Supercapacitors: Review of Materials

and Fabrication Methods

Manisha Vangari 1; Tonya Pryor 2; and Li Jiang 3

Abstract: Supercapacitors are considered to be promising candidates for power devices in future generations. These devices are expected to
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find many future applications in hybrid electric vehicles and other power devices and systems. For supercapacitors to realize their promise, it
is important that their energy and power densities be maximized. An important way to address this is to develop advanced electrode materials
and methods to fabricate these materials. The recent years have seen enormous interest in the research of numerous materials and methods for
their synthesis for applications in supercapacitor electrode technology. In the constantly changing technological landscape, it is relevant to
review the various aspects of supercapacitor devices. This review paper gives an overview of the types of supercapacitors. It describes the
advanced materials and fabrication methods for these devices, including recent developments in these areas, and their implications on
the future of supercapacitor technology. The paper also addresses the principal technological challenges facing the development efforts
in the future. DOI: 10.1061/(ASCE)EY.1943-7897.0000102. © 2013 American Society of Civil Engineers.
CE Database subject headings: Energy storage; Manganese; Polymer; Fabrication.
Author keywords: Energy storage; Energy methods; Electric power; Reviews.

Introduction Supercapacitors have advantages over conventional energy storage

In the past several decades, the rapid strides made in various areas
such as industrialization have resulted in increased demands for
energy. At the same time, the global increase in human population
has contributed to these growing energy requirements. These
factors have combined to place a major strain on the existing power
infrastructure and pose serious implications for the future of
humanity. Until now, petroleum based fuels have been largely used
for the power needs of society. However, with limited petroleum
resources, there is a need for alternate energy sources. In the recent
decades, there has been a significant amount of interest in devel-
oping new technologies to address energy challenges. In this
context, considerable effort has been put into researching and de-
veloping more efficient energy storage devices and systems. An
example of such a device is the supercapacitor, also referred to
as the electrochemical capacitor or ultracapacitor. Supercapacitor
technology has undergone considerable research and development
in the recent years due to its potential to allow the advancement of
energy storage technology.
Supercapacitors employ thin dielectric layers and high surface
area electrodes. Consequently, they exhibit capacitances that are
several orders of magnitude higher than traditional capacitors (Kotz
and Carlen 2000; Burke 2000). Supercapacitors can be employed
in a variety of energy capture and storage applications, either
independently or in combination with batteries or fuel cells.
1
Electrical Engineering Dept., Tuskegee Univ., Tuskegee, AL 36088.
2
Electrical Engineering Dept., Tuskegee Univ., Tuskegee, AL 36088.
3
Electrical Engineering Dept., Tuskegee Univ., Tuskegee, AL 36088
(corresponding author). E-mail: ljiang@mytu.tuskegee.edu
Note. This manuscript was submitted on December 19, 2011; approved
on September 19, 2012; published online on September 22, 2012. Discus-
sion period open until November 1, 2013; separate discussions must be
submitted for individual papers. This paper is part of the Journal of Energy
Engineering, Vol. 139, No. 2, June 1, 2013. © ASCE, ISSN 0733-9402/
2013/2-72-79/$25.00.
devices in terms of their large numbers of charging-discharging
cycles, high power capability, and a robust thermal operating range
(Kotz and Carlen 2000). Supercapacitors can store a large amount
of charge that can be supplied at a higher power rating than re-
chargeable batteries (Stoller et al. 2008). However, the energy den-
sity of supercapacitors is lower than that of batteries and fuel cells.
This necessitates coupling with batteries or other power sources for
applications requiring an energy supply for longer periods of time
(Stoller et al. 2008). Therefore, there is an interest in increasing the
energy density in supercapacitors to a level comparable to batteries.
This is one of the major reasons for the recent significant interest in
the research and development of numerous materials and synthesis
methods in supercapacitor technology. This review paper describes
the advanced materials, their synthesis, and electrode fabrication
methods for supercapacitors. It describes the challenges and future
outlook in these areas, and their general implications on superca-
pacitor technology.
Supercapacitor Types
Supercapacitors can be classified into three types: electrochemical
double layer (EDLC), pseudocapacitor, and a hybrid type formed
by a combination of EDLC and pseudocapacitor (Fig. 1). In
EDLCs, the energy storage and release mechanism is based on
nanoscale charge separation at the electrochemical interface formed
between an electrode and an electrolyte. The charge storage mecha-
nism is nonfaradaic and no chemical oxidation-reduction (redox)
reactions are involved. EDLCs have relatively long cycle lives
because only physical charge transferring occurs. In contrast,
pseudocapacitors are based on faradaic redox reactions involving
high energy electrode materials based on metal oxides, metal-
doped carbons, or conductive polymers (Stoller et al. 2008). These
electrode materials allow supercapacitors with higher energy den-
sity. As a result, pseudocapacitors usually provide higher energy
density at the price of shorter cycle lives and lower rates than

