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CRITICAL REVIEW

A review of electrode materials for electrochemical supercapacitors
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Guoping Wang,*ab Lei Zhang*b and Jiujun Zhangb
Received 4th March 2011
DOI: 10.1039/c1cs15060j
In this critical review, metal oxides-based materials for electrochemical supercapacitor (ES)
electrodes are reviewed in detail together with a brief review of carbon materials and conducting
polymers. Their advantages, disadvantages, and performance in ES electrodes are discussed
through extensive analysis of the literature, and new trends in material development are also
reviewed. Two important future research directions are indicated and summarized, based on
results published in the literature: the development of composite and nanostructured ES materials
to overcome the major challenge posed by the low energy density of ES (476 references).

1. Introduction
With the rapid development of the global economy, the depletion
of fossil fuels, and increasing environmental pollution, there is an
urgent need for efficient, clean, and sustainable sources of energy,
as well as new technologies associated with energy conversion
and storage.
a

College of Chemical Engineering, University of South China,
Hengyang 421001, China. E-mail: wgpcd@yahoo.com.cn;
Fax: +86 734 8282 375; Tel: +86 734 8282 667
b
Institute for Fuel Cell Innovation, National Research Council of
Canada, 4250 Wesbrook Mall, Vancouver, BC V6T 1W5, Canada.
E-mail: lei.zhang@nrc.gc.ca; Fax: +1 604 221 3001;
Tel: +1 604 221 3087

Dr Guoping Wang is an
associate professor at the
University of South China.
He joined the National
Research Council of Canada
Institute for Fuel Cell Innovation as a visiting scholar in
2010. Dr Wang received his
BE and MEng from Sichuan
University and then his PhD
from Chinese Academy of
Science in 2005 in the field of
applied chemistry, under the
direction of Prof. Zuolong
Yu. Since 2002, Dr Wang
Guoping Wang
has been engaged in the
research in the field of electrochemistry. His research interests
focus on battery and supercapacitor materials, chemical engineering and processes. He has published over twenty technical
papers and holds two Chinese patents.

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In many application areas, some of the most effective and
practical technologies for electrochemical energy conversion
and storage are batteries, fuel cells, and electrochemical supercapacitors (ES). In recent years, ES or ultracapacitors have
attracted significant attention, mainly due to their high power
density, long lifecycle, and bridging function for the power/
energy gap between traditional dielectric capacitors (which
have high power output) and batteries/fuel cells (which have
high energy storage).1,2
The earliest ES patent was filed in 1957. However, not until
the 1990s did ES technology begin to draw some attention, in
the field of hybrid electric vehicles.3 It was found that the main
function of an ES could be to boost the battery or fuel cell in a
hybrid electric vehicle to provide the necessary power for

Ms Lei Zhang is a Research
Council Officer at National
Research Council of Canada
Institute for Fuel Cell Innovation. She received her first
MSc majoring in Materials
Chemistry
from
Wuhan
University, China, in 1993
and her second MSc in
Materials/Physical Chemistry
from Simon Fraser University,
Canada, in 2000. Ms Zhang’s
main research interests include
PEM fuel cell electrocatalysis,
catalyst layer/electrode strucLei Zhang
ture, metal–air batteries and
supercapacitors. Ms Zhang is an adjunct professor of Federal
University of Maranhao, Brazil, and Zhengzhou University,
China, respectively. She is also an international advisory
member of the 7th IUPAC International Conference on Novel
materials and their Synthesis (NMS-VII) and an active member
of the Electrochemical Society and the International Society of
Electrochemistry.
Chem. Soc. Rev., 2012, 41, 797–828

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acceleration, with an additional function being to recuperate
brake energy.4 Further developments have led to the recognition that ES can play an important role in complementing
batteries or fuel cells in their energy storage functions by
providing back-up power supplies to protect against power
disruptions. As a result, the US Department of Energy has
designated ES to be as important as batteries for future energy
storage systems.5 Many other governments and enterprises
have also invested time and money into exploring, researching,
and developing ES technologies.
Recent years have yielded major progress in the theoretical
and practical research and development of ES, as evinced by a
large number of research articles and technical reports.6–14
At the same time, the disadvantages of ES—including low
energy density and high production cost—have been identified
as major challenges for the furtherance of ES technologies.
To overcome the obstacle of low energy density, one of the
most intensive approaches is the development of new materials
for ES electrodes. Most popular today are carbon particle
materials, which have high surface areas for charge storage.
But in spite of these large specific surface areas, the charges
physically stored on the carbon particles in porous electrode
layers are unfortunately limited. ES of this kind, called electrostatic or electrical double-layer supercapacitors (EDLS), have
a limited specific capacitance (measured in Faradays per gram
of the electrode material) and a low ES energy density.
Advanced approaches to increase the ES energy density are
to hybridize the electrode materials by adding electrochemically active materials to a carbon-particle-based ES
electrode layer or to completely replace the carbon materials
with electrochemically active materials. ES with electrochemically active materials as electrodes are called faradaic
supercapacitors (FS). It has been demonstrated that faradaic

Dr Jiujun Zhang is a Senior
Research Officer and PEM
Catalysis Core Competency
Leader at the National
Research Council of Canada
Institute for Fuel Cell Innovation (NRC-IFCI). Dr Zhang
received his BS and MSc in
Electrochemistry from Peking
University in 1982 and 1985,
respectively, and his PhD in
Electrochemistry from Wuhan
University in 1988. After
completing his PhD, he was
an associate professor at the
Jiujun Zhang
Huazhong Normal University
for two years. Starting in 1990, he carried out three terms of
postdoctoral research at the California Institute of Technology,
York University, and the University of British Columbia.
Dr Zhang has over twenty-eight years of R&D experience in
theoretical and applied electrochemistry. He holds several
adjunct professorships, and is an active member of the Electrochemical Society, the International Society of Electrochemistry,
and the American Chemical Society.
798

Chem. Soc. Rev., 2012, 41, 797–828

or hybrid double-layer supercapacitors can yield much higher
specific capacitance and ES energy density than EDLS.15
Regarding advanced ES materials, metal oxides such as
ruthenium oxides and manganese oxides are considered the
most promising materials for the next generation of ES.
Therefore, in this review we pay particular attention to metal
oxides and their applications in ES electrodes. First, however,
we provide some introductory background on ES, which we
hope will facilitate our review and analysis of the literature.
Finally, we will discuss the direction that future research in ES
might be expected to take.

2. Fundamentals and applications of ES
2.1 Two types of ES
An ES is a charge-storage device similar to batteries in design
and manufacturing. As shown in Fig. 1, an ES consists of two
electrodes, an electrolyte, and a separator that electrically
isolates the two electrodes. The most important component
in an ES is the electrode material. In general, the ES’s
electrodes are fabricated from nanoscale materials that have
high surface area and high porosity. It can be seen from Fig. 1
that charges can be stored and separated at the interface
between the conductive solid particles (such as carbon particles
or metal oxide particles) and the electrolyte. This interface can
be treated as a capacitor with an electrical double-layer
capacitance, which can be expressed as eqn (1):

Ae
4pd

ð1Þ

where A is the area of the electrode surface, which for a supercapacitor should be the active surface of the electrode porous

Fig. 1 Principles of a single-cell double-layer capacitor and illustration
of the potential drop at the electrode/electrolyte interface.3 (Reprinted
from ref. 3 with permission from Elsevier.)

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layer; e is the medium (electrolyte) dielectric constant, which
will be equal to 1 for a vacuum and larger than 1 for all other
materials, including gases; and d is the effective thickness of
the electrical double layer.
As described in the Introduction, two types of ES exist. One
is the EDLS, in which the electrode material, such as carbon
particles, is not electrochemically active. In other words, there
is no electrochemical reaction on the electrode material during
the ES charging and discharging processes, and pure physical
charge accumulation occurs at the electrode/electrolyte
interface. The other type is the FS, in which the electrode
material is electrochemically active, e.g. metal oxides, which
can directly store charges during the charging and discharging
processes.15–17
2.1.1 Electrostatic supercapacitors (EDLS). The capacitance of the electrode/interface in an electrostatic or EDLS
is associated with an electrode-potential-dependent accumulation of electrostatic charge at the interface. The mechanism of
surface electrode charge generation includes surface dissociation as well as ion adsorption from both the electrolyte and
crystal lattice defects.5 These processes operate solely on the
electrostatic accumulation of surface charge. As shown in
Fig. 1, this electrical double-layer capacitance comes from
electrode material particles, such as at the interface between
the carbon particles and electrolyte, where an excess or a
deficit of electric charges is accumulated on the electrode
surfaces, and electrolyte ions with counterbalancing charge
are built up on the electrolyte side in order to meet electroneutrality. During the process of charging, the electrons travel
from the negative electrode to the positive electrode through
an external load. Within the electrolyte, cations move towards
the negative electrode while anions move towards the positive
electrode. During discharge, the reverse processes take place.
In this type of ES, no charge transfers across the electrode/
electrolyte interface, and no net ion exchanges occur between
the electrode and the electrolyte. This implies that the electrolyte concentration remains constant during the charging and
discharging processes. In this way, energy is stored in the
double-layer interface.
If the two electrode surfaces can be expressed as ES1 and
ES2, an anion as A, a cation as C+, and the electrode/
electrolyte interface as //, the electrochemical processes for
charging and discharging can be expressed as eqn (2)–(5).18,19
On one electrode (say, a positive one):
charging  

ES1 þ A ƒƒƒ!Eþ
S1 ==A þ e

discharging   


S1 ==A þ e ƒƒƒƒƒ!ES1 þ A

ð2Þ

ð3Þ

On the other electrode (say, a negative one):
charging

þ
ES2 þ Cþ þ e ƒƒƒ!E
S2 ==C

discharging

þ
þ 

E
S2 ==C ƒƒƒƒƒ!ES2 þ C þ e

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ð4Þ

ð5Þ

And the overall charging and discharging process can be
expressed as eqn (6) and (7):
charging 

þ 

ES1 þ ES2 þ A þ Cþ ƒƒƒ!Eþ
S1 ==A þ ES2 ==C
discharging  

þ
þ 


S1 ==A þ ES2 ==C ƒƒƒƒƒ!ES1 þ ES2 þ A þ C

ð6Þ
ð7Þ

2.1.2 Faradaic supercapacitors (FS). Faradaic supercapacitors (FS) or pseudocapacitors are different from electrostatic or EDLS. When a potential is applied to a FS, fast and
reversible faradaic reactions (redox reactions) take place on the
electrode materials and involve the passage of charge across the
double layer, similar to the charging and discharging processes
that occur in batteries, resulting in faradaic current passing
through the supercapacitor cell. Materials undergoing such
redox reactions include conducting polymers and several metal
oxides, including RuO2, MnO2, and Co3O4.15,20–22 Three types
of faradaic processes occur at FS electrodes: reversible adsorption (for example, adsorption of hydrogen on the surface of
platinum or gold), redox reactions of transition metal oxides
(e.g. RuO2), and reversible electrochemical doping–dedoping in
conductive polymer based electrodes.15
It has been demonstrated that these faradaic electrochemical
processes not only extend the working voltage but also
increase the specific capacitance of the supercapacitors.23 Since
the electrochemical processes occur both on the surface and in
the bulk near the surface of the solid electrode, a FS exhibits
far larger capacitance values and energy density than an
EDLS. As reported by Conway et al.,24 the capacitance of a
FS can be 10–100 times higher than the electrostatic capacitance of an EDLS. However, a FS usually suffers from
relatively lower power density than an EDLS because faradaic
processes are normally slower than nonfaradaic processes.25
Moreover, because redox reactions occur at the electrode, a FS
often lacks stability during cycling, similar to batteries.
It is worth mentioning that hybrid ES with an asymmetrical
electrode configuration (e.g. one electrode consists of electrostatic carbon material while the other consists of faradaic
capacitance material) have been extensively studied recently to
capitalize on both electrode materials’ advantages in improving
overall cell voltage, energy, and power densities.14,26,27 In this
kind of hybrid supercapacitor, both electrical double-layer
capacitance and faradaic capacitance mechanisms occur simultaneously, but one of them plays a greater role. In both
mechanisms, large surface area, appropriate pore-size distribution, and high conductivity are essential properties of the
electrode materials to achieve large capacitance, as will be
discussed in a later section.
2.2 ES capacitance, voltage, power, and energy density
Fig. 1 shows that the entire cell can be treated as two
capacitors in series. If the capacitances of the two electrodes,
i.e. positive and negative, can be expressed as Cp and Cn,
respectively, the overall capacitance (CT) of the entire cell can
be expressed as eqn (8):11
1
1
1
¼
þ
CT Cp Cn
Chem. Soc. Rev., 2012, 41, 797–828

ð8Þ

799

Even so. In the case of Cp a Cn (the anode and the cathode have two different electrode materials. it can be seen that aqueous electrolytes have a large limitation in terms of improving both energy and power densities due to their narrow voltage window. A higher specific capacitance does not necessarily mean that this material will be a better ES electrode material. a voltage (V) will build up across the two electrodes. this will be discussed further in later sections. both electrode capacitances have to be increased. Cp = Cn. CT is mainly dominated by the one with smaller capacitance. low volatility. low cost as well as availability at high purity. the electrolyte. aqueous electrolytes can be prepared and utilized without stringently controlling the preparing processes and conditions. eqn (10) indicates that the larger the cell internal resistance. aqueous electrolytes (such as H2SO4. while in organic electrolytes the cell voltage is in the range of 3–3. is also one of the most important ES components. the capacitance and stored charge essentially depend on the electrode material used. the concept of specific capacitance has been adopted as an important parameter in evaluating an ES material. To increase the ES’s cell voltage within the electrolyte’s stability window. Compared to aqueous electrolytes. Therefore. ES containing aqueous electrolyte may display higher capacitance and higher power than those with organic electrolytes. Therefore. low resistivity. in order to increase the power density of ES.g. when carbon is used as the electrode material for aqueous electrolytes.8 1 QV E ¼ CV 2 ¼ 2 2 ð9Þ 1 V2 4RS ð10Þ P¼ where Q denotes the stored total charges in the ES and RS stands for the equivalent inner resistance of the ES. the power density of an ES is normally much higher than in batteries.5 V).. KOH. According to eqn (9) and (10). Therefore. However.2 V. increasing the voltage may be more effective than increasing capacitance or reducing inner resistance in terms of raising the ES’s energy and power densities. 2012. Unfortunately. In evaluating an electrode material for ES. when using this high capacitance material to construct a thick layer and thereby achieve high electrode capacitance for energy storage. a material that forms an extremely thin film on the electrode surface can yield a huge specific capacitance value because of its very low weight. This journal is c The Royal Society of Chemistry 2012 . Soc. Here the value of the ES voltage (V) is dependent on the materials used for the electrode and electrolyte (e. low toxicity. high electrochemical stability. In general. which resides inside the separator as well as inside the active material layers. (1) Aqueous electrolyte. View Article Online If the two electrodes are the same. increasing the capacitance is an effective way to improve energy density. (2) Organic electrolyte. Eqn (9) indicates that the energy density of ES is proportional to its capacitance. while organic ones need strict processes and conditions to obtain ultra-pure electrolytes. Nonetheless. the redox processes involving electron and ion transfers are also very fast). In general. reducing inner resistance can always benefit the ES’s performance in terms of power density improvement. the electrode capacitance may not be as high as expected. whereas the operating voltage is determined by the electrolyte’s stability window. because electrode capacitance is also strongly dependent on the electrode layer structure and the electron and ion transfers within the layer. The electrolyte used in an ES can be classified into three types: (1) aqueous electrolyte.5 V. a sum of electrode and electrolyte resistances. C and RS are three important variables determining the ES’s performance. From both eqn (9) and (10). This is the reason why organic electrolytes are often recommended. much lower than those of organic electrolytes. the higher the energy density will be. it can be seen that both energy and power densities are proportional to the square of voltage. one has to put effort in increasing the values of both V and C or reducing the value of RS. probably due to higher ionic concentration and smaller ionic radius. and (3) ionic liquids (ILs). In order to increase ES’s energy density and power density. (2) organic electrolyte. high ionic concentration and low solvated ionic radius.3 Electrolyte As shown in Fig. which can be expressed as eqn (11): Cs ¼ Ci W ð11Þ where W is the weight in grams of the electrode material in the electrode layer. This can be achieved by improving the specific capacitance of electrode materials as well as optimizing electrode layer structures. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. besides the two electrodes. From these two equations. meaning that the higher the capacitance. the overall capacitance CT would be half of either one’s capacitance. Na2SO4 and NH4Cl aqueous solution and so on) can provide a higher ionic concentration and lower resistance. Compared with organic electrolytes. the corresponding ES is called an asymmetric ES). the cell voltage or supercapacitor voltage window is about 1 V. low viscosity. Note that this specific capacitance is the intrinsic capacitance of the material.Published on 21 July 2011. ES’s inner resistance is much smaller than that of batteries due to the rapid combination of positive and negative charges (even in a faradaic-type ES. should be the major focus. therefore. selecting the type of electrode materials and optimizing electrode structures can achieve high cell voltages. When the ES is charged. another generally used definition is the specific capacitance (Cs). a large disadvantage of aqueous electrolytes is their small voltage window as low as about 1. the corresponding ES is called a symmetric ES. with a unit of Faraday per gram (F g1). 41. In addition. 800 Chem. the lower the power density will be. 2. The theoretical (or maximum) energy (E) and power densities (P) of this ES can be expressed as eqn (9) and (10):7. organic electrolytes can provide a voltage window as high as 3. and Ci is the electrode capacitance (anode or cathode). Rev. namely. reducing cell’s internal resistance. In order to increase overall cell capacitance. Furthermore. The requirements for an electrolyte in ES include: wide voltage window. For example. 1. 797–828 developing electrode materials should be one of the key approaches in ES research and development. it can be seen that V.

