REVIEW

published: 08 May 2015

doi: 10.3389/fenrg.2015.00023

A review for aqueous

electrochemical supercapacitors
Cuimei Zhao 1 and Weitao Zheng 2*
1
Key Laboratory of Preparation and Applications of Environmental Friendly Materials, Ministry of Education, College of
Chemistry, Jilin Normal University, Siping, China, 2 Department of Materials Science, Key Laboratory of Mobile Materials,
Ministry of Education and State Key Laboratory of Superhard Materials, Jilin University, Changchun, China

Electrochemical capacitor is the most promising energy-storage device that can meet the
demands of high-power supply and long cycle life; however, low-energy density and high-
fabrication cost limit its further development. Researchers have paid more attention to the
development of electrode material in the past, and very few people attach importance to
the research of the electrolyte, especially the redox electrolyte, which is important for
improving specific capacitance greatly. This paper presents a review of the research
Edited by:
in not only electrode material but also redox aqueous electrolyte and together with an
Peter G. Bruce, important part of supercapacitor device. The advantages and disadvantages for different
University of St. Andrews, UK
electrode material and electrolyte are discussed. And the new trends in supercapacitor
Reviewed by:
development are also summarized.
Jinping Liu,
Wuhan University of Technology,
Keywords: electrode, electrolyte, additive, supercapacitor, energy density, power density, cycling stability
China
Jie Xiao,
Pacific Northwest National
Laboratory, USA Introduction
Shichun Mu,
Wuhan University of Technology, Energy is an important issue all over the world. The rapid deterioration of environment and
China depletion of fossil fuels call not only for more clean and renewable energy sources but also more
*Correspondence:
advanced energy conversion/storage systems. Research efforts have mostly focused on two types
Weitao Zheng, of electrochemical devices: batteries and capacitors. As shown in Figure 1 (Simon and Gogotsi,
Department of Material Science, Key 2008), batteries suffer from low-power density although they have high-energy density, whereas
laboratory of Automobile Materials of conventional capacitors exhibit high power but low-energy density. Supercapacitor, also known
MOE, and State Key Laboratory of as an electrochemical capacitor (EC), has bridged the gap between battery and conventional
Superhard Materials, Jilin University,
capacitor, because of the great advantages including high power and energy supply, long cycle
Changchun 130012, P. R. China
life, flexible operating temperature, and environmental friendliness (Conway, 1999; Burke, 2000,
[email protected]
2010; Frackowiak and Beguin, 2001; Pandolfo and Hollenkamp, 2006; Frackowiak, 2007; Zhang
and Chen, 2008; Zhang and Zhao, 2009; Conte, 2010; Inagaki et al., 2010; Zhai et al., 2011; Chen
Specialty section: et al., 2013a; Zhi et al., 2013). ECs are widely used in consumer electronics, hybrid vehicles, and
This article was submitted to Energy
industrial power/energy managements. However, the disadvantages of low-energy density and high-
Storage, a section of the journal
Frontiers in Energy Research
fabrication cost for ECs have been identified as a major challenge for the capacitive storage science.
To meet the energy demands for practical applications, advanced supercapacitors must be developed
Received: 03 December 2014
Accepted: 24 April 2015
with high-energy density without sacrificing the power density and cycle life. The energy density (E)
Published: 08 May 2015 can be obtained by the total capacitance (C) and the cell voltage (V) based on Eq. 1:
Citation:
Zhao C and Zheng W (2015) A review
E = 1/2CV2 (1)
for aqueous electrochemical
supercapacitors. Therefore, there have already appeared two methods in increasing energy density. First,
Front. Energy Res. 3:23. to improve the total capacitance, the most intensive approaches include the discovery of
doi: 10.3389/fenrg.2015.00023 advanced electrode materials and the improved understanding of ion transport mechanism