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J. Energy Eng., 2013, 139(2): 72-79

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Fig. 1. Schematic representation of supercapacitor types: (a) EDLC type; (b) pseudocapacitor type; (c) hybrid capacitor type (the figure is not to scale)

EDLCs. The hybrid supercapacitor, as the name suggests, incorpo- Materials

rates mechanisms from both EDLCs and pseudocapacitors.
In a basic form, a supercapacitor consists of two electrodes
isolated from electrical contact by a semipermeable membrane
functioning as a separator (Fig. 1). The electrodes and separator
are impregnated with an electrolyte solution, which enables the
flow of ionic current between electrodes while preventing elec-
tronic current from discharging the cell (Stoller et al. 2008). Current
collectors conduct electrical current from the electrodes.
Supercapacitors are governed by the same fundamental equa-
tions as traditional capacitors in which capacitance can be derived
from the conventional capacitance, which is given by
Supercapacitors can be made from different materials, depending
on the type of energy storage required by the application at hand
and the required capacitance ranges. The electrode materials for
supercapacitors can be classified into three types based on their
usage for EDLCs, pseudocapacitors, and hybrid supercapacitors
(Fig. 2). A significant number of materials are presently available
for supercapacitors; the major commercial material is carbon,
which is widely used and can be converted into many forms.

Capacitance; C ¼ εo .εr .Ae =d

where Ae = geometric surface area of the electrode; ϵo =

permittivity of free space; ϵr = relative permittivity of the dielec-
tric material; and d = distance between two oppositely biased
electrodes. Considering an EDLC type supercapacitor, a potential
difference is created at the electrode–electrolyte interface upon ap-
plication of an electric potential to the electrodes. The electrode–
electrolyte interface incorporates a double layer formed between
the electrolyte ions and electronic charges on the electrode
(Arepalli et al. 2005). In this case, d in the preceding equation
is the interplanar distance or the double layer thickness d, which
is very small. Because the capacitance and energy of a capacitor
Fig. 2. Classification of supercapacitor types and their electrode
are inversely proportional to d, supercapacitors are capable of stor-
materials
ing large amounts of energy.

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J. Energy Eng., 2013, 139(2): 72-79