. respectively. bis(trifluoromethanesulfonyl)imide. A salt may be melted. making the wetting process slow. resistance. sometimes exceeding 5 V. one issue which should be kept in mind is that the water content in organic electrolytes must be kept below 3–5 ppm. binders. The electrode. resulting in N-methyl-(2-methyoxyethyl)ammonium tetrafluoroborate. and triethylmethylammonium tetrafluoroborate (TEMABF4) have also been used in ES electrolytes. particularly at the temperatures lower than room temperature. Otherwise. as well as good conductivity. Their desirable properties make them promising candidates for ES electrolytes. the cell is subjected to Chem. could help mesoporous nickel-based mixed rare-earth This journal is c The Royal Society of Chemistry 2012 oxide electrodes to reach a higher power density of 458 W kg1. After the completion of electrolyte filling. namely. the electrode fabrication including an active material coating process is the most important step.5 V. and conductivity at a level of ca. tetraethylphosphonium tetrafluoroborate. Rev. It was also reported that N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide might be a very promising IL because it possesses a wider potential range together with high conductivity at room temperature. Besides. but suffers from environmental and toxic problems. ethyl-methyl-imidazolium-bis(trifluoromethane-sulfonyl)imide was used to investigate the relationship between the pore size of carbon electrodes. a higher energy density of 50 W h kg1. and is relatively labor intensive. The amount of electrolyte in the cell is critical. the heart of the cell. This is because of the nanopore level of internal porosity of active materials. chemical stability and low cost. ‘liquified’. 797–828 801 . because excess electrolyte can lead to excessive gassing and leakage in operation. followed by drying the electrode and rollpressing to achieve a uniform electrode coating layer. wide electrochemical window and low vapor pressure. and (5) welding and sealing.4 and 1. with a separator layer inserted between them. firstly. These properties include low vapor pressure. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. trifluoromethanesulfonate. Salts with less symmetric structures have lower crystal-lattice energy and increased solubility. (2) winding.31 A number of electrodes and devices have been prepared using ILs. Then the electrolyte is filled into this separator. bis(fluorosulfonyl)imide or hexafluorophosphate. a dilution of ILs with organic solvents (such as acetonitrile. Acetonitrile can dissolve larger amounts of salt than other solvents. and so on. typically taking one to two days. ILs mixed with the commonly used PC/TEMABF4 electrolytes showed some improvement in conductivity and therefore higher capacity and enhanced low-temperature power density. by providing heat to the system to counterbalance the salt lattice energy. As a result. Low temperature molten salts based on sulfonium [R3S]+ as well as phosphonium [R4P]+ cations are also explored in the literature.5 V. this approach may give rise to other problems such as safety. aluminium foil is used as the current collector because of its high current-carrying capability. aliphatic quaternary ammonium and pyrrolidinium salts display a wider potential range. acetonitrile and propylene carbonate (PC) are the most commonly used solvents. life expectancy.31 To overcome the issue of insufficient electrolyte conductivity of ILs. Generally. and N-methoxyethyl-N-methylpyrrolidinium bis(trifluoro-methanesulfonyl)imide. the process is slow. and the capacitance.31 The challenge for ILs is to design ILs having a wider potential range together with high conductivity in a wide temperature range. In the process of coating electrodes. to achieve a high wettability of electrodes by ILs. Such a system is called molten salts or ILs. capacity.1 N-Butyl-N-methyl pyrrolidinium bis-(trifluoromethane sulfonyl)imide (NBNMPBTSI). determines the ES performance in terms of self-discharge.28. flammability and narrow temperature regimes and so on. wide electrochemical stability window ranging from 2 to 6 V. as well as asymmetric. aliphatic quaternary ammonium salts with anions such as tetrafluoroborate. (3) filling with an electrolyte.29 low flammability. A pair of such electrodes. To extend the temperature range. and cyclic amines such as aromatic pyridinium. 2012. Once the electrodes are prepared. toxicity. Therefore. there is no solvation shell in ILs. which made them remain in the liquid state down to 35 and 95 1C. Soc.1 The main ILs studied for ES applications are imidazolium. the ES’s voltage will be significantly reduced. propylene carbonate or g-butyrolactone) might be feasible. 2.Published on 21 July 2011. but their conductivity is generally lower than that of 1-ethyl-3methylimidazolium-based ILs which remain liquid down to low temperature (o50 1C) and display higher conductivities as high as 102 S cm1 at room temperature. The electrolyte-filling process generally requires special care. the methoxyethyl group has been introduced on the N atom.34 The use of solvent-free 1-butyl-3-methyl imidazolium hexafluorophosphate. and thus ILs can offer a well identified ion size. allowed hybrid ES to be operated between 3. For example. However. they are brought into a glove box with ultra-low moisture. the interface properties of electrode–IL need to be optimized. hydrophobic and highly cycleable properties within a wide voltage window. However. typically about 4. which has low melting temperature. 41. ion size of the electrolyte. as well as an excellent cycle life (no apparent capacity loss during 500 cycles). Among organic electrolytes. Normally. View Article Online This is a large advantage of organic over aqueous electrolytes. For example. organic salts such as tetraethylammonium tetrafluoroborate. (4) testing. 10 mS cm1.33 1-Ethyl 3-methyl imidizolium bistrifluoromethylsulfonyl imide showed better fluidity than NBNMPBTSI.30–32 Room temperature ILs are usually quaternary ammonium salts such as tetralkylammonium [R4N]+. Furthermore. active materials and conductive additives are mixed to obtain a homogeneous slurry with the desired density.4 ES Fabrication and manufacturing Main processes in the fabrication of cells include five steps: (1) coating the electrode.30 Since ILs are solvent-free. and then the slurry is spread onto an etched aluminium foil. ILs can exist in liquid form at the desired temperatures.35 with good conductivity. is wound around a central mandrel into the desired shape. pyrrolidinium. For example. high thermal and chemical stability. a wide range of operating temperature. pyrrolidinium. strictly controlling the preparation process is necessary for achieving both high performance and durability.30 The chemical–physical properties of these ILs strongly depend on the type of cation and anion. (3) Ionic liquids (ILs). imidazolium and saturated piperidinium. PC-based electrolytes are friendly to the environment and can offer a wide electrochemical window.

In order to match different applications. The principles of voltage balancing have two types: passive and active balancing. During formation. Ci (=Cp or Cn). then measure this electrode in the chosen electrolyte using electrochemical cyclic voltammetry (CV) to record cyclic voltammograms of the material. the difference in self-discharge will make the voltages of all cells unequal. Passive voltage balancing. from which the capacitance can be calculated. If the charge (Q in eqn (9)) accumulated inside the electrode layer is measured using the area under the cyclic voltammogram in either direction in a potential window from E1 to E2. However. 2. Under extreme situations. View Article Online cycling test (for two to five formation cycles).5. of this electrode layer can be obtained by eqn (12): . The normal way to carry out material capacitance measurements is to coat the chosen material onto an inert electrode surface. The cells may be cycled further to establish stable capacity. the life expectancy of ES will be shortened significantly. which may be connected with other modules. some cells’ voltages may be even negative (called ‘‘cell reversal’’). ES cells are connected in series or in parallel to obtain the desired output voltage or energy capacity.Published on 21 July 2011. Some manufacturers will follow formation with evacuation and final welding and sealing. the abnormal cells are removed away. Active voltage balancing is instructed using a controller with an individual charging system. Several ES cells are connected to be one module. If measures are not taken to balance the voltages. depending on applications. which can cause large power loss. These differences among cell voltages can also alter with the change of operating voltage of the ES module. the capacitance. refers to instantly balancing the voltage difference. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59.1 Cyclic voltammetry.5 ES electrode material evaluation 2. while others will pre-seal the cell prior to formation.

.

.

Q .

.

Ci ¼ .

.

ð12Þ E2  E1 .

which often involve irreversible interconversion of the chemical electrode reagents and irreversible phase changes. At low frequency ranges (less than 1 Hz). a pure capacitor should display a parallel line to the imaginary axis of the Nyquist plot. ES have several advantages: (1) High power density. and at the high frequency region the supercapacitors behave like a pure resistance. the impedance implies the conductivity of both active materials and electrolyte. (2) Long life expectancy. Fig. The high-to-medium frequency region (104 to 1 Hz) shows pseudocharge transfer resistance. This Bode plot shows that the capacitance decreases with increasing frequency. It can provide the relationship between the imaginary part of impedance |Z| and f. However.9 From the Nyquist plot. electrochemical impedance spectroscopy (EIS) is also a useful tool for determining the capacitance of ES materials. indicating that the electrolyte ions probably cannot penetrate into micropores under high frequencies.1 Advantages of ES. For example.37 This deviation from the parallel line may be attributed to two reasons: one is the different penetration depth of the alternating current signal in virtue of pore size distribution at both electrodes. log f curve. is plotted against the real part of impedance. 2 compares specific power versus specific energy of modern storage devices. 797–828 Z(f) 0 . challenges. the charge–discharge reaction will not necessarily be limited by ionic conduction into the electrode bulk. a charge transfer resistance can be obtained from the diameter of the semicircle on this plot. Z(f)00 . The capacitance can be calculated using C = 1/(2pf|Z|) using a linear portion of a log |Z| vs.. Since an ES stores electrical charges both at the electrode surface and in the bulk near the surface of the solid electrode.41 (Cited from the permission of Database r2009 IEEE.6. The storage of electrochemical energy in batteries is realized through faradaic reactions. and the energy can be taken from it very rapidly.2 Electrochemical impedance spectroscopy (EIS). 2012. These rapid rates lead to high power density in ES. Compared to batteries. the charging time is normally on the scale of hours.g. Theoretically.36. and applications of ES 2. In addition to cyclic voltammetry. the plot shows a line with the inclined angle between 451 and 901 against the real axis. Rev.1 s. 2. an ES can be fully charged or discharged in seconds (B30 s). Fig. rather than within the entire electrode.) This journal is c The Royal Society of Chemistry 2012 . corresponding to the ion diffusion mechanism between Warburg diffusion and ideal capacitive ion diffusion (pseudo capacitance). so the charging and discharging rates are much faster than the electrochemical redox reactions inside batteries. 2 Specific power versus specific energy of modern storage devices.38 2.6 Advantages. It is clear that ES display a much higher power delivery (1–10 kW kg1) when compared to lithium ion batteries (150 W kg1). At high frequency (larger than 104 Hz). 5 to 10 mV) over a wide range of frequency f (e.39. 1 mHz to 1 MHz). which is associated with the porous structure of the electrodes. within 0. Soc.35. where the imaginary part of impedance.. 802 Chem. in normal cases. The EIS can also be expressed as a Nyquist diagram.19.40 For batteries.. 41.g. leading to abnormal capacitance.29 The most popular way to run EIS measurements is collecting the ES impedance data at the open-circuit potential by applying a small amplitude of alternative interrupting potential (e. giving rise to pseudocapacitance. the impedance plot is the characteristic feature of pure capacitive behavior. the other is the redox reaction at the electrode. which is called the Bode plot.5.

this has been considered a major obstacle to their practical use. compared to other energy storage systems such as batteries and fuel cells. up to 1 000 000. (3) High self-discharging rate. ES maintain their capacitance and thus are capable of being recharged to their original condition. and the energy loss to heat during each cycle is relatively small and readily removed (i.. The life expectancy for ES is estimated to be up to 30 years. including powerful acceleration. (7) Safety. With advantages such as long lifetime and high power density. the coating may be around 150 microns. (6) Environmental friendliness. in particular those with a high surface area.14 not to mention the cost of a rare metal oxide such as RuO2. mobile phones. Most rechargeable batteries if left on the shelf unused for months will degrade and become useless due to self-discharge and corrosion. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. which is much longer than for lithium ion batteries (1000–10 000 cycles and a life expectancy of only 5–10 years).. if ES use organic electrolytes. At present. the separator and the electrolyte can also boost the expense. Rev. ES. although fast redox reactions are involved during charging and recharging. Currently. braking energy recovery. and storage of the energy generated by solar cells. Gore’s electrode.14 (4) High efficiency. environmental friendliness. while for power sensitive applications. ES can run deeply at high rates for 500 000–1 000 000 cycles with only small changes in their characteristics. heat management is easy). If a large energy capacity is required for an application. ES are reversible with respect to charging and discharging throughout their complete operating range of voltage. Moreover. and increased battery life. operating temperatures.43–46 2.14–17. In contrast.2 Challenges for ES.3 Applications of ES. carbon materials. However. In addition. Another advantage of supercapacitors is their long shelf life. in general. 797–828 803 . View Article Online In contrast. shelf life. (4) Industrial standards for commercialization. which is prepared by coating the activated carbon–PTFE composite on an etched aluminium collector. which can give a cell voltage of 2. batteries’ poorer cycle life makes their frequent replacement expensive (adding 20% onto the price of battery operated appliances). It is reported that ES can sit unused for several years but still remain close to their original condition. in particular lithium-ion batteries. so an ES can have almost unlimited cyclability. it is necessary to put some effort on ES standard establishment for different applications.23 Combining ES with batteries can yield improved performance in hybrid electric vehicles. no or negligibly small chemical charge transfer reactions and phase changes are involved in charging and discharging.6.42 (5) Wide range of operating temperatures.47–54 For example. and safety.9. Commercially available ES can provide energy densities of only 3–4 W h kg1. Although ES have many advantages over batteries and fuel cells. Therefore. electrode layer thickness and porosity and so on. efficiency. In normal circumstances.55 In addition. 2. the thickness is probably about 100 microns. exhibits a BET surface density of B1800 m2 g1. a thickness of 0.14. pulse laser techniques. This is advantageous for military applications. (1) Low energy density. driving up the cost. we are still not able to search out generally available industrial standards for ES at this moment. reversibility. The typical operating temperature for ES ranges from 40 to 70 1C. where reliable energy storage is required to run proprietary electronic devices under all temperature conditions during war. For example. electrode structure. ES has the potential to play an important role in complementing or replacing batteries in the Chem. carbon/carbon ES with capacitance of 50–5000 F have become commercially available. when energy is stored in an ES. The costs of raw materials and manufacturing continue to be major challenges for ES commercialization. Thus. due to the variety of applications as well as limited commercial products. excellent cold weather starting. Low energy density is the major challenge for ES applications in the short and medium terms. This performance was achieved when charging the device at 400 W kg1 from 100% to 50% of the rated voltage. for practical purposes carbon and RuO2 are the most common electrode materials used in commercial ES. they also face some challenges at the current stage of technology. ES can solve these problems. ES have a low duration and a high self-discharging rate of 10–40% per day. 2. For example. electrical tools. the requirement for electrode thicknesses should be strongly dependent on the ES applications. ES suffer from limited energy density (about 5 W h kg1) when compared with batteries (>50 W h kg1). their cost is far from negligible.e.3. ES have become very competitive choices for applications such as electric vehicles.23 (3) Long shelf life. This means that the cycle efficiency of ES is high (around 95%) even when operating at rates above 1 kW kg1. Although this kind of ES is commercially available. in battery powered electric vehicles.3 mm and an average pore diameter of B2 nm. although self-discharge over a period of time can lead to a lower voltage. With their many advantages. 2012. ES are much safer than batteries. their life expectancy is also much longer than that of batteries. ES do not need any maintenance during their lifetimes and can withstand a huge number of charge–discharge cycles. In summary. do not contain hazardous or toxic materials. uninterruptible power supplies. batteries with lower power density cannot meet peak load requirements. originating from accelerating or climbing. in memory back-up. ES are superior in the areas of life expectancy (without any noticeable performance degradation after long-term operation). a larger supercapacitor must be constructed. Soc. Such longevity is impossible for batteries even if the depth of discharge is as small as 10–20% of the overall energy. Even for FS. and their waste materials are easily disposed. electric hybrid vehicles. 41. However.31 Actually. power density. ES can function effectively at extremely high and low temperatures.15. This journal is c The Royal Society of Chemistry 2012 (2) High cost.6.23. for energy sensitive applications. as shown in Fig. Gore’s commercial electrode may give us some sense what the standards may look like. digital cameras. it is necessary to establish some general industrial standards such as performance.Published on 21 July 2011. are presently expensive (US$50–100 per kg).25.7 V with a typical specific energy of 4 W h kg1. digital communication devices. the electrolyte used in such kind of ES is acetonitrile. The main cost of an ES arises from its electrode materials.43 In some applications.