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Zhao and Zheng A review for aqueous electrochemical supercapacitors

electronic conductivity, excellent chemical stability, easy process-

ing, lower cost, and wide operating temperature range (Zhang
et al., 2009a). A variety of carbon materials are involved, such
as activated carbon (AC) (Ricketts and Ton-That, 2000; Pognon
et al., 2012), carbon aerogels (Saliger et al., 1998; Wei et al., 2005),
carbon nanotubes (CNTs), carbon nanofibres (An et al., 2001;
Zhang et al., 2009b), and so on. Conventional AC, with a theoret-
ical capacitance of 100 ~ 300 F g−1 , exhibits an excellent cycling
stability in several electrolytes. Recently, graphene nanosheets,
two-dimensional layers of sp2 -bonded carbon, have been found
to be an ideal carbon electrode material for ECs (Stoller et al.,
2008; Zhao et al., 2009a; Zhu et al., 2010; Le et al., 2011), with
an ideal capacitance of 550 F g−1 when the specific surface area
of 2675 m2 g−1 is fully used (Liu et al., 2010).
A lot of research has been done for various carbon materials at
home and abroad, but the study was only limited to improving the
pore size distribution, surface area, and surface functional groups
of the carbon material. However, the specific capacitance cannot
be improved significantly because of double-layer capacitance
mechanisms. At present, the combination of carbon material and
pseudocapacitive material can bring synergistic effect, realizing
the overall system excellent electrochemical performance.

FIGURE 1 | Specific power against specific energy, also called a Metal Oxides/Hydroxides
Ragone plot, for various electrical energy-storage devices. The shaded Based on the faradic pseudocapacitive energy-storage mecha-
curves were obtained from Simon and Gogotsi (2008).
nism, metal oxides/hydroxides, such as ruthenium, manganese,
cobalt, nickel, and vanadium, can provide higher specific capac-
in small pores (Zhai et al., 2011); however, the improvement in itance than conventional carbon materials and better cycling
total capacitance is not significant only by electrode materials. stability than polymer materials.
Very recently, there have been a few reports that redox additives Ruthenium oxide, with wide potential window, high-redox
are introduced into the conventional electrolyte, with additional reversibility and high conductivity shows remarkably high-energy
pseudocapacitive attribution of the additives between the elec- density, power density, and cycling stability (Sakiyama et al., 1993;
trode and electrolyte, the capacitance is obviously enhanced (Su Jia et al., 1996; Kim and Kim, 2006; Lee et al., 2010). For example,
et al., 2009; Roldán et al., 2011; Wu et al., 2012; Chen et al., the capacitance can be as high as 1300 F g−1 for nanotubular
2013b; Senthilkumar et al., 2013). Second, to improve the cell arrayed electrode of hydrous ruthenium oxide (Hu et al., 2006).
voltage, asymmetric supercapacitors combining electric double- However, the high cost for precious metal becomes a major barrier
layer anode and redox reaction cathode show promising capacitive for the commercialization. The present study mainly concentrated
performance. in two aspects: first, composite ruthenium oxide with carbon or
cheap metal oxide material, to improve the utilization ratio of
ruthenium oxide; second, seek cheap metal oxide/hydroxide to
Electrode Materials replace precious metals (Zheng and Jow, 1996; Fang et al., 2001;
Hu and Huang, 2001; Jeong and Manthiram, 2001; Ke et al., 2005;
In principle, capacitive behavior can be classified into two types:
Zhao et al., 2012a; Sellam and Hashmi, 2013). For example, Zhang
the electrical double-layer capacitance (EDLC) arising from elec-
et al. (2014) have reported a facile hydrothermal method without
trostatic attraction between electrolyte and electrode surface; the
reducer to fabricate graphene-RuO2 nanocomposites, achieving
pseudocapacitance associated with fast and reversible faradic reac-
high-specific capacitance in alkaline/acidic/neutral electrolyte.
tions of the active species on the surface of the electrode (Zhang
Wang and Zhang (2004) have designed to load Ru1−y Cry O2 on
and Zhao, 2009; Zhai et al., 2011). Therefore, according to the
the TiO2 nanotubes with a maximum specific capacitance of
fundamental energy-storage mechanisms, the typical electrode
1272.5 F g−1 obtained. Partially due to the discovery of advanced
material is EDLC material, such as various carbon materials. The
electrode materials and new synthetic method, more and more
other is pseudocapacitance material based on transition-metal
electrode materials with high performance have been developed
oxides/hydroxides and conducting polymer. Besides, MXenes and
(Simon and Burke, 2008; Simon and Gogotsi, 2008). In recent
MOF material are the latest electrode material.
years, inexpensive pseudocapacitive active materials, such as
Co3 O4 /Co(OH)2 (Simon and Burke, 2008; Wang et al., 2009; Gao
Carbon Materials et al., 2010; Xu et al., 2010; Yuan et al., 2010, 2012; Anantharamulu
Carbon materials, corresponding to EDLC, are considered the et al., 2011; Asano et al., 2011; Xia et al., 2011a; Huang et al.,
most ideal materials for ECs for high-specific surface area, good 2012), NiO4 /Ni(OH)2 (Song and Gao, 2008; Yuan et al., 2009,