 Other materials include metal oxides such as nickel, cobalt,
manganese, and ruthenium. Conducting polymers have also been
employed in supercapacitors. More recently, supercapacitors are
increasingly based on carbon nanotubes (CNTs). The use of CNTs
and other nanomaterials allows for a significant increase in surface
area, among other advantages.
The other types of commonly used supercapacitor materials are
composites obtained by combining two or more constituent mate-
rials. The composites can include a nanomaterial. An example is a
composite formed by combining CNTs with conducting polymers
or metal oxides.
For the supercapacitor electrodes, there is an interest in nano-
structured materials that have increased surface area and improved
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capacitive performance characteristics. The synthesis of nanoengi-
neered materials is now recognized as a major factor in developing
high performance supercapacitor devices.
Carbon Materials
Activated carbons find application in electrodes for EDLC
supercapacitors, in which they are commonly used materials. These
carbons are known for their large surface area (Pandolfo and
Hollenkamp 2006). Their large surface is due to their highly porous
structure. They are also less expensive than other carbon materials.
The high porosity can cause some problems. Pores that may be
smaller than the electrolyte ions will not contribute to charge
storage (Shi 1996; Qu and Shi 1998). Also, high porosity can
lead to poor conductivity, limiting the maximum power density
(Frackowiak and Beguin 2001). Additionally, a distributed electro-
lyte resistance may be created, which restricts charge and discharge
rates (Pandolfo and Hollenkamp 2006).
CNTs have unique material properties that make them highly
applicable as a supercapacitor material. The most important features
of CNTs are their electronic, mechanical, optical, and chemical char-
acteristics. They exhibit excellent electronic conductivity and some
highly desirable mechanical properties. These aspects, along with
the increased surface area provided by CNTs, are allowing them
to find increasing applications in supercapacitor technology. CNTs
are inexpensive, durable, and readily available. There is an already
established production market for electrodes based on CNTs.
Supercapacitor electrodes made from CNTs have a continuous
charge distribution utilizing most of the surface area, allowing for
an efficient utilization of surface area. This helps the CNT based
electrodes to achieve capacitances comparable to those in activated
carbon electrodes, despite the larger surface area in activated
carbon (Frackowiak and Beguin 2001; Frackowiak et al. 2000).
Another positive factor is the mesoporous nature of CNT networks
in electrodes. This causes electrolytes to diffuse more easily and
contributes to a decreased equivalent series resistance and a higher
maximum usable power (Niu et al. 1997; An et al. 2001).
Carbon aerogels are typically used in EDLC supercapacitors.
They are made of continuous networks of carbon nanoparticles with
interspaced mesopores, which allows them to be used in electrodes
without the need for a binder material. Consequently, electrodes
made of carbon aerogels exhibit lower equivalent series resistance,
which helps in increasing power performance (Arico et al. 2005).
Metal Oxides
Metal oxides have been employed as electrode material in super-
capacitors because of their high conductivity (Kotz and Carlen
2000; Burke 2000; Zheng and Jow 1995). Metal oxide based
supercapacitors show large specific capacitance and long operation
time (Jogade et al. 2011).
74 / JOURNAL OF ENERGY ENGINEERING © ASCE / JUNE 2013
J. Energy Eng., 2013, 139(2): 72-79
Ruthenium oxide is a material of considerable interest in super-
capacitor technology (Lee et al. 2007). Ruthenium oxide, in its
hydrous form, offers higher capacitance than carbon materials
and conducting polymers (Zheng and Jow 1995). It combines
metal-type conductivity and reversible redox reactions, which oc-
cur at the electrode–electrolyte interface and also in the material
bulk (Zheng and Jow 1995; Li 2009). The primary drawback of
this material is its high cost, which is driving research activities
in composite materials and fabrication methodologies to reduce
costs while retaining the performance of ruthenium oxide (Kotz
and Carlen 2000; Burke 2000; Kim and Kim 2001).
Manganese oxide is one of the most promising materials for
supercapacitor electrodes. It allows good capacitive performance
and is relatively inexpensive and environmentally safe (Xia et al.
2011). There has been interest in nanostructured manganese oxides
for supercapacitors (Xia et al. 2011). These oxides have been syn-
thesized by different methods. The primary drawback with this
material is its poor conductivity, unlike ruthenium oxide. Also,
the charge–discharge processes in this material involves surface
atoms only, thereby resulting in low material utilization (Li 2009).
Some efforts have already commenced to address this, primarily by