3. Electrode materials As discussed above. leading to a bright future for ES.23 Other manufacturers of ES include SAFT (France). However. also indicates good capacitive properties for ES.43. the capacitance predominantly depends on the surface area accessible to the electrolyte ions.1 the pore size of electrode materials that yielded maximum double-layer capacitance was very close to the ion size of the electrolyte (with respect to an ionic liquid electrolyte).54. electrical conductivity. Copper (USA). the measured capacitance of various materials does not linearly increase with increasing specific surface area.63–67 and (3) metal 804 Chem. ELIT (Russia).61. the total supercapacitors market generated revenues of about $99. 81 with permission from Elsevier. then make the capacitance of materials with larger pores decreased according to eqn (1). lower cost.69 IrO2.9 million in revenue generated by 2014. suggesting that they are appropriate capacitive materials for ES. ESMA (Russia).75 SnO2.57 The ES market is moving ahead steadily and changing significantly every year.76 V2O5. and 160 mV s1). Maxwell (USA).74 Co2O3. involving both pore sizes and pore-size distribution for a given overall specific area (m2 g1) of the material. The important factors influencing their electrochemical performance are specific surface area. Since not all the specific surface area is electrochemically accessible when the material is in contact with an electrolyte. the market development of ES is still in the early commercialization stage. rather than storing them in the bulk of the capacitive material.. 40. Among these.72 NiO. ES occupy less than 1% of the world market for electrical energy storage (batteries and supercapacitors). PowerSystem Co. a definition called the electrochemical active surface area may be more accurate in describing the electrode capacitance behavior. Therefore. Kold Ban (USA). The advantages of carbon materials include abundance. In general.5 A g1. carbon materials store charges mainly in an electrochemical double-layer formed at the interface between the electrode and the electrolyte. (b) galvanostatic charge–discharge curves of the AMCMBs/CNTs compound electrode at a constant specific current of 0. such as RuO2.6 million. As shown in Fig. Cap-XX (Australia).Published on 21 July 2011. 797–828 oxides. (Japan). Continuing improvements will open new markets. and Panasonic (Japan) occupy a large share of the ES market. Elna (Japan).1 Carbon materials Carbon materials are considered prospective electrode materials for industrialization. Currently. EVANS (USA). 80. Therefore. View Article Online energy conversion and storage fields.59. easy processing. and surface functionality. NESS (South Korea). and both larger and smaller pores led to a significant drop in capacitance.77–79 and MoO. NEC (Japan).) This journal is c The Royal Society of Chemistry 2012 .58 Apparently. good electronic conductivity. the electrode materials of ES can be categorized into three types:15.68.56 Due to their relatively low energy density and high cost. 41.62 (2) conducting polymers. AVX (USA). with $205. ES capacitance strongly depends on the surface area of the electrode accessible to the electrolyte. Thus. The pore size of the electrode material plays an important role in the electrochemical active surface area. 2012. Therefore. In 2007. It is expected that a compound annual growth rate of 10.71.14. Rev.1 The main market targeted by ES manufacturers in the coming decades may be transportation. the capacitance and charge storage of ES intimately depend on the electrode materials used.80 3. Econd (Russia). the capacitance of ES heavily depends on the specific surface area of the electrode materials.3 3. and wide operating temperature range. EPCOS (USA). for those electrochemically accessible surface area or useful surface area. At present. and Chubu Electric Power (Japan). Soc. including hybrid electric vehicles and metro trains. non-toxicity. pore-size distribution.81 cyclic voltammetry curves of carbon materials have good rectangular shapes. Korchip (South Korea). According to Largeot et al. Normally.81 (Reprinted from ref.. pore shape and structure. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. increasing the pore size can also increase the average distance d between the pore wall and the center of an ion. specific surface area and pore-size Fig. higher specific surface area.45.70 MnO2.1 The porosity relevant to the development of high capacitance is itself not a simple parameter.73. further developing new materials with high capacitance and improved performance relative to existing electrode materials is the most important method to overcome these challenges. high chemical stability.9% will be achieved for the next ten years.60 (1) carbon materials with high specific surface area.23 Carbon-based electrochemical capacitors are close to electrochemical double-layer capacitors. Their galvanostatic charge–discharge profile. 3 (a) Cyclic voltammetry curves of an activated mesocarbon microbeads (AMCMBs)/CNTs compound electrode at different scan rates (10. with its triangular symmetrical distribution.

leading to reduced ES performance. 4. resulting in barriers to electron transfer. micropore volume. High surface area carbon materials mainly include activated carbon.122 However. particularly in an organic electrolyte. and contamination. in most cases14 the measured specific capacitances of carbon materials in real supercapacitors are less than those stated in the literature.23 In addition.6 Many methods have been investigated to increase the specific surface area.61. Besides enhanced capacitance.95 The performance of these carbons as ES electrode materials has been described in detail in the literature.125 and 10–35 F g1 for CNTs. introducing surface functional groups or heteroatoms on the surface of carbon materials appears to be an effective way of improving an electrode’s capacitance.96–104 These methods can effectively make micropores and defects on the carbon surface. leading to an increase in the specific surface area. surface functionalization has also been considered an effective way to improve the specific capacitance of carbon materials. and (3) good electrolyte accessibility to the intrapore space of carbon materials. According to these three properties. In this situation.15 the carbon for double-layer type supercapacitors must have three properties: (1) high specific areas. there is still no common understanding or agreement about the effect of optimal pore size on the performance of carbon electrode materials. which lead to a remarkable pseudocapacitance. alkaline treatment.3 leading to a 5–10% increase in the total capacitance. In general. Even today. in the process of selecting supercapacitor electrode materials the general rule is to obtain a high and accessible specific surface area with good electrical conductivity.110..106–115 It is believed that surface functional groups or heteroatoms can help the adsorption of ions and then improve the hydrophilicity/lipophilicity of the carbon materials. Some studies have reported that pore sizes of either 0. and sulfur. their high resistivity. and moderate surface modification so as to optimize overall capacitance and conductivity without compromising stability. depending on the concentration of functional groups.6. leading to enhanced wettability and facilitated rapid electrolyte ion transport within the micropores.123 In summary. the degradation of these materials may be accelerated by possible over-charging/discharging during sustained operation.4 or 0. a high cycle life (>100 000) might not be achievable. Rev. due to the contact resistance between carbon particles. For example. Another way to increase the capacitance is to introduce conducting polymers into the carbon materials. 797–828 805 .105 the match between pore size and ion size was demonstrated through achieving a maximum capacitance. gives rise to a high internal series resistance. specific capacitance can reach 170 F g1 by introducing a polypyrrole into multiwalled carbon nanotubes (MCNTs).84. As suggested by Conway. Soc. Thus. introducing 1 wt% of RuO2 into a carbon electrode material can increase the capacitance of the MCNTs from 30 to 80 F g1 owing to the pseudocapacitive behavior of RuO2. specific capacitance is sometimes not directly proportional to the specific surface area. the surface area inaccessible to electrolyte ions124 also impedes the capacitance performance of carbon materials. the introduction of nitrogen has been investigated most extensively This journal is c The Royal Society of Chemistry 2012 Fig.5 M H2SO4 at a scan rate of 50 mV s1 for multiwalled carbon nanotubes.123 Note that these values are strongly dependent on the microtexture of the nanotubes. This is because not all micropores in the electrode layer are necessarily accessible to electrolyte ions. number of defects. carbon materials with larger specific surface areas have a higher capability for charge accumulation at the electrode/electrolyte interface. 116 with permission from American Chemical Society.88 carbon nanotubes (CNTs). The heteroatoms commonly present in a carbon framework are oxygen. due to the rapid degradation of conducting polymers. and plasma surface treatment with NH3. 41. carbon materials with high surface area and suitable porous structures seem to be ideal materials for ES in terms of specific power and cycle life.82–87 carbon aerogels. rational pore distribution. the presence of functional groups on the surface of carbonaceous materials may induce faradaic redox reactions.91–94 and carbon nanofibres.117–120 It must be noted that the risk of electrolyte decomposition induced by active surface functional groups (especially oxygen-containing acidic groups) is also increased. It is believed that future research areas in carbon materials are development of carbon electrodes with higher specific surface area. with values in the range of 75–175 F g1 for aqueous electrolytes and 40–100 F g1 for organic electrolytes. carbon-supported transition metal oxides may be used for their enhanced stability. At the same time. resulting in limited capacitance values of only 40–160 F g1 for both activated carbon and carbon aerogels.112 In addition.121. Among these. In addition to high specific surface area and appropriate pore size. and the operating ES voltage. However. an electrode modified with RuO2 has also exhibited a longer cycle life compared to that of carbon-polymer composite materials. Chem. As shown in Fig. while a pore size of around 0. steam or CO2 activation. come from the redox reaction (a faradaic process) of oxygenated groups on the surface of carbon nanostructures.9 However.7 nm could be suitable for aqueous electrolytes. the electrode surface area. For example.114.90 templated porous carbons.and interparticle conductivity in porous matrices. nitrogen. the intrinsic electrical resistance of the material may increase because the bonded heteroatoms possess higher reactivity. in the order of 1000 m2 g1.Published on 21 July 2011. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. View Article Online distribution are the two most important factors affecting the performance of carbon materials.84. Moreover.116 (Reprinted from ref.1.116 redox peaks. boron.8 nm might be better for organic electrolytes. (2) good intra. 2012. Unfortunately. including heat treatment. 4 CV plots in 0.89.86 In recent papers.) in the literature.

For example. This is an n–p type ES. and when reduction occurs. and then compromise CPs as electrode materials. When oxidation takes place. 6. 41. However. such as poly(3-fluorophenyl)thiophene. This kind of material is generally classified into two types: conducting polymers and electroactive metal oxides. as a conventional supercapacitor electrode does. 2012. such as polypyrrole/polythiophene.3.8–1 V.148 In addition. and (3) Type III (symmetric).150 These values are much higher than the capacitance of electrodes based on commercial activated carbons.142.19. Because pseudocapacitance may be 10–100 times greater. and adjustable redox activity through chemical modification.147 synthesized a composite material containing PPy. 5. to be 815 F g1. are capable of achieving a peak specific capacitance of over 990 F g1 for a single electrode in an organic electrolyte at a potential scan rate of 50 mV s1. vapor-grown carbon fibres. high voltage window. 797–828 The common electrical CPs in supercapacitor applications are polyaniline (PANI). 3.1 Conducting polymers (CPs). are termed as ‘p-doped’.. these polymers show poor conductivity in the reduced state (at more negative potentials) and produce a low capacitance. which generate delocalized ‘n’ electrons on the polymer chains. This is the reason why they often find use as cathode materials. swelling and shrinking of CPs may occur during the intercalating/deintercalating process.1 V in nonaqueous solutions. not just on the surface. Recently. ions are transferred to the polymer backbone. the selection of a suitable potential range for ES performance is crucial. The corresponding cyclic voltammetry curves are shown in Fig. CPs possess many advantages that make them suitable materials for ES. The voltage window is up to 3. Kim et al. introduced by oxidation on the repeating units of polymer chains. The results indicate that dendritic CPs. where a platinum mesh was used as the counter electrode. CPs-based ES systems have three configurations:15.4-b 0 -dithiophen4-one)). Beyond this strict potential range. Sivaraman et al. respectively. an acidic solution or a protic ionic liquid is required. high storage capacity/ porosity/reversibility. as shown in Fig. Early researchers termed the oxidation–reduction processes of these polymers as ‘doping’. a highly porous. the relatively poor stability of the n-doped state could lead to a continuous decrease of its ES performance upon cycling. Soc.133 Electronic conductivity can thus be induced in such a kind of polymers by oxidation or reduction reactions. Hence. the specific capacitance of This journal is c The Royal Society of Chemistry 2012 . These problems often lead to mechanical degradation of the electrode and fading electrochemical performance during cycling. This type is a p–p 0 ES. the specific capacitance of an electrode modified with pure PANI was reported by Li et al. Consequently. and achieved specific capacitances of B588 and B550 F g1 at potential scan rates of 30 and 200 mV s1.132. 3.2. therefore.4-ethylene-dioxythiophene) (PEDOT)146.140 polypyrrol (PPy). PANI and PPy can only be p-doped since their n-doping potentials are much lower than the reduction potential of common electrolyte solutions. These redox reactions in the conducting polymer come about throughout its entire bulk. the ions are released from this backbone into the electrolyte. the polymer may be switched to an insulating state (un-doped state). and carbon with a thickness of 5–10 nm by in situ chemical polymerization. Unfortunately. PTh and its derivatives are both n.149 was explored as a candidate material for ES because of its high stability. Using an electrochemical deposition method. 806 Chem.and p-dopable. Electrodes use the same polymer which can be both p.. but also undergo fast and reversible surface redox reactions (faradaic reactions). For example.1-b. while negatively-charged polymers generated by reduction are termed as ‘n-doped’. amorphous polymer film on a gold plate was obtained. they are usually employed as the positive electrode with a negative electrode made from another material such as carbon.View Article Online Published on 21 July 2011. This type of ES is named as a p–p ES in which both electrodes use the same p-dopable polymer.151 For polythiophenes. Therefore.152.145 It seems that all CPs can only work (supplying charges) within a strict potential window. CP-based ES often remarkably degrade under less than a thousand cycles.and n-doped in the same molecule. a protic solvent. The positively-charged polymers. When fully charged.144 Substitution at the 3-position of PTh with an aryl group can result in more positive n-doping potentials.146 Table 1 shows the potential windows for various conductive polymers for ES applications. typically in the range of 10–50 mF cm2 for a real electrode surface. such as low cost. Two different p-dopable polymers with a different range of oxidation and reduction electroactivities are used. and as the potential is too negative.15 CPs can be positively or negatively charged with ion insertion in the polymer matrix to balance the injected charge. They not only store charges in the double layer. The voltage window is 0.133. materials based on an electrical doublelayer mechanism have limited specific capacitance.2 Faradaic materials As mentioned above. one electrode is in the full p-doped (positive) state and the other in the uncharged state. which was degraded by B50% in the first 1000 cycles at a constant current density of B2 mA cm2. A typical example is poly(cyclopenta(2.29 It should be noted that PANI requires a proton to be properly charged and discharged. high conductivity in a doped state. the polymer may be degraded at more positive potential.127–131 CPs offer capacitance behavior through the redox process. supercapacitors made of redox-active materials bearing pseudocapacitance are highly desirable126 as the next generation of ES. The potentials of these doping processes are determined by the electronic state of p electrons.153 As shown by P.141 polythiophene (PTh). based on a bithiophene–triarylamine backbone. Type III is considered a significant advance in CPs-based ES in terms of materials design and the stored energy density. considerable efforts have been devoted in recent years to developing electrode materials with pseudocapacitance. the processes are highly reversible. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. poly(3. the ES device formed with PPy electrodes showed an initial capacitance of 120 F g1.57 Because the charging and discharging reactions do not involve any structural alterations such as phase changes. Rev. There are many reports on applying the above CPs to ES. low environmental impact. (2) Type II (asymmetric).143 and their corresponding derivatives.134–139 (1) Type I (symmetric).