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Zhao and Zheng A review for aqueous electrochemical supercapacitors

2011; Zhang et al., 2010; Cao et al., 2011; Jiang et al., 2011; Xia et al.,
2011b; Zhu et al., 2012), MnOx (Ragupathy et al., 2009; Yan et al.,
2010a; Wang et al., 2011; Yu et al., 2011a,b; Lee et al., 2012a, 2013;
Song et al., 2012; Si et al., 2013), Fe3 O4 (Obradovic et al., 2009;
Zhao et al., 2009b; Lee et al., 2012b),and so on have attracted the
attentions of the researchers. Chang et al. (2010) created nanos-
tructure Co(OH)2 electrode, exhibiting a high pseudocapacitance
of 2800 F g−1 and an outstanding rate capability and cyclic stabil-
ity. Wang et al. have reported a facile synthesis of nickel cobalt
layered double hydroxides (LDHs) on conducting Zn2 SnO4 by
CVD and electrochemical deposition. This novel material demon-
strates an outstanding electrochemical performance with a high-
specific capacitance of 1805 F g−1 at 0.5 A g−1 , and an excellent
rate performance of 1275 F g−1 at 100 A g−1 (Wang et al., 2012a).
Zhao et al. (2011) have prepared layered Co(OH)2 , showing a
high-specific capacitance of 651 F g−1 , but only 76% of initial
capacitance remains after 500 cycles at 50 mV s−1 . With higher
specific capacitance, the cycling stability of the pseudocapaci-
tive materials has been sacrificed. This drawback must be over-
come (Simon and Gogotsi, 2008). To improve low conductivity
and poor stability, such inexpensive pseudocapacitive materials
are often incorporated into highly conductive nanostructured
materials. Recently, composite electrode material has been stud-
ied for ECs, showing good electrochemical performance than
that of pure oxide/hydroxide. For example, a facile strategy is
designed to deposit Co(OH)2 nanoparticles on graphene sheets in
a water-isopropyl alcohol system. The specific capacitance of the
grapheme/Co(OH)2 nanocomposite reaches 972.5 F g−1 , leading
FIGURE 2 | Discharge curves of (A) the Ni foam/graphite
to a significant improvement compared to each individual coun-
nanosheets/Ni(OH)2 electrode at the current density of 60 A g−1 for
terpart (Chen et al., 2010). Yan et al. (2010b) have composited 700 cycles and (B) the Ni foam/Ni(OH)2 electrode at the same current
graphene and Co3 O4 , exhibiting a high cycle stability (95.6% density for 500 cycles. The inset in (A) shows the charge–discharge curves
specific capacitance is retained after 2000 cycles); however, the of the composite electrode. The curves were obtained from Wang et al.
specific capacitance is only 243.2 F g−1 . Unfortunately, most of (2012b).