employing this material in composite form with CNTs (Wang et al.
2005; Xie and Gao 2007).
Conducting Polymers
Conducting polymers are employed in supercapacitors because their
relatively high capacitance and conductivity and low equivalent
series resistance. Conducting polymers have redox storage capability
and provide a large surface area; therefore, they are employed in
supercapacitors for high capacitance. These compounds can be
doped to have metallic conductivity, which is a desirable property
for supercapacitor electrode materials. In some aspects, they are
considered superior to some carbon materials, including activated
carbons (Arbizzani et al. 2001; Frackowiak et al. 2006). Some of
the commonly used conducting polymers include polypyrrole, poly-
aniline (PANI), and poly-(3,4-ethylenedioxythiophene) (PEDOT),
which have been shown to exhibit specific capacitance comparable
to that of metal oxides like ruthenium oxide (Zou et al. 2007; Fan
and Maier 2006; Gupta and Miura 2006; Xu et al. 2006). The
challenges with conducting polymers include a lack of efficient
n-type doped (negatively charged) conducting polymer material
(Mastragostino et al. 2001). Another problem is the insufficient
mechanical stability during charge–discharge cycles due to mechani-
cal stress (Arbizzani et al. 2001; Frackowiak et al. 2006).
Composites
Composite materials are used in hybrid type supercapacitors.
Composite materials involve combinations of carbon materials with
either metal oxides or conducting polymers, thereby incorporating
aspects of both EDLC and pseudocapacitor materials; namely,
a capacitive double layer of charge and faradaic mechanisms.
Supercapacitor electrodes made of polypyrrole and CNT combina-
tions exhibit superior capacitance to electrodes that are either
wholly based on polypyrroles or on CNTs (Frackowiak et al. 2006;
Jurewicz et al. 2001).
Fabrication Methods
There are several different methods to synthesize supercapacitor
materials. They include electrochemical deposition, chemical bath
deposition, chemical vapor deposition, and the sol-gel method.
Similarly, there are several methods to fabricate supercapacitor
 electrodes, including spray coating, inkjet printing, and direct
writing. The ensuing sections will discuss both material synthesis
and electrode fabrication methods.
Material Synthesis
The most basic form of electrochemical deposition is the electro-
deposition method, in which a coating or film of material is
produced on a surface by the action of electric current. The material
is deposited on a substrate by placing a negative charge on that
substrate when it is immersed in a solution of salt of the material
to be deposited. The ions of the salt have a positive charge and are
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attracted to the cathode or the negatively charged substrate. Upon
reaching the substrate, the salt ions obtain electrons from the
substrate (cathode) and undergo reduction to form material. Fig. 3
shows a schematic representation of a basic two-electrode electro-
deposition cell used to deposit a metal from an aqueous solution of
metal salt.
A more complicated variation of the basic two-electrode set-up
is the three-electrode configuration, which allows for accurate po-
tential settings (Fig. 4). This configuration can be used to deposit
supercapacitor materials. The substrate can be the working elec-
trode, a platinum foil or carbon rod can be the counter electrode,
and a silver/silver chloride or saturated calomel electrode can be
Fig. 3. Schematic representation of a basic electrodeposition process
setup for the deposition of a metal film on a surface (the figure is not to
scale)
Fig. 4. Schematic representation of a three electrode electrodeposition
process setup, where WE is the working electrode, CE is the counter
electrode, and RE is the reference electrode (the figure is not to scale)
J. Energy Eng., 2013, 139(2): 72-79
used as the reference electrode (Xia et al. 2011). This setup allows
the anodic deposition of manganese oxide from an acidic or neutral
electrolyte containing Mn2þ such as MnSO4 , MnðCH3 COOÞ2 , and
MnðNO3 Þ2 (Shinomiya et al. 2006; Chou et al. 2006).
The benefits of the electrodeposition method include mass pro-
duction, low capital investment costs, and precise control on param-
eters such as film thickness, uniformity and deposition rate (Wei
2007). In addition to manganese oxide films, the electrodeposition
method has also been used to synthesize RuO2 thin film for super-
capacitor applications (Lee et al. 2007; Zhitomirsky et al. 2007).
Some reports have indicated specific capacitance values of
788 F=g for electrodeposited RuO2 films in 0.5 M H2 SO4 (Lee
et al. 2007). Electrodeposition has also been employed to deposit
conducting polymers such as PANI. Some reports have indicated
that growing highly ordered films of PANI improves the capaci-
tance characteristics of PANI (Zou et al. 2007). Ordered PANI films
synthesized by a three-step electrochemical deposition process
