cable car is
equipped with its own supercapacitor-based energy system
that supports accommodations (e.g., lights and air condi-
tioning) for tourists. The energy system is rapidly charged at
each station to power the 5-min cable car ride (Hubley, 2012).
As another example, three Japanese companies have collab-
orated to build stand-alone, environment-friendly LED street
lamps. The LED lamps consist of solar panels to harness
the solar energy and supercapacitors to store the energy
during the day. At night, the energy is discharged to power
the LED lamps (Nippon-Chemi-Con, 2010). The combina-
tion of long-life LED lamps and supercapacitors provide
maintenance-free street lamps for years at a time.
6.4 Public transportation applications
The prospective utilization of supercapacitors began with
public transportation. Heavy vehicles such as buses and
trucks frequently stop during their operations, wasting enor-
mous amounts of heat energy. Supercapacitors would be
capable of harnessing and storing this instantly released
Handbook of Clean Energy Systems, Online C 2015 John Wiley & Sons, Ltd.
This article is C 2015 John Wiley & Sons, Ltd.
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DOI: 10.1002/9781118991978.hces112
21
momentum when it is transformed into electrical energy.
Then, the charged supercapacitors can discharge the energy
to assist acceleration, reducing overall fuel consumption and
CO2 emissions. Regenerative breaking involving superca-
pacitors has already been applied to many public transporta-
tion vehicles. In Switzerland, 1 ton of supercapacitors was
installed onto a tram to capture its brake energy. The stored
energy was successfully deployed to power the vehicle for a
short distance without an external source (Railway-Gazette,
2012). Similarly, supercapacitors are also implemented on
trams in Paris. The trams, holding a bank of 48 supercapac-
itors on each vehicle, were able to travel between stations
via regenerative braking and short charging during the idling
time at each station (∼20 s) (Hondius, 2009). On the road
side, Sinautec developed 41-seat municipal buses powered
entirely by supercapacitors. The buses can traverse a few
miles to the adjacent stop where the buses can be recharged
again. On the basis of a vehicle’s expected 12-year life, a
supercapacitor bus can save up to $200,000 in fuel than a
diesel bus and it is 40% cheaper than a lithium ion battery
bus when considering capital costs (Hamilton, 2009).
6.5 Future applications
Scientists and entrepreneurs are exerting much effort into
uncovering innovative applications for supercapacitors.
Volvo developed lightweight structural energy storage
components composed of carbon fibers and polymer
resins. The components, behaving like supercapacitors, are
considerably lighter than the conventional batteries already
used in electronic vehicles. In addition, the energy storage
components can be easily molded into desired shapes (e.g.,
car chassis). Volvo’s S80 prototype replaced its trunk lid and
plenum cover for these supercapacitive materials to store
the brake energy (Ingram, 2013). Another development
in electric vehicles arouse when South Korean scientists
synthesized extremely porous graphene supercapacitors
that can exhibit similar energy densities to that of lithium
ion batteries. A charge time of only 16 s was required for
this supercapacitor. One gram of this extremely porous
graphene has a surface area of a basketball court, which
translates to an extremely high energy density. Incorporating
this graphene supercapacitor to electric vehicles will allow
effective storage of the braking energy, but scaling-up the
production of this specialized graphene for commercial
application remains a challenge (Estes, 2013). Alternatively,
the concept of wearable electronics as shown in Figure 28 is
becoming more realistic as scientists are integrating super-
capacitor technology into clothing. Li from the University
of South Carolina created a T-shirt that functioned like a
supercapacitor. Li purchased a T-shirt from a local store
22 Electrochemical Storage
Power communication
devices that control your
phone/music player
Harvest energy from
+
body movements to
keep your textile-
supercapacitor
−
charged
Energy storing material
made as a textile with
seamless knitting
Figure 28. Concept of integrated energy storage in wearable elec-
tronics. Source: Reproduced with permission from CRCS Publica-
tions (Jost et al., 2013).
and soaked it in fluoride solution, then baked it at a high
temperature in the absence of oxygen. The surfaces of the
clothing fibers transformed into AC, exhibiting supercapaci-
tive behavior. Additionally, Li deposited manganese dioxide
on the activated-carbon T-shirt to further enhance its energy
performance (Powell, 2012).
7 CHALLENGES AND PERSPECTIVES
As the world explores new options for clean and safe energy
sources, the supercapacitors’ contribution is becoming more
evident. Supercapacitors can instantly charge/discharge with
high power and retain its performance even after half a
million cycles.
Despite these benefits, commercialization of supercapac-
itors is currently limited by several challenges. Insufficient
energy density of supercapacitors is a pitfall for this type
of energy system, which restricts its potential application.
Comparatively, lithium ion batteries stores up to 20 times
more energy than supercapacitors at given size or mass
(Harrop, 2013). High power density and long life cycle prop-
erties of supercapacitors are not appealing enough for indus-
tries and consumers to totally replace batteries with superca-
pacitors. Another hindrance to the ubiquity of supercapaci-
tors is its cost. Over 200 lithium ion battery manufacturers
are established internationally, massively producing their
devices, whereas only 80 supercapacitor companies exist
to supply the demands (Harrop, 2013). As of this moment,
supercapacitors cannot surpass lithium ion batteries in terms
of price per performance. Another challenge to nation-
ally implement supercapacitors is the deficit of supporting
Handbook of Clean Energy Systems, Online C 2015 John Wiley & Sons, Ltd.
This article is C 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces112
infrastructure. For example, electric vehicle markets would
greatly benefit from the numerous prospective opportunities
from supercapacitors. However, commercialization of these
vehicles will require installation of new charging stations
throughout the nation, which may take several years for
implementation (De Angelis, 2013).
Nevertheless, the future of supercapacitors is expected to
grow as significant resources have been invested in techno-
logical research and in the initiation of entrepreneurial appli-
cations. Supercapacitor companies such as Ioxus raised $15
million equity for research and development in 2013 (Harrop,
2013). Scientists at the University of Illinois have experi-
enced great success in transforming forest waste to super-
capacitors in an environment-friendly way (Yates, 2013).
Therefore, otherwise unusable forest waste can now be recy-
cled into energy storage devices. Overall, industries foresee
that the supercapacitor market will increase at a compound
annual growth rate of 19.85% through 2016 (De Angelis,
2013). In addition, numerous supercapacitor manufacturers
will expand in the distant future, which will in turn increase
the supply, as well as lower the price of supercapacitors. The
preference for supercapacitors in commercial applications
is continuously growing. For example, Maxwell Technolo-
gies is selling $100 million of supercapacitors every year for
use in windmills, transit buses, and automobiles (Batzdorf,
2013). Similarly, the new 2014 Mazda 3 vehicles incorpo-
rate a regenerative braking system utilizing supercapacitors
called i-Eloop. Brake energy from the car is stored in the
supercapacitors and then discharged to supply power to the
interior electrical systems (Gastelu, 2013).
Currently, many potential developments are underway in
the world to make supercapacitors more viable and afford-
able. Within a few years, supercapacitors will be a major
energy source, alongside batteries, to offer the world more
options for clean and efficient energy storage.
RELATED ARTICLES
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Introduction - Energy Storage
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Barriers for the development of energy storage systems
Rechargeable Battery Energy Storage for Clean Energy
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Metal Air Batteries
Battery Recycling
Sodium-Sulfur Batteries
Lithium-ion batteries
Electric Vehicles as a Mobile Storage Device
 Electrochemical Supercapacitors for Energy Storage and Conversion
Energy storage as part of the energy system and system
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