the reported oxide/graphene materials have been prepared by

chemical precipitation method, there exist some problems, the
particles are agglomerated easily and a binder is often required, area, allowing rapid and effective ion charge transfer; (2) Ni(OH)2
that could decrease the active surface area and increase the inter- or Co(OH)2 nanosheets with high-electrochemical activity are
nal resistance of the ECs. To overcome the disadvantages, we have directly grown on graphene, with the covalent chemical bonding
focused on binder-free Ni(OH)2 /graphene/Ni foam (Wang et al., (C–O–Co or C–O–Ni) formed, favoring the electrochemical sta-
2012b) or Co(OH)2 /graphene/Ni foam (Zhao et al., 2012b) elec- bility; (3) graphene has been directly deposited on the Ni-foam
trode prepared by a combination of PECVD and electrodeposition collector, can avoid increasing the contact resistance between the
method, which could be explored as a promising material for ECs electrode and the collector. In order to further improve capacitive
because of high-electrochemical activity and cycle stability. From properties, the effects of crystallinity and electroconductivity of
the discharge curves of Figures 2A,B, the Ni(OH)2 /graphene/Ni carbon nanomaterials on Co(OH)2 are explored (Zhao et al.,
foam electrode maintains 93.3% of the initial specific capacitance 2013a). As shown in Figure 4, the Co(OH)2 nanosheet has been
after 500 cycles at a high-current density of 60 A g−1 , while under electrochemically deposited on graphene nanosheets (GNS) or
the same conditions only 54% specific capacitance retains for the amorphous carbon (APC). The electrochemical test results are
Ni(OH)2 /Ni foam electrode, which shows the obvious improve- listed in Table 1, Co(OH)2 /GNS exhibits a high cycling stabil-
ment of cycling stability for the composite electrode (Wang et al., ity, which is due to that the GNS with high conductivity and
2012b). In addition, a highly porous Co(OH)2 /graphene film on excellent flexibility can transfer smooth electrons and accom-
Ni foam has been obtained, as shown in Figure 3. The correspond- modate the volume expansion/contraction for Co(OH)2 in the
ing electrochemical measurement technology also confirmed that charge–discharge process. By contrast, Co(OH)2 /APC shows a
the introduction of graphene between Co(OH)2 and Ni foam high-specific capacitance, which can be ascribed to the lower con-
demonstrates an obvious enhancement of electrochemical sta- ductivity for APC, leading to the larger nanosheets of Co(OH)2 ,
bility compared with Co(OH)2 /Ni foam (Zhao et al., 2012b). promoting the complete redox reaction of Co(OH)2 (Zhao et al.,
The excellent pseudocapacitive behavior can be explained to the 2013a). The carbonaceous supports can not only act as a template
following (Wang et al., 2012b; Zhao et al., 2012b): (1) graphene to direct the growth of the as-deposited hydroxide but also affect
can provide high-electrical conductivity and high-specific surface the conductivity of the whole electrode, which may provide a

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Zhao and Zheng A review for aqueous electrochemical supercapacitors

FIGURE 3 | (A,B) SEM images for Co(OH)2 /GNS on Ni foam and (C) TEM images for Co(OH)2 /GNS. Obtained from Zhao et al. (2012b).

technical reference for improvement in the pseudocapacitance corresponding derivatives, due to its advantageous properties
behaviors and controllable preparation of composite electrode of low cost, high-voltage window, and high-doping rate during
material in the future. Besides hybrid metal oxide with carbon charge–discharge process. However, high resistance and low
material, a novel hybrid metal oxide core/shell nanowire arrays stability limit the wide application. Especially, swelling and
for ECs has been constructed. For example, Liu et al. choose shrinkage may occur during charge–discharge processes, leading
MnO2 and Co3 O4 as the shell and core materials, respectively. to mechanical degradation of the electrodes and fading of the
The hybrid nanowire array exhibit a high capacitance (480 F g−1 capacitive performance.
at 2.67 A g−1 ) and good cycle performance (97.3% capacitance Fabricating composite electrode materials to improve the
retention after 5000 cycles), which is 4 ~ 10-fold increase respect conductivity and stability become the new development direc-
to pristine Co3 O4 array. With this electrode design method, the tion. For example, a high-performance polyaniline electrode has
functions of each pseudocapacitive constituent are effectively uti- been prepared by electrochemical deposition on a porous carbon
lized, and realize a synergistic effect. Growing from the Co3 O4 monolith, showing the advancement of high-specific capacitance,
nanowire scaffold directly, the surfaces of MnO2 nanosheets are excellent rate capability, and good cycling stability. A capacitance
well separated, making active material fully available to the Li+ in value as high as 2200 F g−1 is obtained at a current density of
the electrolyte. As ultrathin MnO2 nanosheets construct a highly 0.67 A g−1 , and the specific capacitance is still up to 1270 F g−1
porous structure on Co3 O4 nanowire, the Co3 O4 core nanowires even at the high-current density of 66.7 A g−1 (Fan et al., 2007).
can be accessed by OH− and initiate the redox reaction (Liu Tao et al. (2014) have developed PPy/MnO2 composite through
et al., 2011). The concept opens up the possibility of constructing a simple electrodeposition process. The highest areal capacitance
high-performance pseudocapacitive materials without using any of the PPy/MnO2 electrode is about 2.45 F cm−2 at a current
carbon-based or conducting media. density of 0.2 mA cm−2 , and the capacity retention is 98.6% after
1000 cycles.
Conducting Polymers
Conducting polymers can provide capacitance behavior through Latest Electrode Materials
the faradic process. When oxidation takes place, ions are Recently, MXenes have been prepared combining hydrophilic
transferred to the polymer backbone, and when reduction surfaces with good conductivities. MXenes are synthesized by
occurs, the ions are released from this backbone into the the extraction of the “A” layers from the layered carbides or
electrolyte (Sharma and Bhatti, 2010). Conducting polymers carbonitrides known as MAX phases. MXenes show promise
widely used in supercapacitor mainly contain polyaniline as electrode materials for Li-ion batteries and Li-ion capacitors;
(PANI), polythiophene (PTh), polypyrrol (PPy), and their however, many are theoretically predicted (Khazaei et al., 2012;