were found to exhibit superior specific capacitance values com-
pared to those of films made by a single-step electrodeposition pro-
cess (Zou et al. 2007). For example, PANI films grown on carbon
substrates by a three-step process showed a specific capacitance of
437 F=g in 0.5 M H2 SO4 at a scan rate of 10 mV=s, compared to a
value of 181 F=g in films made by a one-step process (Zou
et al. 2007).
An alternative to electrolytic deposition is electroless deposi-
tion, which is an autocatalytic variant of electrochemical deposi-
tion, performed without the application of an electric field. In an
electrodeposition process, the source of electrons is an external
power supply, whereas in an electroless process, the electrons
are supplied by a reducing agent in the solution. Electroless
processes have been used to synthesize ruthenium oxide–carbon
composites for supercapacitors (Ramani et al. 2001). The electro-
less process is suitable for certain situations requiring electrochemi-
cal deposition of material on nonconducting surfaces. Another type
of electrochemical deposition is a process called electrophoretic
deposition. This method involves the movement of charged
particles suspended in liquid medium toward an electrode under
an electric field. Upon reaching the electrode, the coagulation of
the particles results in the deposition of material. This method
can also be employed in supercapacitor material synthesis and
fabrication.
Chemical bath deposition (CBD) is a low temperature technique
that allows for relatively inexpensive deposition of material on
large-area substrates (Khallaf et al. 2009). The CBD method in-
volves the direct deposition of a material from a solution medium
without the application of current or voltage. CBD occurs on a
substrate immersed in a solution by means of a reaction from
the solution containing different precursors dissolved either in
ionic or molecular form. These react chemically on the substrate,
resulting in film formation by nucleation.
Recently, PANI thin films have been deposited by microwave
assisted CBD; namely, by the oxidation of aniline in domestic mi-
crowave oven (Deshmukh et al. 2011). A maximum specific
capacitance of 753 F=g was obtained at a scan rate of 5 mV=s
in cyclic voltammetry studies in 0.5 M H2 SO4 medium. The
CBD method has also been used to synthesize ruthenium oxide
for supercapacitor electrodes. Thin films of RuO2 synthesized
by room temperature liquid phase CBD have been reported to
exhibit a specific capacitance of greater than 400 F=g at a scan rate
of 5 mV=s in 0.5 M H2 SO4 (Lee et al. 2007).
In addition to the relatively low cost, large substrate area, and
low temperature processing of CBD, another advantage is its
relative simplicity, especially when compared to electrodeposition.
Among its drawbacks, the flexibility of the CBD method has been
JOURNAL OF ENERGY ENGINEERING © ASCE / JUNE 2013 / 75
 limited due to insufficient fundamental understanding and control
of the underlying chemistry. However, recent efforts have been
trying to address this (McPeak et al. 2010). Another drawback
of CBD when employed in a conventional beaker configuration
is the low material yield for film formation. In this configuration,
the volume to surface ratio is high, with only a small portion of the
solution participating in film formation and the remaining solution
contributing to colloid formation in the solution bulk. This problem
can be addressed by performing the CBD process between two sub-
strates with a small spacing filled with solution (Nair et al. 2001).
This configuration can then be considered two-dimensional without
limitations on area.
In its simplest form, the chemical vapor deposition (CVD)
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process is achieved by exposing a substrate to appropriate precur-
sors (typically gas molecules) in the presence of energy (thermal
or plasma) in a reaction chamber (Fig. 5). The precursors undergo
reaction and/or decomposition on the surface of the substrate and
form the desired solid thin film or powder. Any volatile by-products
resulting in the process are removed by flowing gas through the
chamber.
In the context of supercapacitor devices and their fabrication,
the CVD process is primarily used to synthesize carbon materials,
including CNTs and nanofibers. Carbon film deposition by the
CVD process generally employs precursor molecules such as
acetylene, ethylene, carbon monoxide, and methane.
The CVD method has been used to synthesize multiwalled car-
bon nanotubes and has been employed in flexible supercapacitor
electrodes (Reddy et al. 2008). In the formation of CNTs by
CVD, an appropriate catalyst material is incorporated in the
substrate (Li et al. 2001). Some commonly used catalyst materials
for CNT growth include cobalt (Chatterjee et al. 2003), iron, and
nickel. The growth and the subsequent properties of the resulting
CNTs are influenced by the properties of the catalyst, such as its
type and thickness (Li et al. 2001; Chhowalla et al. 2001). The
CVD method also allows the synthesis of graphene-type materials.