4 0–0. Ag|AgCl) 0.0 M M M M H2SO4 Na2SO4 H2SO4 H2SO4 0. II: defined by A. PMeT: poly(3-methylthiophene).2–0. SCE) 0–1. Fig.5 (vs. PC: propylene carbonate. SCE) 1. SCE) 0–1.5 0. 6 Cyclic voltammetry curves normalized to specific capacitance (F g1) for TTPA electrochemically polymerized on Au/PI with charge densities of 44 mC cm2 (A) and 16 mC cm2 (B).1 A g1 174 151 175 176 1.2–0.6–0.) Fig. SCE) 0–0.6 5 mV s 163 670 (3-Electrode) 344 (Type I) 506 (3-Electrode) 192 (Type I) 230 (3-Electrode) 290 (3-Electrode) 276 (Type I) 87 (Type II) 433 (3-Electrode) 165 (Type I) 427 (3-Electrode) 197 (3-Electrode) 103 (3-Electrode) 302 (3-Electrode) 602 (3-Electrode) 740 (3-Electrode) 158 (3-Electrode) 207 (3-Electrode) 320 (3-Electrode) 1030 (3-Electrode) 409 (3-Electrode) 120 (Type I) 80 60 160 (AC as the negative electrode) 1.5 mA cm2 50 mV s1 3 A g1 0. SCE: saturated calomel electrode. 41.) the poly(3–methyl thiophene)(PMeT) ES could be decreased by 16. Hg|HgO) 0. PANI: polyaniline.154 PANI could also suffer from a similar serious problem derived from the volumetric changes during the doping/dedoping process. nanorods.2–0.0 M H2SO4 2 mV s1 2 mV s1 2 mV s1 3 mA cm2 0..62 A g1 1 mV s1 1 A g1 5 mV s1 10 mA cm2 168 1.0 1. AgCl|Ag) 5.5 M M M M M M M M LiClO4 KCl KCl LiClO4 in AC KOH NaCl Na2SO4 Na2SO4 0. Chem. It seems that nanostructured CPs such as nanofibers.138 Another report showed This journal is c The Royal Society of Chemistry 2012 that the PMeT polymer.6 0.4–0.22 wt% mica Ppy-67.8 (vs.5–0. Rev.8 V.8 (vs.150 (Reproduced by permission of the Royal Society of Chemistry.8–0. PFPT: poly[3-(4-fluorophenyl)thiophene]. Type I.0 M H2SO4 0–0.0 6.2 A g1 1.0 (vs.4–0.9 A g1 40 mA cm2 2 mV s1 164 177 146 0–1.0 1.0 0. Ag|AgCl) 0.0 0.5 0.7 (vs. Hg|Hg2SO4) 0.6 (vs.0 1. AN: acetonitrile.0 M M M M M M H2SO4 H2SO4 H2SO4 KOH TEABF4 in AN TEABF4 in AN 0.6 (vs..6 (vs. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59.0–0(vs. which was synthesized with a template by electrochemical polymerization of 3-methyl thiophene.2–0. AgCl|Ag) 0.36 wt% mica Ppy-RuO2 Ppy-MnO2 PANI-Ti PANI-80wt% graphene PANI-50wt% graphene PANI-10wt% graphene MPANI/CNTs PANI-Si PEDOT-MCNTs (70 : 30) PEDOT-MCNTs (80 : 20) Specific capacitance/F g1 Electrolyte Voltage window/V Current load or scan rate 1 Reference 320 (Type II) 1.5 (vs.5 2. TEABF4: tetraethylammonium terafluoroborate.View Article Online Table 1 Specific capacitance of CPs-based composites CPs-based composite Ppy-20wt%MWNTs/ PANI-20wt% MWNTs PANI-20 wt% MWNTs Ppy-20 wt% MWNTs Published on 21 July 2011. 5 Scanning electron microscopy image of pTTPA films electrochemically deposited with cyclic voltammetry between 0 and 1 V at a rate of 100 mV s1 (A) and enhanced magnification image (B). decreased by B16% the specific capacitance of the PMeT/PVDF|PC/EC/1 M LiClO4|PMeT/PVDF ES (type III) within 150 cycles.0 M H2SO4 5 mV s1 169 170 171 172 173 Note: PPy: polypyrrole.0 1.2% during the first 200 cycles. PTh: poly(thiophene).5 1.0 1. the following ways have been investigated: (1) Improving CP materials’ structures and morphologies.4–0. To mitigate the challenge of low stability.2 0–0.0 1.0 0.0 1. Rudge et al. 3-electrode: standard 3-electrode cell.139 PEDOT: poly(3. Hg|HgO) 0–1. low cycling stability is a very serious problem for CP materials when they are used in ES. PEDOT-Ppy (5 : 1) Ppy-CNTs//PmeT-CNTs PPy-65 wt% carbon Ppy-graphene Ppy-MCNTs Ppy-29. The loss of specific capacitance of the PANI nanorods could be as high as 29. Soc.5% after only 1000 cycles between 0.0 0.2 and 0.155 Apparently.150 (Reproduced by permission of the Royal Society of Chemistry.4-ethylenedioxythiophene).8 (vs.7 (vs.0 6. 797–828 807 . 2012.0 1.8 (vs. SCE) 0. Ag|Ag+) 0–0. AC: activated carbon.

Furthermore. and then a high specific capacity.147. current load.7 V (vs. large surface area.156 (2) Hybridizing ES. more effort is still needed to optimize these parameters to achieve optimized electrochemical properties for these CP-based composites for ES applications. and mass ratio of the components as well as cell configuration.158. 164 with permission from Elsevier. They not only store energy like electrostatic carbon materials but also exhibit electrochemical faradaic reactions between electrode materials and ions within appropriate potential windows.159 For example. scan rate. From Table 1. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59.) 5000 cycles) between 0.Published on 21 July 2011. 3.164 (Reprinted from ref. and (4) using CNTs with special mechanical properties as a support can reduce the cycle degradation caused by mechanical problems or volume changes.137. 41.151 Regarding composite electrodes. SCE) at 10 mA in a 1 M H2SO4 electrolyte.164 From this figure. four points can be summarized:164–167 (1) the superior conducting network consisting of CNTs allows for efficient charge transport in the composite electrode.143.155 Zhang et al. the ES based on two identical MnO2/PPy nanocomposite electrodes. a hybridized ES with a p-doped polythiophene derivative as the positive electrode and activated carbon as the negative electrode could maintain a good performance cyclability of over 10 000 cycles with a better performance than double-layer carbon-based ES in terms of power density. and superior conductivity had high specific capacitance (1030 F g1). adding carbon. mechanical stability and processability. a relatively stable performance was seen for the subsequent 4000 cycles at a constant current density of 2 mA cm2.2 Metal oxides/hydroxides. Since CPs in the n-doped state possess poorer stability than those in the p-doped state. as well as mitigating mechanical stress. (2) the metal can exist in two or more oxidation states that coexist over a continuous range with no phase changes involving irreversible modifications of a 3-dimensional structure.) 808 Chem. and nanotubes could reduce cycling degradation problems caused by volumetric changes or mechanical forces through providing a relatively short diffusion length to enhance the utilization of electrode materials. hierarchical porous structure.. (2) the high specific surface area and the nanometre size ensure high utilization of electrode materials. 8. especially carbon nanotubes. which could reduce the cycle degradation problems of PANI caused by volume changes or mechanical problems. initially gave a much higher specific capacity of B180 F g1. It was demonstrated that composite CP electrodes could enhance the cycling stability by improving their chain structure. Soc. Some examples of these composites and their electrochemical properties are given in Table 1.164 showed that a PANI/CNT composite electrode (Fig. which are also dependent on the parameters such as the constituents of composites. ordered nanometre-scale PANI whiskers only showed about 5% of capacitance loss after 3000 consecutive cycles at a current density of 5 A g1. in comparison with pure PPy electrodes whose loss in specific capacitance was close to 50%. This journal is c The Royal Society of Chemistry 2012 . Because the properties of CPs can be greatly improved through preparing a CP-based composite.161–163 For example.4% loss from their initial specific capacitance after 1000 cycles.157 replacing an n-doped polymer at the negative electrode by a carbon electrode seemed feasible. and other metal compounds. and high stability (5. electrolytes used. only showing 5. metal oxides can provide higher energy density for ES than conventional carbon materials and better electrochemical stability than polymer materials. Rev. (3) the hierarchically porous structure can enhance the ionic conductivity. conductivity.164 (Reprinted from ref. 7 SEM images of (a) CNT array and (b) polyaniline/CNT array composite. 164 with permission from Elsevier. into CPs is also believed to be an effective solution for improving the mechanical and electrochemical properties of electrodes. recent studies mainly focus on CP-based composites which involve carbon. The roles of the CNT array in this composite are schematically shown in Fig.2 and 0.178 The general requirements for metal oxides in ES applications are:15 (1) the oxide should be electronically conductive. 8 Schematic representation of the microstructure and energy storage characteristics of a polyaniline/carbon nanotube (PANI/CNT) composite electrode. This was attributed to the use of MWCNT with exceptional mechanical properties as a support and the formation of the charge-transfer complex. one can see that the composite materials can give a wide distribution of capacitance values. 797–828 Fig. Therefore.2. the sulfonated multi-wall carbon nanotube (MWCNT) in the composites can greatly improve the cycle stability of PANI.146 For example. View Article Online nanowires. inorganic oxides/hydroxides. For example.5% capacity loss after Fig. 2012. superior rate capability (95% capacity retention at 118 A g1). In general. in a three-electrode cell with a 1 M H2SO4 solution as the electrolyte.160 (3) Fabricating composite electrode materials. and also showed a relatively stable performance degrading only by B10% in the initial 1000 cycles. 7) with nanostructure.

3.204 (3) The crystallinity of RuO2xH2O. Normally. highly reversible redox reactions. 2012. To date. one of the most effective ways to increase the specific capacitance is to increase the specific surface area of RuOx. the changes in the valency state of RuO2 are quite different. and RuO4. Soc. The higher the specific surface area.200 As reported in the literature.View Article Online Published on 21 July 2011. which in turn show different sensitivities toward crystallinity. These hydrous regions can allow appreciable protonic conduction for highenergy and high-power electrochemical capacitors.196 Thus. amorphous ruthenium oxide materials in the H2SO4 electrolyte exhibited a maximum capacitance of 720 F g1 upon calcination at 150 1C.179–181 With RuO2 electrodes.59. such as depositing RuO2 films on substrates with a rough surface. The pseudocapacitance of RuOx comes mainly from the surface reactions.202 also demonstrated the importance of hydrous regions (either interparticle or interlayer). inhibiting proton intercalation and leading to a decrease in specific capacitance. the capacitance dropped to 29 F g1 and the anhydrous phase displayed a capacitance of only 0.. hydrous ruthenium oxide is a good proton conductor (H+ diffusion coefficient reaches 108–1012 cm2 s1).5H2O 2 5 20 50 200 500 24 22 19 18 16 15 124 112 93 82 68 61 342 331 316 304 280 256 Chem. etc. good thermal stability. so it prevents protons from Table 2 Specific capacitance obtained by cyclic voltammetry at various scan rates for RuO2xH2O202 (reprinted from ref.182 For a crystalline state in a KOH electrolyte. double-layer charging only contributes to about 10% of the accumulated charge. and vanadium oxide. RuO4 . while electrolytically formed RuO2 can have more hydrated oxide states in which a substantial volume fraction of Ru atoms is redox active.201 hydrous ruthenium oxide (RuO20. and (3) the protons can freely intercalate into the oxide lattice on reduction (and out of the lattice on oxidation). Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59.197–199 and fast ionic conduction via hydrous micropores. The maximum specific capacitance of the RuO2xH2O film electrode was as high as 786 F g1. RuOx has been the most extensively studied candidate due to its wide potential window.1 RuO2.5H2O) showed a capacitance as high as B900 F g1. so the transfer of cations in the solid phase is critical for a RuO2 electrode. manganese oxide.190–194 For example.125 A specific capacitance as high as 1300 F g1 was also reported for nanotubular arrayed electrodes incorporated with hydrous ruthenium oxide.183 The corresponding mechanisms were suggested to be as follows. rapid reversible electron transfer is accompanied by electro-adsorption of protons on the surface of RuO2 particles. chemically formed RuO2 is redox active only within a fraction of the surface Ru atoms.5 F g1. have been explored to maximize the surface area of RuO2 by creating micropores large enough for ion diffusion. when the water content was decreased to RuO20. As implied by eqn (13). Sugimoto et al. cobalt oxide. nickel oxide. where Ru oxidation states can change from Ru(II) to Ru(IV):15. according to eqn (13).9 for a room-temperature dried product. the following factors play key roles in the electrochemical behavior of Ru oxides: (1) Specific surface area. It was reported that cation diffusion in hydrated electrodes could occur via hopping of alkaline ions and H+ ions between H2O and OH sites. The results are shown in Table 2. long cycle life. 797–828 809 . x.3H2O RuO20. The quasimetallic conductivity of RuO2 allows facile electron transfer into and through the electrode matrix. or the interlayer does lead to an increase in the capacitive behavior. The pseudocapacitive behaviors of ruthenium oxides in acidic and alkaline environments involve different reactions.2 V voltage window. in parallel with which the redox pseudocapacitance mechanism can occur. depending on the conditions. However. and tri.03H2O.182. Among the transition metal oxides. coating a thin RuO2 film on high-surface-area materials.191 Elsewhere.189 No matter what kind of electrolyte is used.183. suggesting that the hydrogen atoms were relatively mobile in RuO2xH2O samples as compared to those in rigid samples.182 Several approaches. A well crystallized structure has difficulty in expanding or contracting. hydrous ruthenium oxide (RuO2xH2O) thin-film electrodes electrodeposited on titanium substrates exhibited high reversible characteristics.15 The water content. In fact. 202 with permission from American Chemical Society) Specific capacitance/F (g-RuO2)1 Scan rate/mV s1 RuO2 RuO20. the reversible redox transitions strongly depend on the processes of proton/cation exchange and electron-hopping.2. For example. mesopores. allowing facile interconversion of O2 2 OH. a maximum capacitance of 710 F g1 was obtained by calcinating ruthenium oxide at 200 1C.184–188 RuO2 + xH+ + xe 2 RuO2x(OH)x (13) However. and when it is discharged these high valency state compounds will be reduced to RuO2. metallictype conductivity. three distinct oxidation states accessible within a 1. and superior power characteristics. Rev. The water content in RuO2xH2O strongly depends on the preparation process and conditions. in an alkaline solution. the combined water in RuO2 is expected to enhance the diffusion of cations inside the electrode layer.195 (2) The combined water in RuOx. excellent cycle stability. In acidic electrolyte solution.200 Increasing the annealing temperature can result in a lack of chemically bound water. Obviously. The pseudocapacitance of RuO2xH2O materials is also closely related to the degree of crystallinity. 41.125. It has been suggested that when the carbon/ruthenium composite is charged the RuO2 in  the composite electrode will be oxidized to RuO2 4 . leading to a redox specific capacitance of 914 F g1. metal particles prepared using the polyol method were small and uniform in size as well as highly This journal is c The Royal Society of Chemistry 2012 dispersed on a carbon surface. remarkably high specific capacitance.203.and dihydrated phases can also be obtained. and high rate capability. of RuO2xH2O is typically 0. those investigated include ruthenium oxide. making nanometre-sized oxide electrodes.2. high proton conductivity. the more the metal centers will be capable of providing multiple redox reactions and the higher the specific capacitance will then be.

182 (4) The size of RuO2xH2O. View Article Online permeating the bulk material. when the annealing temperature exceeds 175 1C.206. Using a colloidal method. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. Particles prepared from this process were found to be uniform in size and distribution. regardless of the RuO2 loading in the electrode layer. the smaller the particle size. Using a template method. their activities are quite low due to their low conductivity. As a result. and enhance the electro-active sites. For example. the polyol process also appears to be a promising alternative for preparing nanosized RuO2. the RuO2 electrode may behave like a double-layer capacitor. and the capacitance of RuO2 with good crystallinity comes mainly from the surface reaction. ruthenium oxide can be brought close to its theoretical capacitance by deploying the RuO2 in a nanostructure to increase its surface area and pathways for diffusion. Electrolyte concentration can also have an effect on the performance of RuOx electrodes. its costliness is a practical impediment.215 Therefore.5 M.. 2012.213 varying the deposition temperature and/or pH can control the cluster size in the process of electroless deposition.21.200. depending on the preparation method.202.125 Obviously. in a soft template situation.5 M. the particle size of RuO2xH2O can be controlled by altering the template size.211 The particle size of RuO2xH2O can be controlled in different ways.2.207 For example. A similar trend was also observed by Kim and Popov. the higher the gravimetric capacitance and utilization efficiency.195. when the temperature is close to the crystallization temperature of ruthenium oxide. for a particle with a diameter of 3 nm.214.207 In a word.200. It was also reported that RuO2 particles prepared via NaHCO3 titration were smaller than those produced by NaOH titration. when KOH electrolyte concentration was higher than 0.221.3 Therefore. in other electrolytes. Rev. many researchers216–222 have focused their efforts on reducing Ru usage and increasing its utilization.183. MnO2.Published on 21 July 2011. and the specific capacitance of a composite with 50 wt% RuO2 can reach 642 F g1. and reversible faradaic reactions are compromised. which can lead to well crystallized RuO2 with a small amount of water. However. 797–828 particles can be adjusted by the RuO2 content in the composites as well as the alkali used in the preparation procedure.182.201.208 The optimal annealing temperature is reported to be about 150 1C.206 Temperature is another important factor controlling the crystallinity and water content of RuO2xH2O materials. the number of active sites is decreased due to crystallization and water loss. the capacitance increased linearly with increasing KOH concentration. Therefore.195. the size of RuO2 810 Chem. RuO2xH2O obtained via a vapor procedure has exhibited better crystallinity and lower specific capacitance than that obtained via a solution procedure. 41. the ionic concentration in electrolytes must match the needs of both the electrical double layer and the faradaic reactions. For example.215 reported that nanostructured crystalline RuO2 particles prepared using a SiO2 hard template had a narrow size distribution. RuO2xH2O can remain amorphous and hydrous. and a relatively low specific capacity of 229 F g1 for 40 wt% Ru at 10 mV s1. assuming the particle is spherical (where redox reactions can occur to a depth of 2 nm from the surface of the particle). even though water is still retained in the oxide. a nanometre-sized crystalline RuO2.223–228 and fabrication of ruthenium-based composite materials in which particles of hydrous ruthenium oxide are deposited on other This journal is c The Royal Society of Chemistry 2012 .21. when the particle diameter is 10 nm only 49% of the total particle volume can contribute to the total capacitance. leading to a diffusion limitation. Under a higher heat treatment temperature. the annealing temperature can be as low as 100 1C. specific capacitance values as high as 1300 F g1 were achieved. However. However.205 In contrast.2. has shown a specific capacitance of up to 900 F g1.2 RuO2-based composites.207 With a conventional sol–gel method. the particle size of RuO2xH2O can be altered by the amount of NaHCO3 and the reaction time.208 In addition to the soft template method. the fast.209 By deploying RuO2 into a nanostructure to increase its surface area and paths for diffusion.200. For example. Soc. whereas when the concentration was lower than 0.182 The crystallinity of RuO2xH2O depends on the synthesis procedure.214 Therefore. Rough calculation has indicated that 90% of a superconductor’s cost comes from the electrode material. anchored on CNTs using a simple supercritical fluid deposition method. The specific capacitance values of RuOx electrodes can be changed by using different electrolytes in the surpercapacitor.210 The presence of ordered nanopores can also lead to better electrolyte diffusion into the electrode material and then improve the completion of the redox reaction. close to its theoretical value. it should be noted that a hard template is often accompanied by a higher pyrolysis temperature.210 (5) Electrolytes used.190. Cui et al. the capacitance decreased sharply with declining concentration. Despite the exceptional properties of ruthenium oxide and its high theoretical capacitances (1360 F g1 for RuO20. which is why an amorphous composite exhibits far superior performance when compared with crystallized structures. one of the key points is to cut RuO2 particles down to a nanosize and maintain high electrical and protonic conduction throughout the particles. and displayed a specific capacitance of 914 F g1 when the Ru loading was 20 wt%. For example.g. RuOx materials can display pseudocapacitance behavior that is dependent on the RuOx content. this value can reach 96%. increase the specific surface area.). although the particles and pores are not as regular and ordered as in those samples prepared using a hard template. the specific capacitance will drop rapidly due to the formation of a crystalline phase.5H2O)..212 According to Ramani et al. Thus. a soft template is advisable for preparing nanosized RuO2 composites. the redox reaction of an amorphous composite occurs not only on the surface but also in the bulk of the powder. NiO etc. a disordered form is an essential parameter improving the capacitance of RuO2xH2O. resulting in higher pseudocapacitance.212 In some electrolytes. continuous. Although active sites can be obtained at a lower heat treatment temperature. Two approaches have been demonstrated in the literature: synthesis of mixed-oxide composites by doping base metal oxides into ruthenium oxide (e. 3. and Lin et al. Smaller sized particles not only can shorten the diffusion distance but also can facilitate proton transport in the bulk of ruthenium oxide. According to the literature.