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Zhao and Zheng A review for aqueous electrochemical supercapacitors

FIGURE 4 | SEM images for (A) GNS, (B) APC, (C) Co(OH)2 /GNS, and (D) Co(OH)2 /APC before discharge/charge cycles; (E) Co(OH)2 /GNS and
(F) Co(OH)2 /APC after 2000 discharge/charge cycles. Obtained from Zhao et al. (2013a).

Kurtoglu et al., 2012). Maria et al. have reported an intercalation- LiCl, and KOH). Only in LiOH electrolyte, did the Co-based MOF
induced high capacitances of Ti3 C2 Tx paper electrodes in aqueous shows an interesting pseudocapacitive behavior with a specific
electrolytes (KOH or NaOH), 350 F cm−1 at 1 A g−1 and 60% rate capacitance of 150 ~ 200 F g−1 and 98.5% capacitance retention
capability from 2 to 100 mV s−1 achieved (Lukatskaya et al., 2013). after 1000 cycles. However, to date, it is difficult to find that MOFs
The Ti3 C2 Tx material opens the door for the use of MXenes in electrode materials is clear advantaged in performance, durability,
energy-storage devices. As noted, the reported capacitances are or cost compared to other materials. For real breakthroughs,
probably far from the maximum values possible for MXenes in MOFs will probably need to be designed and optimized, with con-
general. A variety of ions should be accommodated between the trolling the MOF particle size, improving conductive character,
MXene layers. and so on.
Compared to inorganic high-surface-area materials, MOFs
offer the theoretical advantage of 100% utilization and improved Electrolyte
accessibility of the metal-cation centers due to their regular 3D
dispersion in an openstructure. For example, the introduction of Besides two electrodes, electrolyte plays an important role in
MOFs in EDLCs has been reported only recently (Diaz et al., 2012; capacitor performance, such as ion supplementary, electric charge
Lee et al., 2012c). Lee et al. have synthesized a Co-based MOF from conduction, and electrode particles adhesive. The requirements
cobalt nitrate and terephthalic acid, and the capacitive behavior for an electrolyte in ES include wide voltage window, high-
was investigated in various 1M aqueous electrolytes (LiOH, KCl, electrochemical stability, low resistivity, low toxicity, and so on.