Three-dimensional networks of graphene have been prepared by
CVD using ethanol as a carbon source (Cao et al. 2011). These
networks have been used a templates to make grapheme/metal
oxide composite supercapacitor electrodes showing specific
capacitance of 816 F=g at a scan rate of 5 mV=s. Graphitic
nanofibers have also been deposited by the CVD process for
supercapacitor applications (Hulicova-Jurcakova et al. 2008).
Plasma-enhanced CVD (PECVD) is a variant of the CVD tech-
nique, which can be used to grow vertically dense aligned CNTs at
lower temperatures than CVD. The PECVD method has been used
to synthesize aligned CNTs on a stainless steel surface coated by
ferric nitrate for supercapacitor electrodes exhibiting 160.9 F=g at a
potential range of −0.2 to 0.8 V and a scan rate of 1 mV=s in
1mol=L sodium sulfate aqueous solution (Chen et al. 2010).
Sol-gel, or solution gelling, is a method used to form solid thin
films. In its basic form, the sol-gel technique is achieved by dip
Fig. 5. Schematic representation of a thermal CVD system (the
diagram is not to scale)
76 / JOURNAL OF ENERGY ENGINEERING © ASCE / JUNE 2013
J. Energy Eng., 2013, 139(2): 72-79
coating a surface in a solution. Subsequently, polymeric or particu-
late inorganic precursors are concentrated on a surface by a
complicated process involving gravitational draining with simulta-
neous drying or solvent evaporation and continued condensation
reactions, ultimately resulting in the formation of a solid film
(Brinker et al. 1991). Among its advantages, the sol-gel method
allows for control of the texture, composition, homogeneity, and
structural properties of resulting materials (Brinker and Scherer
1990). Also, compared to other methods such as CVD, the equip-
ment requirements for a sol-gel dip coating process are significantly
less, translating to lower costs (Brinker et al. 1991).
The sol-gel technique has been employed to synthesize elec-
trode materials for supercapacitors. For example, carbon aerogels
are obtained from the carbonization of organic aerogels, which are
synthesized by sol-gel polycondensation of specific organic mono-
mers (Moreno-Castilla and Maldonado-Hodar 2005). Other mate-
rials, such as high-surface area carbon-ruthenium xerogels, have
also been derived from sol-gel methods and used to make electro-
des with a specific capacitance of 256 F=g in carbon–metal
oxide supercapacitors (Lin et al. 1999). Among other materials, tin
dioxide (SnO2 ) nanocrystallites doped with antimony were syn-
thesized by a sol-gel process and employed in SnO2 based super-
capacitors (Wu 2002). Amorphous hydrous ruthenium oxide/active
carbon was prepared by a sol-gel based procedure and a specific
capacitance of up to 715 F=g was obtained (Zhang et al. 2001).
Amorphous manganese dioxide (MnO2 ) made by the sol-gel
method by reducing sodium permanganate (NaMnO4 ) with solid
fumaric acid has been employed as an electrode material (Reddy
and Reddy 2004).
In a fundamental form, the chemical precipitation method in-
volves the formation of a solid material from solution by means
of a reaction. A solid substance is formed from a solution by
one of two mechanisms: by the conversion of the substance into
an insoluble form or by modifying the solvent composition to
reduce the solubility of the substance in it. This method has
primarily been used in supercapacitor technology to synthesize
electrode materials. For example, supercapacitor electrodes have
been developed showing a maximum capacitance of 107 F=g,
based on composites of nickel oxide–carbon materials prepared
by chemically precipitating nickel hydroxide on active carbon
and heating the hydroxide at 300°C in air (Lota et al. 2011).
Similarly, manganese dioxide nanofibers synthesized by chemical
precipitation have been employed in electrodes made by impreg-
nating these fibers and multiwalled CNTs into porous nickel plaque
current collectors (Li et al. 2010). Specific capacitances as high as
185 F=g have been observed with these composite electrodes. In
supercapacitors employing manganese oxide–CNT composites
as electrode materials, the manganese oxide has been synthesized
in amorphous form by chemical precipitation of Mn(VII) and Mn
(II) in a water medium, yielding small particles with high surface
area (Raymundo-Pinero et al. 2005). Fig. 6 summarizes the differ-
ent electrode synthesis methods in terms of materials, advantages,
and disadvantages.
Electrode Fabrication
In supercapacitor fabrication, electrodes can be made by printing
processes, which are basically additive methods. Printing tech-
niques include spray painting on a surface directly or through a
template, inkjet printing, and casting. An advantage of printing
methods is that surfaces with larger areas can be coated with
materials. Another important advantage is that it is possible to de-
posit materials on unconventional surfaces such as flexible sheets
of polymer or paper and fabric. A solution of printable material
 Synthesis Methods Materials Advantages Disadvantages