1 Mixed-oxide composites. a Ru–Co mixed oxide electrode exhibited a superior performance of 570 F g1 when compared to a RuO2 electrode (475 F g1). As a result. 41. Soc.2. (iii) ‘‘between-particle’’ electron-hopping resistance between particulates. the following five key factors have been proposed to determine the capacitive performance of Ru-based oxide composites:21. showing layers of mixed Nb:Ru oxides (500 nm field of view). the utilization of RuO2 can be greatly enhanced by loading it on TiO2 nanotubes. One of the functions of the additive metal oxides is to aid in electron and proton conduction. RuO2 particles can provide electrically conductive pathways and niobium oxide possesses good proton diffusion. Sugimoto et al. At the same time.182. It was reported that the structural support from Co species facilitated electronic conduction within the metal oxide. the ruthenium and niobium oxide species could homogenously disperse throughout the film. the aggregation of RuO2 grains exists in the composite.) Chem.218.227 also demonstrated enhanced supercapacitive properties by doping with vanadium.5 F g1 was obtained with the proper amount of Ru1–yCryO2 loaded on the TiO2 nanotubes. when niobium contents reached 50% (1 : 1 Nb : Ru) and 66. many studies have focused on combining RuO2 with cheap metal oxides such as SnO2.View Article Online Published on 21 July 2011. proton conduction through the mixed oxide. 2012.236–240 (i) the electrochemical kinetics of electron transfer for active materials.49 Amorphous Ru1–yCryO2/TiO2 nanotube composites were also synthesized by loading various amounts of Ru1–yCryO2 on TiO2 nanotubes via a reduction reaction of aqueous Ru1–yCryO2 with RuCl3. NiO. VOx. 242 with permission from Elsevier.223 reported that the specific charge of a RuO2 (33%)–VO2 (67%)/Ti electrode was about 50 times higher than for a RuO2/Ti electrode. As a result. Fig.242 This journal is c The Royal Society of Chemistry 2012 Hence. (ii) ‘‘in-particle’’ electron-hopping resistance within every RuO2 particulate. 9. WO3. MoO3. 797–828 811 . at higher potential scan rates (500 mV s1). However. a specific capacitance of 710 F g1 in a KOH electrolyte183 was reported for a SnO2–RuO2 composite electrode wherein RuO2 was deposited by an incipient wetness precipitation method. (iv) electron-hopping resistance at the interface between active materials and current collectors. at 33. and efficient utilization of ruthenium. The introduction of V not only extended the electrochemical window of the Ru0. The dispersion of ruthenium oxide can benefit from doping with other metal oxides. TiO2. Furthermore. It was reported that the optimum composite consisted of roughly equal amounts of ruthenium and niobium.227. 9 Compositional mapping using TEM-EDS. and the overall capacitance loss of these mixed oxides was much less significant than for pure RuO2.2. and CaO to form composite oxide electrodes. B95% niobium could result in a film without discernable RuO2 grains. In the attempt to reduce the cost of precious metal use.179.228 For instance. Takasu et al.235 The results demonstrated that the three-dimensional nanotube network of TiO2 offered a solid support structure for Ru1–yCryO2. low-cost materials (e. As shown in Fig. Rev.242 (Reprinted from ref. In addition to providing extra pseudocapacitance. With their large surface area TiO2 nanotubes not only help the transportation of ions but also facilitate double-layer charging. and (v) barriers to proton diffusion within oxide composites and particulates.207.241 In composites of ruthenium oxide and niobium hydroxide.3% niobium (1 : 2 Nb : Ru). the additive metal oxides can simultaneously function in the composite as follows: (a) To facilitate electron and proton conduction in the oxides.2.183.1 V but also increased the utilization of Ru species as well as the electrode’s electrochemical stability. the dispersion of ruthenium increases significantly.229–234 3.64O2 electrode from much less than 1. (b) To enhance the dispersion of ruthenium oxide. MnO2. For example.242 with a greater niobium content.195.g..186. the Ru/Nb oxide composite maintained a high specific capacitance with increasing potential scan rate. there is an optimization among electrical conduction through interconnected RuO2 grains. Kuo and Wu225 successfully developed an electrochemical capacitor electrode containing highly dispersed RuO2 electroplated on a conductive mesoporous tin oxide substrate. Only if concentrations of mixed metals are moderate can a higher specific capacitance be expected.7% (2 : 1 Nb : Ru). Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59.0 V to 1.184. allowing the active material to be readily available for electrochemical reactions while at the same time improving the active material’s utilization.226 In summary. It was reported that a maximum specific capacitance of 1272.36V0. carbons with different surface textures and conductive polymers).

126 the average particle size of RuO2 can be decreased by increasing the Sn content.2.2O2xH2O. compromising the utilization of RuO2.213. and specific surface area will exert different influences on the electrochemical behavior of RuO2. 41.262.234.231. the contribution of RuO2 increases the specific capacitance. the corresponding particle sizes grew from 1. even though their specific surface areas were small.9.6Sn0. Kim et al. and SnO2xH2O—the mean particle sizes of the primary particulates.2O2xH2O. while the latter was amorphous with a smaller particle size (1–1. Although the RuO2 composites with amorphous carbon exhibited lower conductivity than those with crystalline carbon.233.4O2xH2O. For materials like RuO2xH2O.201 It is necessary to point out that many investigators utilized a very high annealing temperature to obtain RuO2/carbon composites.0.263 The former showed some crystallization and larger particle size (2–4 nm). and higher specific capacitances have been achieved. and the RuO2 loading was increased from 0 to 15 wt% on microporous carbon and from 0 to 40 wt% on mesoporous carbon.193 B850 F g1 for carbon–RuO2 composite electrodes.263 As shown by Kim et al. specific capacitance and power characteristics) of binary oxides is strongly affected by their molar ratio. showed a strong interaction between RuO2 and the surface carboxyl groups of carbon. reducing the ion intercalation distance to nanometres when a thin layer of RuO2 was coated on CNTs.206 Increase in RuO2 particle size is often This journal is c The Royal Society of Chemistry 2012 . Ru0. Therefore.223. carbon nanofibres.262 It was reported that oxide deposited on crystalline carbons is texturally different from oxide deposited on amorphous carbons. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59.5 W h kg1 at a specific power > 1.2 RuO2/carbon composites.244 Liu et al. RuO2 existed in the form of particles with sizes less than 0. increasing the faradaic reaction sites of the RuO2 nanoparticles. Accordingly.247 Obviously. respectively. the specific capacitance remains nearly constant in the range of 0–20 wt% RuO2. carbon aerogels. 797–828 carbon nanotubes. a carbon support mainly plays the following roles: (i) A carbon support seems to favor the dispersion of amorphous RuO2xH2O particles. Ru0.193. and then affecting the pseudofaradaic reactions of those nanoparticles. their specific capacitance increases linearly with increasing RuO2 content.8Sn0. crystallinity.225 It can be seen from the above-mentioned roles of doping metal oxides that the capacitive performance (e. For instance. for microporous carbon-derived composites. CNTs. and a higher specific capacitance of 850 F g1 is obtainable with a Sn content of 0. When microporous and mesoporous carbons were used as supports. usually 3–15 nm in size. which contributed to the high dispersion of RuO2 nanoparticles.4 to 4 nm and from 1. In RuO2/carbon composites. For instance.2 mm either on SnO2 crystalline surfaces or forming skeletal structures within voids.2. the specific capacitance of the composites also increased with increasing RuO2 content. synthesis conditions need to be optimized. In recent years.) have been intensively studied as ES materials. the main factor influencing the total specific capacitance is their composition. i. For carbon nanofibres.2.260 The conductivity of the dispersed MCNTs can also increase the electrical conductivity of the composite..2.263 the carbon support can enable easy penetration of the electrolyte up to the oxide primary particles.126 3. near grain surfaces. View Article Online (c) To minimize the RuO2 particle size. When carbon nanofibres were used to construct a RuO2 composite. (b) The particle size of supported RuO2 often increases with increased RuO2 loading.247 647 F g1 with 60% RuO2 in Ketjenblack. giving rise to a higher specific surface area. when RuO2 loading was 0–11 wt%. niobium can induce a decrease in RuO2 particle sizes. were 3.262 the particle size increased from 2 to 4 nm. within a range that depends on the type of carbon used. 2.123. which decreased with increasing Sn content.Published on 21 July 2011. a RuO2–SnO2 composite electrode achieved a specific capacitance of 930 F g1 in 1 M H2SO4 and an overall specific energy of B0. It was also observed that the highly dispersed RuO2 nanoparticles exhibited increased capacitance. placing more RuO2 in electroactive regions. When the RuO2 content is greater than 20 wt%. and SnO2xH2O.5 kW kg1.e. For example. the surface functional groups of CNTs may also enable the electrode to easily transport the solvated ions to the electrode/electrolyte interfaces. By inducing more porosity. and 1. its redox capacitance and surface utilization were dramatically increased.208 obtained a capacitance of 642 F g1 from a composite with a molar ratio of Co : Ru = 1 : 1 at 150 1C. Ru0.192 carboxylated carbon nanotubes can prevent RuO2 particles from agglomerating and contribute to the high dispersion of RuO2 nanoparticles by forming a bond between RuO2 and the surface carboxyl groups of the 812 Chem. However when loading was increased beyond these ranges.193 Besides introducing more porosity to the electrode. Ru0.245–262 The quantity of RuO2 required in the electrode layer has thereby been reduced significantly.2. as mentioned previously.g. the incorporation of vanadium diminished the particle size of Ru oxide. (ii) A carbon support can facilitate the transfer of ions and electrons in the electrode layers. Soc. composites containing RuO2 and carbon materials (such as carbon. 1.5 nm) and had a large specific surface area (450 m2 g1). because the protons were able to access the inner part of RuO2. 2012.242 In addition.221.193 For RuO2/carbon composites. The addition of other metal oxides can affect the particle size of RuO2. such as 256 F g1 with 14% Ru in a carbon aerogel.8 nm.6Sn0. The porous morphology of MCNTs allows excellent electrolyte access in three dimensions.243 According to Hu et al.8Sn0. two points should be noted: (a) Carbons with different porosity.4O2 xH2O..4 to 1. their specific capacitances were found to be larger. It was also observed that when RuO2 was electroplated and dispersed onto a highly conductive mesoporous SnO2 matrix. This is because the increase in specific capacitance due to the increased RuO2 content is balanced out by the decrease in specific capacitance owing to the decrease in the carbon’s specific surface area.6 nm.256 628 F g1 with RuO2/MCNTs in a ratio of 2 : 1. high temperature will lead to higher crystallinity.. Rev.192.209. etc.186 and 900 F g1 for RuO2 oxide powder pressed on conductive carbon.206 In the case of mesoporous carbon-derived composites. In a supercapacitor test. in a series of Ru oxide materials—RuO2xH2O. the particle size of RuO2xH2O was found to remain constant (generally 4 nm). respectively.

279 The proposed mechanism is expressed in eqn (14):269..274–277 The capacitance of manganese oxides comes mainly from pseudocapacitance. Eqn (14) suggests that both protons and alkali cations are involved in the redox process. RuO2/polymer composites have also received more attention.207.2. particle size can be conveniently tuned by adjusting the mass ratio of the carbon precursor. In general.4-ethylenedioxythiophene) nanotube composite that displayed a high specific capacitance and rapid charging/discharging capability.240. (a) MnO2 obtained by using CNT and (b) MnO2 obtained by using mesoporous carbon. and MnOa(OC)b and MnOad(OC)b+d indicate MnO2nH2O in high and low oxidation states. hydrous RuO2 particles. its drawbacks. Recently. and then provided a short diffusion distance for ion transport. and when it was used as the electrode material in a supercapacitor. (iv) providing an efficient route to deliver proton species. and V2O5. K+) in the electrolyte.280–282 MnOa(OC)b + dC+ + de+ 2 MnOab(OC)b+d (14) where C+ denotes the protons and alkali metal cations (Li+. prevent it from being used in the commercialization of supercapacitors. Fe3O4. This RuO2-based composite reached a high specific capacitance of 1217 F g1. 2012.g.283. and (v) improving the adhesion of RuO2xH2O to the current collector.285 (Reprinted from ref. We here review in detail several physical and chemical factors that affect the pseudocapacitance of MnOx electrodes: (1) Crystallinity. Fortunately.2.218 3. For example. analogous to non-faradaic energy storage mechanisms. researchers have put significant effort into finding cheaper and environmentally friendly materials that exhibit electrochemical behavior similar This journal is c The Royal Society of Chemistry 2012 to that of RuO2. microstructure and surface morphology) and chemical factors (valence and the hydrous state of the oxide) affect the pseudocapacitive performance of Mn oxides. while their specific capacitance is governed primarily by their chemically hydrous state. NiO.287 both physical properties (e. and Mn(VI)/Mn(IV) within the electrode potential window of the electrolyte.266 3.4-ethylenedioxythiophene)-doped poly(styrene sulfonic acid) exhibited a high specific capacitance of 653 F g1. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. electrochemically loaded into poly(3.View Article Online Published on 21 July 2011. and environmental safety.174 reported a nanostructured polypyrrole/RuO2 composite that achieved a specific capacitance of 302 F g1.268–272 Since the early report by Lee and Goodenough in 1999. (iii) networked pores inside electrode layers (proton conduction). Polymers are claimed to play several roles in RuO2/polymer composites: (i) preventing the aggregation of RuO2xH2O particles by steric and electrostatic stabilization mechanisms. as the polymer’s density is relatively low compared with that of hydrous ruthenium oxide.2.2.286.209 In conclusion. 797–828 813 .195. Soc. 285 with permission from Elsevier.3. (ii) networked particles with good connections (electronic conductivity). hydrous structures (solid-state proton diffusion). when RuO2-based composites are used as ES electrode materials for practical applications. increase electrical conductivity.267 As an alternative approach. It was found that the cycle stability of Mn oxides is mainly controlled by their microstructure. Mn(IV)/Mn(III). maintaining 80% of the maximum energy density (28 W h kg1).272 Despite the clearly redox nature of the energy storage mechanism.265 synthesized a RuO2/poly(3. Although high crystallinity can give rise to higher conductivity. Liu et al. manganese oxides (MnOx) present relatively low cost.264 Unfortunately.3 MnO2.2. such as relatively high cost and environmental harmfulness. as well as high theoretical capacities ranging from 1100 to 1300 F g1. (ii) uniformly distributing RuO2xH2O particles on the polymer matrix. 10 presents an example).270. a high power density of 20 kW kg1 was achieved. low toxicity. Although amorphous hydrous RuO2 can provide extremely high specific capacitance. respectively. they should possess the following properties: (i) nanosized.) Chem. the addition of carbon to an Ru oxide based electrode layer may improve the homogeneity of the electrochemical reaction.2. Similar to ruthenium oxide. the protonation (or deprotonation) reaction will be limited. Na+. (iv) high packing density (volumetric energy density). and (v) mechanical stability (cycle stability).288 3. (iii) increasing the active surface area of RuO2xH2O. and consequently further increase the power and energy densities of the corresponding supercapacitor. which is attributed to reversible redox transitions involving the exchange of protons and/or cations with the electrolyte. if the crystallinity is too high in MnOx.284 As reported in the literature. reduce the ionic resistance of the metal oxide. and that the MnOx material must have high ionic and electronic conductivity.3 RuO2/polymer. expand the active sites.264 Zang et al.183. amorphous. Rev. the accompanying volume increase caused by the polymer in the RuO2 composite is undesirable for light and compact energy devices.272.45. associated with decreased specific capacitance.278. 10 Cyclic voltammograms of MnO2-based electrodes in a 1 M Na2SO4 electrolyte at a potential scan rate of 5 mV s1. loss of surface area occurs Fig.2. Another critical problem is swelling and shrinking of the polymer during the supercapacitor cycling process. The high power capability and specific capacitance were attributed to the special hollow nanotube structures and their thin walls.1 Factors affecting the pseudocapacitance of MnOx.206. MnOx-based electrodes can also demonstrate typical rectangular-shaped cyclic voltammetry curves (Fig. 41.278. In summary. as well as the transitions between Mn(III)/ Mn(II).273 MnOx has attracted major attention and is considered a promising alternative class of materials for ES applications. These alternative materials include MnO2. which allowed ions to readily penetrate into the composite material and access their internal surfaces.