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Zhao and Zheng A review for aqueous electrochemical supercapacitors

TABLE 1 | Electrochemical properties of Co(OH)2 /GNS, Co(OH)2 /APC and mainly carbon//carbon, Ru//Ru, and cheap metal symmetric
Co(OH)2 /GNS-APC.
supercapacitor.
Active mass Co(OH)2 /GNS Co(OH)2 /APC Co(OH)2 / Electric double-layer capacitor contains carbon material with
GNS-APC high-surface area as the electrode material in aqueous or organic
electrolytes. Compared to organic electrolytes, aqueous electrolyte
Current density is believed to high-ionic conductivity, low cost, and convenient
2 A g−1 692.0 F g−1 1287.2 F g− 1 784.0 F g−1
assembly of ECs in air. However, EDLCs only utilize the electro-
4 A g−1 653.1 F g−1 1194.9 F g−1 754.9 F g−1
8 A g−1 610.9 F g−1 1051.6 F g−1 724.4 F g−1 static charge at the electrolyte–electrode surface to store electric
16 A g−1 567.3 F g−1 904.7 F g−1 692.4 F g−1 energy so that the capacitance is limited. Very recently, an effective
32 A g−1 517.8 F g−1 762.2 F g−1 651.6 F g−1 approach has been reported wherein redox additives are intro-
Maintained capacitance 74.8% 59.2% 83.1% duced into the conventional electrolyte to enhance the capacitance
2 ~ 32 A g−1
via extra redox reaction between the electrode and electrolyte. Yu
capacitance after 2000 cp 95.7% 83.8% 93.2%
at 40 A g−1 et al. (2012) have doped m-phenylenediamine into a conventional
KOH electrolyte for carbon-based ECs. The specific capacitance
Bold are the best pseudocapacitive properties including cycling stability, specific capac- of the supercapacitor based on the new electrolyte is 78.01 F g−1 ,
itance, and rate capability among the three materials, further confirmed that different
carbon nanomaterials have different influences on the electrochemical properties of showing an increase of 114.16% over that of a supercapacitor
Co(OH)2 . based on a conventional KOH electrolyte. Similarly, Roldán et al.
This table was obtained from Zhao et al. (2013a). (2011) have reported that via adding electrochemically active
compound quinone/hydroquinone (Q/HQ) into the H2 SO4 elec-
The electrolyte used in ECs manly includes aqueous electrolyte, trolyte, an ultrahigh specific capacitance of 5017 F g−1 achieved
organic electrolyte. for carbon-based EC. The significantly improved capacitance
attributes to that the faradaic reactions of the Q/HQ couples
Aqueous Electrolytes 2H+ 2e−
(HQ ←→ Q) contribute pseudocapacitance to the electrode.
As far as the electrolytes are considered, aqueous electrolytes (such
However, working condition is not easily maintained, leading
as KOH, H2 SO4 , Na2 SO4 aqueous solution, and so on) have the
to a poor electrochemical stability. Senthilkumar et al. (2013)
advantages of high-ionic conductivity, low cost, non-flammability,
have improved the capacitance for AC materials through adding
non-corrosiveness, safety, and convenient assembly in air, com-
either KI or KBr into 1M H2 SO4 or Na2 SO4 electrolyte. With an
pared to organic electrolytes, which are believed to be less con-
improved specific capacitance, there is also a problem with the
ductive, expensive, usually flammable, and higher toxic. However,
electrochemical stability for only relying on the pseudocapacitive
the potential window (~1.2 V) for aqueous electrolytes is far lower
contribution from additive for EDLCs.
than that of organic electrolyte. According to Eq. 1, low-potential
Although more attention has been paid to investigating redox
window is the reason of low-energy density that limits its market
electrolyte for enhancing the EDLCs, no any efforts have been
application. The introduction of redox active substance in aqueous
done to improve pseudocapacitors. We have aimed at improv-
electrolytes can effectively enhance the capacitance via extra redox
ing the pseudocapacitive behavior of Co(OH)2 /GNS electrode
reaction between the electrode and electrolyte, which is shown in
through adding K3 Fe(CN)6 into KOH electrolyte, in our CV test
the part of symmetric supercapacitors.
result, two symmetric anodic/cathodic pairs are superimposed
on a broad redox background, corresponding to the redox reac-
Organic Electrolyte tion of Co(OH)2 electrode and K3 Fe(CN)6 electrolyte, respec-
The restriction of aqueous electrolytes is the limited operating tively, indicating that reversible redox reactions of Co(OH)2
voltage (about 1.2 V). By contrast, organic electrolytes can provide solid electrode and K3 Fe(CN)6 liquid electrolyte occur simul-
a high-operating voltage up to 4 V. High-potential window is taneously and independently (Zhao et al., 2013b). The cycling
a large advantage for organic electrolyte. Among organic elec- stability for Co(OH)2 /GNS electrode either in KOH electrolyte or
trolytes solvents, acetonitrile (AN) and propylene carbonate (PC) K3 Fe(CN)6 + KOH electrolyte is examined by charge–discharge
are the most common. Besides, organic salts such as tetraethylam- tests for 2000 cycles at a high current density of 80 A g−1 . Both
monium tetrafluoroborate and tetraethylphosphonium tetrafluo- systems exhibit a high cycling stability, with retention of 94.4 and
roborate have also been used in ECs electrolytes. However, there 91.1% initial capacitance after 2000 cycles. This indicates that the
exist the following problems for organic electrolyte: first, high addition of K3 Fe(CN)6 into KOH electrolyte does not affect the
resistance limits the power density of capacitor; second, high water stability of the electrode material. In addition, the system can
content limits the working voltage of capacitor. be charged quickly, and discharged slowly, which means that the
promise can be offered to realize a high-performance battery-type
Supercapacitor supercapacitor.
Although the cost is relatively high, Ru//Ru symmetric super-
Symmetric Supercapacitors capacitor shows large specific capacitance, high potential win-
Symmetric supercapacitors with positive and negative electrode dow, and excellent cycling stability. For example, Xia et al.
material identical or similar can be divided into electric double- (2014) have developed 1.8 V symmetric supercapacitor using
layer capacitor and faradic capacitors according to electrode nanocrystalline Ru films as both negative and positive electrodes.
material working mechanism. Symmetric supercapacitors are The Ru//Ru symmetric supercapacitor exhibits a large areal