Electrochemical Metal oxides Mass production; low Process set up; current

deposition method Conducting costs; precise control on or voltage required

polymers film thickness and

Ruthenium uniformity

oxide-carbon
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composites

(electroless

deposition)

PANI Simplicity; Limited flexibility; low

CBD Ruthenium oxide low temperature; material yield

inexpensive; large-area

substrates

Carbon materials High material yield Expensive equipment

CVD (CNTs, nanofibers, than CBD; good and relatively high costs

and graphenes) film uniformity

Sol-gel Carbon aerogels Low costs; controllable Complicated process

Carbon-ruthenium film texture, composition,

xerogels homogeneity, and

SnO2, MnO2 structural properties

Ruthenium structural properties.

oxide/active carbon

Chemical precipitation Nickel Allows synthesis of May generate a waste

oxide/carbon composite electrode product

MnO2/nanofibers materials; efficient;

MnO2/CNTs easily implemented

Fig. 6. Different electrode synthesis methods in terms of materials, advantages, and disadvantages

(material in a solvent) is sprayed or inkjet printed on a substrate,
followed by the evaporation of the solvent. For supercapacitor
fabrication, an example of printable material is an ink or solution
of CNTs in a suitable solvent. A printed film of CNT networks can
function as a supercapacitor electrode.
The spray technique has been used to make networks of single-
walled CNTs on plastic substrates that function as both electrodes
and charge collectors (Kaempgen et al. 2009). An inkjet printing
process has been employed to print inks of single-walled CNTs on
flexible surfaces and fabrics to make thin film electrodes (Chen
et al. 2010). The process, conducted by using an off-the-shelf inkjet
printer, allows for controlled pattern geometry of the features, con-
trollable thickness, and tunable electrical properties. In the same
way, ruthenium oxide nanowire/single wall nano tube hybrid film

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J. Energy Eng., 2013, 139(2): 72-79

 electrodes have also been inkjet printed on similar substrates, show-
ing a specific capacitance of 138 F=g (Chen and Zhang 2010). In a
type of printing method, a direct writing or drawing process by a
graphite rod or pencil was used to fabricate supercapacitors on
cellulose paper (Zheng et al. 2011). The advantage of this method
is that it is solvent-free and can find specific applications. The
drawback is the serial nature of the method; it may find practical
feasibility when automated for parallel or batch processing.
Technology Challenges and Future Outlook
The preceding sections of this review describe some of the research
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and development efforts in supercapacitor materials and their syn-
thesis methods. These efforts are necessary to maximize superca-
pacitor energy and power densities and need to be continued in
future. The current supercapacitor technology at this juncture is still
some distance away from the ideal power and energy densities that
are possible. One reason preventing power density from reaching
its theoretical limits in a supercapacitor is its equivalent series
resistance. This needs to be decreased. Some efforts have already
been made to address this, including employing thin film electrodes
made by highly concentrated colloidal suspension of CNTs (Du
et al. 2005). Another factor from the perspective of materials is
the electrolyte, which has to be optimized (Zheng 2003, 2005). This
is because its resistance can limit power density. Also, the ion
concentration and operating voltage can be limiting factors on the
energy density.
The materials and methods that are selected to fabricate a super-
capacitor must yield devices that have uniformity in electrical char-
acteristics during the entire lifespan of the device. This factor plays
an important role in actual applications of supercapacitors, in which
one of the challenges is the high voltage requirements in many
scenarios (Kotz and Carlen 2000). For these applications, many
supercapacitors have to be employed in series configuration.
However, if capacitance and leakage resistance vary in individual
devices during their lifespan, some may experience an overvoltage
and sustain damage (Kotz and Carlen 2000). This may lower the
performance of the whole system.
Conclusions
Supercapacitors offer promising solutions to future energy storage
requirements. A variety of methods and materials are available
for the development of supercapacitors. Several supercapacitor
electrode materials and relevant fabrication methodologies have
been reviewed here. An appropriate combination of materials
and methods can be selected based on the application at hand.
For example, if thin film based supercapacitors are desired for mass
production, then the suitable methods to employ include CVD,
CBD, and printing.
The review of pertinent literature described in this paper
indicates that challenges exist for supercapacitor technology. There
appears to be a gap between the theoretical benefits of supercapa-
citors and practical value possible by current technology. Some of
the major factors include materials and fabrication methods. These
influence other factors such as device performance and cost of
production, which place limitations on the applications for super-
capacitors. It is anticipated that most future research and develop-
ment efforts will address these challenges. One can already witness
the presently burgeoning interest in tailoring new materials and
composites, specifically nanomaterials. As these efforts progress,
supercapacitors will become increasingly viable in a growing
number of practical applications. For the present time, however,
78 / JOURNAL OF ENERGY ENGINEERING © ASCE / JUNE 2013
J. Energy Eng., 2013, 139(2): 72-79
supercapacitors will find specific applications such as those involv-
ing some hybrid configurations with batteries.
Acknowledgments
This work of literature review is supported in part by the US
National Science Foundation (NSF) award #ECCS-1039629,
cooperative award #EEC-0812072 and US Army Research Office
award/contract #W911NF-11-1-0214. The authors are grateful to
Dr. Naga S. Korivi for helpful discussions.
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