For example.) 814 Chem.71. However.294 the majority of materials yielded specific capacitances of only 20–30 F g1.301 In the literature.292 Depending on the morphology.309 Using an anodic deposition method. the more compact and dense phase).291 Fig.45. there should be a trade-off between electrical conductivity in the solid phase and ionic transport in the pore. 11 by birnessite). g-. although one high specific capacitance of 240 F g1 at a current density of 1 mA cm2 was reported.305 nanobelts. and d-MnO2 has a relatively open layered structure (as shown in Fig.296.0 V using a 0. In a hydrothermal reaction.1 M Na2SO4 aqueous electrolyte solution.1 F g1 at a current density of 300 mA g1.302–304 nanorods.283.299. such as nanowires. d-MnO2 obtained via a hydrothermal synthesis process exhibited a much higher specific capacitance than g-MnO2 and b-MnO2. Thus. 11 Manganese dioxide structural transitions induced during material synthesis. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59.291. Crystallized MnO2 materials have several crystalline structures. various morphologies are obtainable by adjusting the precursors and conditions. For example. the morphology of MnOx can be controlled by altering the preparation process or reaction conditions. With respect to crystallinity-dependent electrical conductivity.296. the annealing temperature plays an important role in achieving optimal conductivity. and lower specific capacitance at low scan rates. b-.290 (2) Crystal structure. although lower crystallinity can result in a highly porous microstructure.45 the morphology of manganese oxide prepared from manganese acetate solutions is controllable by varying the deposition current density. 797–828 It has been recognized that different preparation conditions can result in different MnOx structures. it was reported by Hu and Tsou278 that an amorphous hydrous manganese oxide (a-MnO2nH2O) fabricated from an MnSO45H2O solution via anodic deposition yielded a specific capacitance in the range of 265–320 F g1 when measured in a potential range between 0 and 1. Normally.1 mol L1 Na2SO4 electrolyte.298 Besides these two methods. 2012. using a soft template method. amorphous MnO2 made from an Mn(CH3COO)2 solution showed a capacity of 195–275 F g1 in a 2 M KCl solution and 310 F g1 in 2 M (NH4)2SO4. the electrical conductivity of the resulting MnOx will be low. At a high scan rate. View Article Online simultaneously. the product is mainly a d-MnO2 phase. Soc. b-. 41. Consequently..291 With a-MnO2. excellent pseudocapacitive behavior can be obtained when Mn oxide is treated at an appropriate annealing temperature. and d-MnO2.292 Single-crystal a-MnO2 prepared by hydrothermal reaction of KMnO4 under acidic conditions exhibited a specific capacitance of only 71. Obviously.307 nanobundles.310 This journal is c The Royal Society of Chemistry 2012 . gradually increasing the precursor acidity can lead to a progression from layered d-MnO2.291 d-MnO2 synthesized through a redox reaction between MnSO4 and KMnO4 in an aqueous medium gave a specific capacitance of 236 F g1 at 0. These structural changes in MnO2 give rise to significant changes in electronic and ionic conductivity. Furthermore. and g-MnO2 have a tunnel structure (2  2 octahedral units for a-MnO2.295 The two-dimensional layered structure of d-MnO2 can facilitate cation intercalation/deintercalation with little structural rearrangement.306 flower-like microspheres. When compared with those not heat-treated.Published on 21 July 2011. Rev. prepared manganese oxides have many different morphologies. the obtained material’s specific surface area can range from 20 to 150 m2 g1. In an NaOH or KOH solution. Among them. affecting the material’s pseudocapacitive behaviour. a d-MnO2 compound was obtained using sonochemistry and exhibited a specific capacitance value exceeding 350 F g1. MnOx heat-treated at 200 1C showed a higher specific capacitance at high scan rates. the morphology of MnO2 changes by varying the reaction time at a given molar ratio of reactants.5 mA cm1 in 0. 291 with permission from Elsevier. including a-. On the other hand. nanostructured a-MnO2 synthesized via a hydrothermal technique under mild conditions yielded a specific capacitance of 168 F g1 at a potential scan rate of 1 mV s1.13.291 (Reprinted from ref.297 Several methods for synthesizing d-MnO2 have been developed.289 This phenomenon might be attributable to the fact that films treated at 200 1C possess both lower open porosity and lower surface area. 1  1 octahedral units for b-MnO2. to a more compact and dense b-MnO2. diffusion of H+ and Na+ ions is limited and some pores and voids become inaccessible. the relatively large tunnel structured phase.276. a-. the morphology of MnO2 plays a determinant role in its electrochemical performance.308 and flower-like nanowhiskers.300 (3) Morphology.293 For g-MnO2 based materials. through the relatively large tunnel structured phase a-MnO2. There is no doubt that the morphology of MnO2 closely relates to the specific surface area and therefore the specific capacitance.

offering large specific surface areas. Rev. short transport/diffusion path lengths for both ions and electrons can be realized.039 F cm2 268 far from the requirements for practical applications. At the same time. For example. For example.01 M Mn acetate solution at various deposition current densities on Au-coated Si substrates).311 In a microemulsion process. When this thin layer was used for ES electrodes.52.317 The second MnO2 morphology is porous spherical particle materials. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. the entire electrode can only provide a capacitance of 0. the better the cycle stability is. The major benefits of thin layers can involve (i) lower series resistance due to shorter transport paths for the diffusion of protons (low concentration polarization of the electrolyte). 2012. Prasad and Miura. more active sites for charge transfer.318 Based on the above and the literature.56 This journal is c The Royal Society of Chemistry 2012 For instance.280 A thin layer of an MnO2 electrode prepared by dip-coating colloidal MnO2 exhibited a specific capacitance value close to 700 F g1. Templated electrosynthesis. Furthermore. The third morphology is an Mn oxide film with a rodlike structure (prepared through anodic deposition from a 0.210 A specific capacitance as high as 1300 F g1 was reported with thin MnO2 deposits (on the scale of nanometres) because the reaction kinetics was no longer limited by the electrical conductivity of MnO2. which need high power and energy. View Article Online the solvent used. (ii) easy access of the electrolyte to the active surface of manganese dioxide. and short transport/diffusion distance for proton diffusion. (5) Specific surface area and pore structure. and so forth. the more ordered hexagonal NiAs-type crystal structure possesses fewer electrochemically active sites available for fast ionic transport and charge transfer. The first is one-dimensional nanostructured MnOx. In general. larger surface area implies more faradaic active sites and thereby higher pseudocapacitance.195. 41.288 It is worth pointing out that both the surface area and the pore-size distribution of MnO2 can be controlled by adjusting the reaction time and the surfactant content in the aqueous phase.320 Some researchers have also pointed out that the thicker MnO2 films deposited at higher potential are different from the thin films obtained at lower potentials.291. K2SO4. 797–828 815 . which shows good cycling stability because pillaring agents are not favored for significant structural or mesostructural change during the intercalation and de-intercalation processes.332 (6) Chemical factors (the hydrous state of the oxide and valence). Soc.323–329 A thin MnO2 layer prepared by a sol–gel method (MnO2 loading of B4 mg cm2) showed a specific capacitance of 700 F g1 in a potential window of 0. Hence. for one-dimensional nanostructured materials. Further. There are quite a number of publications on this issue. can also be employed for MnOx synthesis. high power density and stability were achieved. Na2SO4. Hence. leading to less electrochemical polarization and therefore minimal dissolution of Mn oxide. the porous structure of the material can offer more channels for the electrolyte.322 reported a thin amorphous MnO2 film obtained by potentiodynamic deposition that exhibited a specific capacitance of 482 F g1. capacities vary in the range of 70–150 F g1.269.312 precise control of particle size and shape can be achieved.315 Another example is one-dimensional nanobelt materials. That may be the reason why they have a higher capacitance of 350 F g1 compared with nanorods’ capacitance of 243 F g1. the temperature of the reaction.330 Unfortunately. protecting the electrode from physical damage. Normally. a fibrous electrode has a high surface area and contains more active sites for redox reactions. even though this kind of MnO2 thin layer can exhibit an extremely high specific capacitance of 1330 F g1.314 For example. or KOH..288.331 For example. it is obvious that the thicker the film. nanowires with smaller diameters can offer larger specific surface area for the access of electrolyte ions. The difference between their specific capacitance can be as large as 100 F g1. leading to faster kinetics. the MnO2 thin layer yielded a high specific capacitance of 149 F g1 even at the high potential scan rate of 500 mV s1.45 The fourth is a petalshaped manganese oxide. high porosity can easily relieve the internal stress created during the charging and discharging processes. whose maximum capacitance is 185 F g1. (4) Thickness of the electrode layer. Most reported MnO2 thin layers have exhibited specific capacitances as high as B600 F g1 or more within a potential window of 0. the specific capacitance of a metal oxide material will increase significantly as its surface area increases. and resulting in high charge/discharge capacities. leading to capacitance fading. Thus.268. The fifth morphology is MnO2-pillar layered manganese oxide. but also better accommodate large volume changes. the more fibrous or porous the oxide. the lower the specific capacitance.321 Therefore.313 which is widely used as an effective pathway to form one-dimensional porous structures using anodic aluminium oxide and polycarbonate membranes. Physically and chemically bound water is believed to be helpful for the transportation of electrolyte ions. resulting in improved cycle performance for cathode materials.316. the loss of water content caused by heat treatment will result in Chem. As with RuO2. leading to high capacity and fast kinetics.9–1. high specific capacitance and rate capability can be achieved.9 V. one-dimensional nanostructured materials with special morphologies and large surface areas are necessary for potential applications in ES. and (iii) higher electronic conductivity. depending strongly on the thickness of the electrode layer.2 V in aqueous electrolytes containing KCl. the specific capacitance of a MnO2 layer prepared from the oxidation of MnSO4 decreased from 220 to 50 F g1 as the MnO2 loading was increased from 100 mg cm2 to 4 mg cm2. In general. which may not be a good choice for ES material because it could reduce the specific surface area. when the deposited loading of nanostructured MnO2 was increased from 50 to 200 mg cm2 the specific capacitance decreased from 400 to 177 F g1. According to Donne et al. leading to enhanced stability of the layered structure. They not only offer large electrode surface area and provide conducting pathways for ions.Published on 21 July 2011.319 For birnessitelike compounds prepared by electro-oxidation of acidic aqueous solutions of MnSO4. especially when a thin MnO2 layer is uniformly dispersed on conductive and porous carbonaceous materials with a high surface area.270 Besides nearly perfect cyclic performance.. Several morphologies of MnO2 and their effects on specific capacitance are worth discussing here. the specific capacitance decreases with increasing thickness of the electrode layer (or film) due to the low conductivity of MnO2.301 these are better than platelet particles.

In actuality.296 The factors mentioned above are all related to the MnOx preparation processes and conditions. Mn2O3. crystallinity.277 It was reported that when g-MnO2 was transformed to a-Mn2O3 and Mn3O4 by mechanical grinding. mechanical milling processes.288. MnO2 can be dispersed over a large area.311.13. Several typical techniques reported in the literature are thermal decomposition.334 3. nanoplates. Besides this method.51.3.2. Another concern is the low surface areas and poor electronic conductivity of MnOx materials. if the cobalt oxide content was too high. the literature also shows that MnO2 exhibits much better performance than Mn(OH)2. CNTs. (2) Low surface area and poor electronic conductivity.331 In addition.51 and Mo80 seems to be helpful. sol–gel processes.278. leading to excellent electrochemical capacitance and long cycling durability.273.350–360 For instance. hierarchical hollow nanospheres of MnOx yielded a specific surface area of 253 m2 g1.347 In this way. In a nanostructured nickel–manganese oxide composite.281. View Article Online poor ion conductivity as well as loss of pseudocapacitance if the heat treatment temperature is too high.275 reported that when MnO2 This journal is c The Royal Society of Chemistry 2012 . The most important feature of the supporting strategy is that these conductive supports can form a three-dimensional porous conducting network to effectively assist electron transfer and ion transport within MnOx. MnO2 oxide electrodes suffer from capacitance degradation.335–338 Among these. To improve these.345. electrodeposition.348 Increase in the surface areas of MnOx materials can also be realized by introducing Co into MnOx or by adding a surfactant such as sodium lauryl sulfate or Triton X-100.341 The dissolution reactions can be expressed as eqn (15) or (16):269 Mn2O3(s) + 2H+ .362 Mn oxide/CNT composite electrodes355 reached a specific capacitance of 415 F g1 because CNTs were able to provide electronic conductive paths and form a network of open mesopores.295. the presence of conductive supports not only improves the electrical conductivity of MnOx but also increases its active surface area.333. MnOx involving trivalent Mn(III) shows a rather lower conductivity when compared with MnO2 or amorphous manganese oxides involving Mn(IV). and Mn3O4. and then were coated using electropolymerization of a conducting polymer to yield coaxial rods. and conducting polymers have also been utilized to support manganese oxides in an attempt to promote their conductivity.349 To address the issue of enhancing manganese oxides’ poor electrical conductivity.327 The Mn oxidation state is another very critical factor affecting the electrochemical performance of Mn oxides.2 Challenges for Mn oxides. For example. The presence of a conducting polymer suppresses the dissolution of Mn oxide and improves its resistance to failure.Mn2+ (aq) + MnO2(s) + H2O (15)  2MnO(OH) . several approaches have been carried out in ES material development.Mn2+ (aq) + MnO2(s) + 2OH (16) or Several approaches have been carried out to prevent Mn oxides from dissoluting during cycling.340.344 It was demonstrated that this Mn oxide/ CP coaxial core/shell electrode could exhibit a specific capacitance of 285 F g1 with 92% retention after 250 cycles in 0.335.280.333 However.286.334 Consequently. For example. graphite.283. the presence of Mn3+ results in reduced specific capacitance..302. and the chemical state of Mn oxides should be an important approach.272 Elsewhere it was also suggested that heat treatment can be optimized to possibly enhance overall pseudocapacitive behavior.2.333 For instance.269. leading to both enhanced capacitance and high cycling rate capability. Mn oxide rods were first synthesized through anodic 816 Chem. the doping nickel increased the Mn oxide surface area by about 46% and the specific capacitance by 37%.203 nickel. 797–828 deposition from an Mn acetate solution. To improve Mn oxides’ pseudocapacitive performance.22. several challenges must be addressed to make them usable in practice: (1) Dissolution problem. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59.16 In addition to the above two methods (new electrolytes and material coating).347. Owing to the partial dissolution of MnO2 in the electrolyte during cycling.278.44. In addition to doping. Owing to the Jahn–Teller distortion of the Mn(III)O6 octahedron. 41. and nanorods.302. a large surface area can be achieved by introducing multilayered film electrodes containing transitionmetal composite materials.151. depending on the duration of mechanical grinding. Regarding Mn oxides as ES materials. doping other metals into MnOx is a proven effective way to increase the surface area.342.269.54. doping with ruthenium. it was reported that heat treatment at a temperature up to 200 1C could result in the removal of both physically and chemically adsorbed water.343 Another approach is to apply a protective shell to the Mn oxide surface.346 leading to both high cycling stability and higher power when measured at a high scan rate of 200 mV s1. which is much better than uncoated Mn oxide rods. it was reported that inert cobalt oxide also suppressed the dissolution of Mn into electrolyte and stabilized MnOx. co-precipitation.Published on 21 July 2011. a rectangular shape in a cyclic voltammogram361 and a volumetric specific capacitance of 253 F cm3 can be obtained from a manganese oxide/carbon composite electrode.5 M Na2SO4 at 20 mV s1. a significant reduction in the specific capacitance was observed. 2012. the specific capacitance decreased linearly as the amount of g-MnO2 decreased. new electrolyte salts have been developed to avoid forming acidic species in solution. Using a supporting strategy. the formed Mn oxides have high electrochemical activities. developing more favorable preparation processes to optimize the microstructure.311.334 With respect to this issue. Babakhani and Ivey16 prepared a Mn oxide/CP coaxial core/shell electrode. Rev. with different nanostructured manganese oxides synthesized via a precipitation technique using KMnO4 and various alcohols. Soc. and hydrothermal synthesis. the hydrothermal route has been proven to be an effective and controllable method to produce Mn oxides with various nanostructures such as nanowhiskers.339 Note that the mechanical milling process can lead to a sequential phase transition from g-MnO2 to the thermodynamically stable a-Mn2O3 and subsequently to Mn3O4.268. Li et al.50. highly conductive supports such as active carbon. preventing its further growth by agglomeration and ensuring high utilization of the active materials in addition to providing double-layer capacitance.