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Zhao and Zheng A review for aqueous electrochemical supercapacitors

TABLE 2 | Electrochemical performance of the asymmetric supercapacitors based on conventional electrode materials.

Electrode Electrolyte Capacitance Potential Energy density Power density Stability Reference
(F g−1 ) window (V) (Wh kg−1 ) (kW kg−1 )

NaMnO2 //AC Na2 SO4 38.9 1.9 19.5 0.13 97% (10,000 cp) Qu et al. (2009)
K0.27 MnO2 //AC K2 SO4 57.7 1.8 25.3 0.14 98% (10,000 cp) Qu et al. (2010)
NiO//AC KOH 38 1.5 – – 50% (1000 cp) Wang et al. (2008)
MnO2 -AC//AC Na2 SO4 33.2 2.0 18.2 10.1 92% (2500 cp) Gao et al. (2011)

TABLE 3 | Electrochemical performance of the asymmetric supercapacitors based on new electrode materials.

Electrode Electrolyte Capacitance Potential Energy density Power density Stability Reference
(F g−1 ) window (V) (Wh kg−1 ) (kW kg−1 )

rGO//MnO2 -rGO Na2 SO4 59.9 1.6 21.2 0.82 89.4% (1000 cp) Wu et al. (2014)
MnO2 -NF//G Na2 SO4 – – 30.2 14.5 83.4% (5000 cp) Gao et al. (2012)
NiCo2 O4 -Co0.33 Ni0.67 KOH 87.9 1.6 31.2 396 82% (3000 cp) Xu et al. (2014)
(OH)2 //CMK-3
MnO2 –NPG//PPy–NPG LiClO4 193 1.8 86 25 85% (2000 cp) Hou et al. (2014)
Co(OH)2 //VN KOH 62.4 1.6 22 19.5 80% (4000 cp) Wang et al. (2014a)
NiO-GF//HPNCNTs KOH 116 1.4 32 0.7 94% (2000 cp) Wang et al. (2014b)
CoO-PPy//AC NaOH – 1.6 43.5 5.5 91.5% (20,000 cp) Zhou et al., 2013
NiCo2 O4 -rGO/AC KOH 99.4 1.3 23.3 0.32 93% (2500 cp) Wang et al. (2012c)