Nanostructured MnO2 materials have been intensively investigated.309 The synthesis techniques exploited include hydrothermal. 797–828 817 . (1) Nanostructured MnO2. View Article Online particles were partially coated on the surfaces of MCNTs through a hydrothermal process. Some single-crystal a-MnO2 nanotubes. displayed a specific capacitance as high as 310 F g1 at 2 mV s1. was able to deliver a high specific capacitance of 502 F g1 and excellent cyclic stability. the increased effective interfacial area between MnO2 and the electrolyte. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. great effort has been invested into nanostructured MnOx materials.71. as well as the contact area between MnO2 and graphene.366–368 Nano-MnO2 can exhibit an electrochemical performance superior to its bulk counterpart because it possesses higher specific surface area and the short transport/diffusion path lengths of ions and electrons. Mn oxide nanowire arrays with high aspect ratio and high surface area. it should be noted that the specific capacitance of the composite electrode can be compromised by the low faradaic reaction activity of the conductive supports. the combination of MnO2 with other materials such as graphite and CNTs has also been investigated extensively.386 As a result. For example.363 To improve their ionic conductivity. which is almost three times higher than that of pure graphene (104 F g1) and birnessite type MnO2 (103 F g1). promoting ionic transportation within the electrode. the composite electrodes can display higher specific capacitances.372 KBH4. large specific surface area.305 In addition.284 In addition.391 much higher than that of activated carbon/MnO2 electrodes.354 In summary.277 ethylene glycol.4 F g1 at a current density of 1 A g1 in 1 M Na2SO4. Compared to non-aligned CNTs.374 sol–gel methods.. The MnO2/C composite electrode also exhibited highly stable performance up to 10 000 cycles.2 F g1.376 as well as sonochemical synthesis. and high electrical conductivity. However. and guarantee an effective utilization of MnO2. 41. For example. leading to improved pseudocapacitive behaviour with high retention of a rectangular shape during charging/discharging.387 In this case. extend the working potential.389. surfactants and heat-treatment. In addition to nanostructured MnO2.3 New developments in MnO2. even at the high potential scan rate of 100 mV s1. aligned CNT-based electrodes could show advantages such as low contact resistance. the fabrication of a flexible nanoarchitecture by coating an ultrathin film (several nanometres) of MnO2 to highly electrical conductive Zn2SnO4 nanowires grown on carbon microfibers. The poor ionic conductivity of Mn oxides is another challenge that hinders their practical application in ES. higher energy and higher power densities. In recent years. an excellent specific energy of 36. a nanoscopic MnO2 phase can minimize solid-state transport distances for ions going into the oxide. kinetic reversibility. a specific power of 32 kW kg1 at 40 A g1 as well as a good long-term cycling stability. 3. fumaric acid. respectively. such as methanol and ethanol.369 which were synthesized by a hydrothermal method without the assistance of templates. highly ordered mesopores.1 nm could give a specific capacitance of 466 Fg1 and high cycling efficiency as well at a current density of 10 mA cm2 370. a specific capacitance of 550 F g1 was obtained. complicated operations. Graphene–MnO2 composites (78 wt% MnO2). MnOx based electrode materials can be modified through depositing MnOx onto carbon materials with high surface areas. A specific capacitance of 642 F g1. and Pluronic P123 as a structure-directing agent etc. long and vertically aligned CNTs (with high specific surface area). displayed a specific capacitance of 254 F g1.378–385 The introduction of other materials into MnO2 can improve the electron conductivity of the electrode. to achieve high energy and power densities for ES.375 thermal decomposition.390 For example. respectively.388 With respect to CNT composite materials.333 A uniformly dispersed fibrous manganese oxide electrode. Soc. a-MnO2 nanowires with a diameter of 30 to 40 nm and mean pore diameter of 3.and Ni-doped MnO2 deposited by a potentiodynamic method have also been explored. Amade et al. some intensive studies on MnO2 nanostructured and MnO2 composite materials as well as their asymmetric ES have been carried out as outlined below.272.391 prepared a nanostructured composite electrode with dense.326.373 electrodeposition.269 template synthesis. which had a unique nanoporous structure. This high capacitance was mainly attributed to CNT’s high surface area and conductivity. prepared on anodic aluminium oxide templates. showing specific capacitances of 621 and 498 F g1.2. multilayered MnO2 with a macropore surface and an interlayer space yielded high ionic conductivity.3.2. and electrochemical reaction homogeneity. coupled with a thinner layer of MnO2 by optimizing the CNT preparing parameters and electrodeposition processes of MnO2. (3) Poor ionic conductivity. Therefore. composites with a single-walled CNT support showed excellent cycling capability even at a high current of 2 A g1. which were prepared by redox reaction between graphene and potassium permanganate under microwave irradiation. R. and fast electron transfer kinetics.391 Chem. which can then yield high specific capacitances. at a scan rate of 10 mV s1. The improved electrochemical performance might be attributed to the increased electrode conductivity in the presence of graphene network.386 was obtained at a scan rate of 10 mV s1.377 However. time/energy-consuming and expensive reagents seemed to be serious obstacles for the industrialization of nano-MnO2. could result in a maximum specific capacitance of 642. most of the reports dealt with non-aligned and disordered CNTs.Published on 21 July 2011. 2012. or MnSO4.365 This is because the high porosity structure enhanced electrolyte accessibility.371 Nano-structured MnO2 can be prepared from the reduction of KMnO4 either by alcohols. a-MnO2 nanorods with a diameter less than 50 nm showed This journal is c The Royal Society of Chemistry 2012 good cycling stabilities and could deliver a maximum capacitance of 166.8 W h kg1. For example. (2) MnO2 composite materials. at a high scan rate of 200 mV s1 they yielded 377 and 307 F g1. could possess a high specific capacitance.364 Nanostructured Co. Rev. the crystalline Zn2SnO4 nanowires grown on carbon microfibers served as highly electrical conductive cores to support MnO2 shells with highly electrolytic accessible surface area and to provide reliable electrical connections to the MnO2 shells. it is necessary to develop some simple and cost-effective processes.

407 while single crystal Co3O4 nanorods exhibited a high capacitance of 456 F g1 at a current density of 1 A g1.4 Co3O4 and Co(OH)2.414.2. Co3O4 nanorods with nanoporosity could give a specific capacitance of 280 F g1 at 5 mV s1 in 2 M KOH. R¼ mþ C  DE ¼ m Cþ  DEþ ð17Þ where m+ and m are the masses of the electrode materials. high conductivity. This operating voltage window could be divided into two distinct parts: an approximate symmetric scale ranging from 0 to 1. MWCNT/Co3O4.398 The pseudocapacitance of Co3O4 originates from the following redox reaction:399 Co3O4 + H2O + OH 2 3CoOOH + e (18) With respect to this. as reported by Gao et al. 3. prepared through electrodeposition. nanotubes as well as thin films are all seen in the recent studies on Co3O4. synthesized using a facile complex– precursor solution procedure followed by a sequential thermal decomposition at atmospheric pressure.386 For an active carbon/MnO2 composite electrode.404 Recent studies have been concentrated on Co3O4 with special morphology and microstructure.393 However. For example. as expressed in eqn (19) and (20):178.394–397 Therefore. Al-substituted This journal is c The Royal Society of Chemistry 2012 ..406 Using a facile and efficient hydrothermal method.402 Hexagonal Co3O4 nanosheets. Soc.405 Co3O4 nanowire arrays prepared on nickel foam. large surface area.408 Co3O4 thin films. could give a specific capacitance of 227 F g1 at 1 A g1.401 For example.417 It seems that Co(OH)2-based materials show much higher specific capacitances than Co3O4-based materials. crater-like Co3O4 microspheres with a BET surface area of 60 m2 g1 were synthesized by L. and good corrosion stability.416 To further improve the specific capacitance.400 These recent studies suggest that the appropriate morphology and microstructure are necessary in achieving an enhanced performance of Co3O4-based ES. and achieved a specific capacitance of 200 F g1.Published on 21 July 2011.8 m2 g1 showed the maximum specific capacitance of 370 F g1. For example. prepared with an addition of an epoxide. displayed a specific capacitance of 574 F g1 at 0.37 Co3O4 nanotubes with an outer wall diameter of 300 nm and a wall thickness of 50 nm. nanosheets. A Co3O4 film deposited using a solution spray pyrolysis technique exhibited a specific 818 Chem.411–413 Two plausible reactions can occur. mesoporous Co3O4 nanoparticles with a BET surface area of 184.410 Aerogel-like mesoporous Co3O4. (1) Co3O4. (2) Co(OH)2. this material had a smaller inner resistance of about 0. Microspheres. Co3O4-based materials have been assessed by many groups for ES applications. giving a high capacitance of 609 F g1. one of the challenges is to optimize the mass proportion of the composite. For example. asymmetric cells coupling with electrodes operating reversibly in different potential ranges have been presented as a promising way to increase voltage in aqueous electrolyte. exhibited a specific capacitance of 235 F g1 at a scan rate of 20 mV s1. resulting in an incremental increase in specific capacitance. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. mesoporous Co3O4 microspheres with a unique crater-like morphology were synthesized using mesoporous silica material as a template. Recently. The specific energy power densities of such thin film-based ES were 4.1 A g1.75 prepared a cobalt oxide film from a cobalt chloride precursor and obtained a specific capacitance of 165 F g1 in a 1. exhibited a high specific capacitance of 600 F g1.1 to 2. long-term performance. which promises high surface area and a fast ion insertion/desertion rate. respectively. a flexible nanoflake film of porous cobalt hydroxide was deposited by galvanostatic electrodeposition on a stainless-steel mesh.0 M aqueous KOH electrolyte at a scan rate of 10 mV s1. showed a maximum specific capacitance of 746 F g1 at a current density of 5 mA cm2. C+ and C are the specific capacitances. Wang et al. it has been considered an alternative electrode material for ES. 797–828 capacitance of 74 F g1.400. It should be noted that a specific capacitance higher than that of RuO2 can be achieved in many cases where Co oxide based materials are in the electrode. nanowires.2 Kandalkar et al. allowing the maximum potentials for both electrodes to be close to the acceptable stability values.392 a hybrid ES (with a composite MnO2 and activated carbon as the positive electrode and activated carbon as the negative electrode) extended the operating voltage to 2 V in a 0. designing positive electrodes with enhanced capacitance according to the following formula seemed to be challengeable.0 W h kg1 and 1.403 This relatively low capacitance was attributed to the anhydrous nature of Co3O4.392 (3) Asymmetric cells.1 V and an asymmetric scale from 1. Co3O4 seems to exhibit excellent reversible redox behavior. synthesized by chemically depositing cobalt hydroxide in anodic aluminium oxide templates and thermally annealing. 41.415 Co(OH)2 + OH 2 CoOOH + H2O + e (19) CoOOH + OH 2 CoO2 + H2O + e (20) Some publications exist on Co(OH)2-based materials for ES. View Article Online To simultaneously achieve both high energy and power densities. Rev.. When tested. Shan and Gao399 reported a MWCNT composite electrode.4 O and could provide a specific capacitance of 102 F g1. leading to high energy density as expressed in eqn (9). respectively.402 A specific capacitance of 118 F g1 for a cobalt oxide electrode was obtained by chemically coating cobalt oxide thin films on copper substrates. 2012. to reduce the R value. the optimal mass proportion of active carbon in the positive electrode was found to be 15%.5 M Na2SO4 aqueous solution.409 In addition. By optimizing the mass ratio (R) between the positive and negative electrodes. Eqn (17) is based on the equivalence of charge passed through both electrodes.2.396. nanorods. the best performance for asymmetric MnO2/actived carbon ES was obtained with R = 2. For example.33 kW kg1.5 and V (cell voltage) = 2 V. and E+ and E– are the potential windows for the positive and negative electrodes. A Co3O4 electrode prepared by a sol–gel method gave a specific capacitance of 291 F g1. Co(OH)2-based materials are attractive due to their layered structure and large interlayer spacing.0 V. some modifications were carried out on the microstructure of cobalt hydroxide.

430 As a result.2% of the specific capacitance was lost after 1000 cycles at a current density of 10 mA cm2.421–424 environment friendliness. (1) NiO.49 mA cm2 its specific capacitance decreased from 160 to 140 F g1 after 5000 cycles. more crystallization takes place and the value of x decreases.4 V. Nickel oxide is considered an alternative electrode material for ES in alkaline electrolytes due to its easy synthesis. The composite material.178 Another example is a nickel oxide film prepared via an electrochemical method.5% of the specific capacitance was lost due to degradation of the material’s microstructure.74 NiO + OH 2 NiOOH + e (21) It is recognized that the electrochemical surface reactivity of nickel oxide is strongly dependent on its crystallinity. However. synthesized via a chemical process..429 The challenges in using NiO-based electrode materials for ES involve: (i) Poor cycle performance. To address this issue. Only 0.32 2. such high specific capacitance is only located in low potential ranges. It has also been shown that the preparation process can strongly influence the electrochemical behavior of NiO. Soc.18 1. This exceptionally high specific capacitance was attributed to the special ordered mesoporous nanostructure of Co oxides. showed a high specific capacitance of 569 F g1 at a discharge current density of 10 mA cm2 in a 1 M KOH aqueous solution.19 1.. Chem. 3. Co(OH)2-based ES electrodes can give much higher specific capacitances than Co3O4.08 This journal is c The Royal Society of Chemistry 2012 because the open hierarchical porous texture permitted ions easy access to the electrode/electrolyte interface. the capacitance retention ratio of nickel oxide improved at a high potential scan rate Table 3 Effect of calcination temperature on the specific capacitance calculated from constant current discharge curves (charging at 0.8 2. relatively high specific capacitance (theoretical specific capacitance of 3750 F g1).425 The redox reaction of nickel oxide in a KOH electrolyte can be expressed as eqn (21):426–428. In a nickel oxide/ CNT nanocomposite. Hg/HgO for 10 minutes)429 (reprinted from ref.420 Therefore. making composites of NiO with conductive carbon materials seems to be an effective approach. This composite electrode displayed excellent cycle stability as well. To address this degradation. when a Ni(OH)2/CNT electrode is heated to 300 1C. prepared by a potentiostatic deposition process.74 For example. The prepared nano-NiO materials include nanocolumns. 41.435–441 In particular. as shown in Fig.2.Published on 21 July 2011. the porous structure of hollow nanospheres can act as an ‘‘ion reservoir’’. porous nanowall arrays as well as hollow nanospheres. 797–828 819 . even at a discharge current density of 100 mA cm2 as was excellent charge–discharge cycle stability.60–0. Unfortunately. and after being annealed at 250 1C its specific capacitance reached 696 F g1.432 A recent trend in NiO is to develop nanostructured materials. exhibited low resistance and a high-specific capacitance of 331 F g1 as well as high cyclic stability. leading to slow electrochemical processes in charge storage and delivery. which also exhibited poor cycle performance. approximately 4.418 who presented a specific capacitance up to 2646 F g1 when an ordered mesoporous cobalt hydroxide film electrodeposited on foamed Ni mesh was used as the electrode material. nanorings. most of the specific energy achieved is located in low potential ranges.432 (ii) High resistivity. However. while porous NiO428 obtained by a sol–gel method exhibited a specific capacitance of 200–250 F g1. after 400 cycles.6 V vs. a hexagonal nanoporous Ni(OH)2 film prepared by electrodeposition gave a specific capacitance of 578 F g1. At above 280 1C.36 1. yielded a specific capacitance of 843 F g1 in a potential window between 0 and 0.419. and low cost. nickel oxides with a hierarchical porous texture have been developed. the value of x. As shown in Table 3. Hg/HgO) Heating temperature/1C 2 mA cm2 10 mA cm2 20 mA cm2 x in NiOx 110 200 250 280 300 350 400 450 592 636 696 586 546 494 382 157 419 469 521 420 383 302 270 106 377 404 479 373 340 269 235 88. hierarchical porous nanoflowers. For example. a specific capacitance as high as 541 F g1 was achieved.00 V vs. Rev. However.423 The electrochemical behaviour of Ni–Co oxides was found to be dependent on the composition of the oxides. which is approximately three times higher than the B350 F g1 obtained for a NiOx thin-film electrode. 2012. which limits the materials’ practical application in ES. As a result.50 1. an increase in the specific energy in the high potential range would be the key for their practical application in ES.433 The conductivity of nickel oxide can also be improved by introducing cobalt ions into the nickel oxide matrix. which was formed by thermally decomposing nickel and cobalt nitrates directly onto the surface of a CNT/graphite electrode. nanoflakes. As a result. NiO with a cubic structure.2.5 NiO/Ni(OH)2. had a maximum specific capacitance of 167 F g1.5% of its initial capacitance. the capacitance decreases significantly. nanostructured Co–Ni/Co–Ni oxides with a cauliflower shape.434 For example. For instance.432. losing 12. a maximum specific capacitance of 696 F g1 can be reached at 250 1C.413 One of the most impressive results was obtained by Zhou et al.429 during synthesis the calcination temperature can significantly affect the crystalline structure of NiOx.431 At a current density of 0. a supporting strategy was explored using Co and CNT as supports to form a composite. View Article Online a-cobalt hydroxide. 12. the NiOx-normalized specific capacitance of a NiOx/CNT electrode can reach a specific capacitance as high as 1000 F g1. nano/microspheres. which can limit the transportation of electrolyte ions. In summary. Another challenge for NiO electrodes is their high resistivity (low electrical conductivity). To improve the unsatisfactory porous structures of Ni oxides.46 the CNT conducting network significantly improved the electrical conductivity of the host NiO. CNTs’ high specific surface area can also increase the active sites for redox reactions. and the specific capacitance. nanosheets. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59.15 1. 429 with permission from Elsevier) Specific capacitance/F g1 (0.06 1.

in aqueous 2 M KCl electrolyte. In an attempt to improve electronic conductance. in dilute KCl solution.625 A g1. window can be obtained and the composition of binary oxides can be accurately controlled. For example. which is a simple and template-free hydrothermal method.) This journal is c The Royal Society of Chemistry 2012 . Kong et al.444 Hu et al. then studied the behavior of this material in aqueous KCl solutions. which was capable of delivering a specific capacitance of 2055 F g1 at 0. and excellent cycling stability as well. this method is usually too complicated and time-consuming because of the process of acid/base erosion or calcinations. 12 (a)–(d) SEM images of nanostructured Co–Ni oxides at different magnifications. and 2 M NaCl () electrolytes at a scan rate of 5 mV s1.452 The challenge for V2O5 is its low conductivity. resulting in an extremely high specific capacitance of 2570 F g1 at a current density of 5 mA cm2. It has been determined that Ni(OH)2 and a Co(OH)2–Ni(OH)2 composite can yield much higher specific capacitances than NiO. a solution of 2 M KCl seems to be the best.2.41Ni0.443.442 Regarding the synthesis. Lee and Goodenough450 prepared amorphous V2O5 by quenching V2O5 powders heated at 950 1C. This result was also supported by Wee et al. Fig. due to the low cost of raw materials and high specific capacitance. 190 F g1. or carbonaceous materials. Co/Ni composites should be promising materials in ES applications as long as a wide potential 820 Chem. the addition of CNT could increase the capacitance to almost three-fold that of simple vanadium oxide. which have a larger specific capacitance than pure V2O5. Among the aqueous electrolytes employed. metal oxides. ensuring steady supply of ions for Faradic reactions at high current densities. 13 CV curves of V2O5 in 2 M KCl (—). the template-based method is the most common method for preparing NiO hollow nanospheres. Soc.6 V2O5. V2O5-based composites. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59.448. the specific capacitance of V2O5 material was further improved to 250 F g1 in an organic solution containing an LiClO4 electrolyte.443 In summary. in terms of specific capacitance. 451 with permission from Elsevier. 13 451 shows that the specific capacitance of V2O5 is dependent on the electrolyte used.452 In their work. the chargetransfer resistance was greatly reduced.443 reported that an electrodeposited nickel hydrous oxide film could exhibit a specific capacitance as high as ca. both Ni(OH)2 and Co(OH)2–Ni(OH)2 should be satisfactory materials for ES. However. When it was combined with V2O5 to form a composite. the potential window of these materials is too narrow. much better performance can be achieved.. 797–828 3. V2O5 nanofibres showed the highest specific capacitance. showing high specific capacitances of 770 F g1 and 585 F g1 at the discharge currents of 2 A g1 and 5 A g1.423 (Reprinted from ref. 423 with permission from Elsevier.445 For a Co0. 2012. The specific capacitance obtained was 350 F g1. a microwave-assisted gas/liquid interfacial method.453–457 For example. Unfortunately. Recently. In addition.449 For example. Jayalakshmi et al. Similarly.440 (2) Ni(OH)2. was used to prepare a flowerlike NiO hollow nanosphere. Rev. respectively. three times higher than that of a V2O5xH2O thin-film electrode (300 F g1).) leading to not only high surface area but also better mass transportation. Vanadium oxides have also been investigated for their potential use in ES due to their variable oxidation states. For example. 1000 F g1. if the micropore structure of this kind of materials is optimized.444 reported a nickel hydroxide material with a mesoporous structure of interconnected nanoflakes. A V2O5 sample prepared by a sol–gel method451 exhibited a maximum specific capacitance of 214 F g1 at a scan rate of 5 mV s1 in a 2 M KCl solution.447 Therefore.457 demonstrated that at a scan rate of 100 mV s1. CNTs have been explored as a compositing material to form V2O5/CNT composites.2.446 For further improvement.451 (Reprinted from ref. compared to 1 M H2SO4 (106 F g1) and 2 M KOH (8 F g1). a V2O5xH2O/CNT film electrode also showed a high specific capacitance of 910 F g1 at a potential scan rate of 10 mV s1. 41. which contain materials with higher electronic conductivity such as metal fibres. have been developed.View Article Online Published on 21 July 2011. which can yield surface/bulk redox reactions.458 SnO2 has also been explored as a composite material.59 layered double hydroxide the specific capacitance reached 1809 F g1 at 1 A g1. the electronic properties were significantly improved. a SnO2–V2O5–CNT electrode provided a specific capacitance Fig. Fig. as it is semiconductive and has conventional redox properties. After introducing mesoporous carbon into the Ni hydroxide to form a nickel hydroxide/mesoporous carbon composite. In the case of Co(OH)2–Ni(OH)2/Y-zeolite composites. 2 M LiCl (—). the specific capacitance was estimated to be as high as 1710 F g1.

3 and 1.462 Again.463 However.2.8% after 500 cycles of charging/ discharging. Their application as ES electrode materials seems unrealistic at the present stage of technology.2.8 Iron oxides (Fe2O3 and Fe3O4). the major disadvantage for SnO2 material is its small potential.466 However.473. When the scan rate was changed from 2 to 200 mV s1. its price is even higher than that of RuO2.472 An LiMn2O4 cathode showed a specific capacity of 130–100 mA h g1 at 10–100 C rate within 0.470 while 554 F g1 was achieved at a high scan rate of 100 mV s1. a high specific capacitance of 1200–1400 F g1 was obtained when tested at a scan rate of 2 mV s1. Chem.469 Its specific capacitance behavior was found to be comparable to that of RuO2.0.3 V. although the introduction of Al2O3 into SnO2 can expand its potential window. A Bi2O3 electrode exhibits good electrochemical supercapacitive characteristics as well as high stability in aqueous NaOH solution.475 The asymmetric ES cell containing LiMn2O4 (cathode) and MnFe2O4 (anode) showed a maximum operating voltage window of ca. a Fe3O4 film prepared via a hydrothermal process displayed a typical pseudocapacitive behavior in a 1 M Na2SO3 solution. It was reported that a hybrid supercapacitor consisting of MCNTs and a-Fe2O3/MCNT thin-film electrodes yielded a high specific energy density of 50 W h kg1 at a specific power density of 1000 W kg1 over the potential range of 0–2.457 The above results demonstrate that the electronic properties of V2O5 can be favorably changed with a suitable choice of additive in the electrode material. a-Fe2O3 is another candidate for ES electrode material. Recently. Even a SnO2/RuO2 composite could only give a specific capacitance of 33 F g1 at a scan rate of 50 mV s1. However.9 Other materials.7 V) due to its electrochemical decomposition. 2012. offering low cost and minimal environmental impact. Unlike MnO2-based materials. yielded a specific capacitance of 140 F g1. This journal is c The Royal Society of Chemistry 2012 3. a Fe3O4 electrode synthesized using electrocoagulation and a reflux method exhibited a specific capacitance of only 5.472 The new materials investigated include MnFe2O4.474 This nanocrystalline MnFe2O4. similar to RuO2. 1. much higher than a V2O5–CNT electrode. the specific capacitance of a nanoscaled SnO2–Al2O3 composite can reach 119 F g1 in a 0.459 A Sb-doped SnO2 nanocrystallite synthesized by a sol–gel process460 had a specific capacitance of only 16 F g1 in a 1 M KOH electrolyte even at a low scan rate of 4 mV s1. showed a specific capacitance of 99 F g1.471 (3) New materials. was 10 and 5. its low specific capacitance is a limitation for practical application. acting as an anode material. (2) Transition metal nitrides. In this case.. transition metal nitride materials have attracted much attention due to their high electrical conductivity (B106 O1 m1) and chemical stability (excellent resistance to common acids and alkali).467 One-dimensional MoO2 nanorods.472 The energy density of LiMn2O4 decreased very fast with rising current density because the large diameter of the solvated Li+ could lead to difficulty of Li+ solvation and desolvation at high current densities.462 3.4 F g1 at a scan rate of 100 mV s1. 41. Rev. Many other metal oxide materials. poor electronic conductivity restricts its applications in high-power storage devices.2 F g1 between 1 and 0. The incorporation of MCNTs into a-Fe2O3 nanospheres seems to be a way to improve its conductivity. its specific capacitance is much lower than other metal oxides’. whose pseudo-capacitance essentially comes from amorphous MnO2.79 Using a nanostructured vanadium nitride.465 Neither Fe2O3 nor Fe3O4 seem realistic materials for ES due to their poor capacitance and cycle stability.8 kW kg1. lithium-ion ES technology has been introduced. a SnO2 composite electrode synthesized by impregnating tin oxide sol into resorcinol–formaldehyde wet gels or by impregnating tin tetrachloride solution into carbon aerogel electrodes displayed a specific capacitance of only 66–70 F g1. Ag/AgCl/saturated KCl(aq. molybdenum nitride (MoN) was explored as an ES electrode material in sulfuric acid solution. respectively.View Article Online Published on 21 July 2011. and it retained 70% of its original capacitance value even when the potential scan rate was increased from 30 to 300 mV s1. Soc.8 V. a specific capacitance of 118. 797–828 821 . Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. This device shows advantages such as reduced mass and volume as well as increased operating voltage over traditional ES technology. For example.468 All of these metal oxide materials present faradaic pseudocapacitance to a moderate extent. and 101 F g1 at a high scan rate of 200 mV s1. LiMn2O4 and NaMn2O4. The highest specific capacitance achieved with electrodeposited Bi2O3 films was 98 F g1.7 SnO2.5 W h kg1 at 0. SnO2 has also been explored as an alternative ES electrode material. leading to better ion diffusion.1 V. Bi2O3. and a capacitive retention of 88. of 121.3–0.2.464 Recently. In recent years.15 For example. such as IrO2.2. which is much greater than pure SnO2. This cell could reach the maximum specific power and energy densities when the mass ratio between the anode and the cathode was B4. the specific capacitance dropped from 100 to 8 F g1.463 Fe3O4 is another inexpensive material exhibiting pseudocapacitance in alkali sulfite electrolytes. have also been explored as electrode materials for ES.2.9 V (vs. For example. Vanadium nitride seems to be a promising ES electrode material. For example. MoN has a substantially smaller operating voltage range (only 0.1 M NaCl solution. based on the total mass of two electrodes. Unfortunately. the specific capacitance was reduced by 90% when the potential scan rate was increased. hydrous IrO2 showed a specific capacitance close to 550 F g1. However. The oxides of multivalent metal iridium exhibit a large faradaic pseudocapacitance.)). Its specific capacitance was found to be 161 F g1 at 30 mV s1. (1) Other metal oxides. but they suffer from one problem or another. the specific cell energy density. and MoO2. 3. prepared by thermal decomposition of tetrabutylammonium hexamolybdate (((C4H9)4N)2Mo6O19) in an inert atmosphere.2.461 Furthermore. amorphous nanostructured SnO2 synthesized using electrochemical deposition showed a specific capacitance value as high as 285 F g1 at a scan rate of 10 mV s1.3 F g1 in a 1 M Na2SO4 solution.472 It exhibits high power delivering capability and superior cycling stability in aqueous electrolytes. MnFe2O4 exhibits pseudo-capacitance in crystalline form. However.225 However. owing to poorer electron transport within the a-Fe2O3 film and the reaction’s comparatively sluggish kinetics.

Nanoscale Res. P. Carlen. N.. M. and metal oxides. Consequently. 2009. Met. Schnyder. Rodatz. Taberna. Several important ES electrode materials that should be mentioned are carbon-based materials. the obtained composites can overcome the drawbacks of the individual substances and embody the advantages of all constituents. 3 R. expanding active sites. 2010. 11. P.472 An NaMnO2 cathode showed two redox couples in 0. 39. Pandolfo and A. the cell also exhibited a low self-discharge rate as well as a good cycling stability.. Chem. the electrochemical utilization of the material and ionic transport throughout the internal volume of the thicker electrode layer will be limited. 4 R. H. 2008. and rate capability due to increased electrical conductivity. Electrochim. meaning more active sites. and more electroactive sites for faradaic energy storage. Tanaike. Power Sources. resulting in high charge/discharge capacities even at high current densities. and given the commercially available ES. conductive polymers. higher specific surface area and rational pore distribution have been achieved. To overcome this challenge. Regardless of the materials for ES electrodes. 937. Garcia. inducing porosity. S. Zhang and X. 45.. although their capacitances (or energy densities) are still low. O. in a real ES they may not necessarily be ideal electrode materials. preventing particles from agglomerating. With respect to metal oxides. Carbon. extending the potential window. and so on. 564. Regarding conductive polymers. Chem. Power Sources. backup power sources. the advantages of high power density. nanospheres. which were ascribed to the intercalation– deintercalation of Na+ into and from the solid lattice. Inagaki. 195. 10 E. 7. Acta. The porosity of ES materials should be particularly emphasized here. 2007. Hence. Bu¨chi. Beguin. They can provide short transport/diffusion path lengths for ions and electrons. (3) low internal electrical resistance for efficient charge transport in the composite electrode. In particular. Gogotsi.445–447 But it is worth to point out that the reverse effects may also take place in the process of making composites. 845. there should be a compromise among the composition of individual substances and an optimized molar ratio of constituents for every composite material. Nano-micropores are necessary to achieve higher specific surface area. However. 2483. Proc. more efficient contact of electrolyte ions. high efficiency. For carbon materials. 6 E. References 1 C. and (4) better electrochemical and mechanical stability for good cycling performance. P. Trends in ES With increasing demands for clean. 7 L. 41. P. Rev. leading to faster kinetics. Largeot. Gogotsi and P. Mater. Material morphology is closely related to the specific surface area and the diffusion of ions in the electrode. Recent trends in ES also involve the development of nanostructured materials. Portet. Electrochem. Chem. and the combined water is believed to be helpful for ion transport. (2) Nanomaterials. Simon and Y. improving cycling stability. with dimensions matching the size of solvated anions and cations are crucial for ES electrode materials. one of the key challenges for ES is their limited energy density.. and burst-power generation in electronic devices has been demonstrated. and long life expectancy have made electrochemical supercapacitors one of the major emerging devices for energy storage and power supply. 2520. becoming a large obstacle to the film’s practical use in ES electrodes. protecting active materials from mechanical degradation. such as nanoaerogels. D. Am. 7880. F. 130. Synth.5 W h kg1 at a power density of 130 W kg1. pore network. 21. The asymmetric ES containing active carbon and NaMnO2 electrodes exhibited a specific capacitance of 38. (2) suitable pore-size distribution. and one-dimensional nanostructure materials seem to be very promising for ES application due to their reduced diffusion paths and larger specific surface areas. 2730. combining different materials to form composites should be an important approach because the individual substances in the composites can have a synergistic effect through minimizing particle size. Nanostructured materials possess high specific surface area. 9. two important research directions in ES electrode exploration are: (1) Composite materials. 822 Chem. This journal is c The Royal Society of Chemistry 2012 . Y. C. 38. and these micropores must be ensured to be electrochemically accessible for ions. 797–828 It is worth pointing out that although thin films can achieve very high surface area. J. 654. 9 M. Ba¨rtschi. J. 2001. Soc. pore network. Ko¨tz. 2008. 2 S. the favored properties of ES electrode materials include: (1) high specific surface area.. J. Dietrich. J. G. and pore length for facilitating the diffusion of ions at a high rate. Frackowiak and F. These values are based on the total mass of the active electrode materials (including anode and cathode). V. the availability and wettability of pores. Chem. Hollenkamp. Lett. C. facilitating electron and proton conduction. Konno and O. leading to a short ES lifetime. high specific capacitance (>2000 F g1). 2010. which show high specific capacitances. 2001. 8 H. In the case of RuO2-based materials. amorphous structures can possess high specific surface areas and favor the diffusion of ions into the material’s bulk.Published on 21 July 2011. 11 A. Hermann and R. A. G. Phys. 2000.9 F g1 and an energy density of 19. Kandalkar. Lokhande. S. Barrade. 157. Mu¨ller. the major challenges are their swelling and shrinking during charge/ recharge. Dhawale. This is because when a film is used to construct a thicker electrode layer. J. Rev. 1774. Soc.5 M Na2SO4 within the potential range of 0–1. 1299. Scherer. High capacities over 1700 F g1 have been reported on the basis of composite materials. 5.475 4. Soc. a major focus of ES research and development should be to discover new electrode materials with high capacitance and a wide potential window. Feng. Soc.. although they have high capacitances. As a result. 2006. Tsukada. sustainable energy.1 V. Downloaded by LAMAR UNIVERSITY on 03/02/2015 23:13:59. Simon. B. nanoplates. their feasibility for practical applications in hybrid power sources. 2012. In the design of ES electrode materials. and providing extra pseudocapacitance. Frackowiak. Kim and C. 2010. The specific capacitance of the NaMnO2 electrode was found to be 140 F g1. Zhao.. 160. Chmiola. View Article Online Meanwhile. Nat. Li and Y. 5 P. which has hindered their wider application in the field of energy storage. G. Phys. To develop new materials with optimal performance. Gallay. Ko¨tz and M. 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