capacitance (68 mF cm−2 ), high cycling stability (no capacitance (Qu et al., 2009, 2010), AC//NiO (Wang et al., 2008), AC//MnO2
loss after 2000 charge–discharge cycles), and good rate capability. (Gao et al., 2010), and so on. Table 2 summarizes the electrochem-
Similarly, a novel symmetric RuO2 /RuO2 supercapacitor with a ical performances of these conventional asymmetric supercapaci-
high-operating voltage of 1.6 V is also built using the nanocrys- tors. For these asymmetric supercapacitors, AC is commonly used
talline hydrous RuO2 electrode, exhibiting an energy density of as a typical negative electrode material, metal oxides are employed
18.77 Wh kg−1 at a power density of 500 W kg−1 (Xia et al., 2012). as the positive electrode material. The poor specific capacitance
For other inexpensive transition-metal oxides symmetric of AC and low stability of metal oxides/hydroxides would also
capacitors, working potential window are relatively low (no greatly restrict the supercapacitor performance, resulting rela-
more than 1 V), leading to relatively low-energy density. The tively low-energy density (10 ~ 30 Wh kg−1 ), power density, and
researchers try to improve working potential window for the cycling stability. Recently, partially due to the discovery of new
cheap metal oxides symmetric supercapacitor, but the effect is electrode materials and new synthesis method, advanced superca-
not obvious. For example, Reddy et al. (2009) have synthesized pacitors with high performance have been developed. As shown in
Au–MnO2 /CNT hybrid coaxial nanotube arrays and prepared Table 3, asymmetric supercapacitors with high-performance elec-
MnO2 //MnO2 symmetric capacitor. CNTs serve as an additive trode materials as cathode and anode materials show significant
for improving the electrical conductivity of the manganese oxide, superiority in energy density (~90 Wh kg−1 ), power density, and
leading high-specific capacitance, power density, and cycling sta- cycling stability.
bility; however, the potential window is only 0.7 V. Lu et al.
(2012) have synthesized nickel–cobalt oxide (NCO) nanosheets
on FTO substrates and prepared a symmetric supercapacitor Trends in ES
based on two NCO electrodes, exhibiting a high-specific capac-
Electrochemical capacitors with high-power density and cycling
itance of 89.2 F g−1 at 0.17 A g−1 , but a low-potential window
performance have bridged the gap between conventional capaci-
of 0.5 V.
tors and batteries. However, one of the key challenges for ES is the
limited energy density. To overcome this challenge, ECs research
Asymmetric Supercapacitors should focus on improving the specific capacitance and widen
As an improvement to symmetric supercapacitors, asymmetric potential window.
supercapacitors combining electric double-layer anode (carbon
materials) and redox reaction cathode (such as metal hydrox- (1) Improve the specific capacitance. One common strategy is
ide/oxide materials, Li-ion battery materials, composite electrode to design and synthesis new materials, which must satisfy
material) show promising capability to enhance the energy den- the following conditions: first, good conductivity for efficient
sity, that is because asymmetric supercapacitors can make full charge transport; second, high-specific surface area for more
use of the different potential windows of the two electrodes to active sites; third, good mechanical and electrochemical sta-
increase the operation voltage and enhanced specific capacitance bility for good cycling performance; last, favorable pores-ize
in the cell system. More recently, to obtain higher energy density, distribution for high-rate ions diffusion. The ECs electrode
considerable research efforts have been devoted to the various of material exploration directions are composite materials and
asymmetric capacitor systems, mainly including AC//LiMn2 O4 nanomaterials, with coating active materials with conductive

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Zhao and Zheng A review for aqueous electrochemical supercapacitors

carbon or constructing a novel hybrid metal oxide nano- ion-diffusion rate in solid-state electrolytes, large resistance of the
structure electrode for ECs. Nanocomposite can real- electrode material. Asymmetric capacitors with redox electrolyte
ize synergistic effect, facilitating electron and proton can exhibits large specific capacitance and wide potential window,
conduction, enhancing specific surface area, expanding resulting in an enhanced energy density. The supercapacitor can
active sites, inducing porosity, protecting active materials be regarded as a novel hybrid supercapacitor application that
from mechanical degradation, improving cycling stability. combines two energy-storage processes: the double-layer capaci-
Another effective one is to pursue new electrolyte with tance or faradaic pseudocapacitance characteristic from electrode
high-electrochemical activity and reversibility, contributing materials and the faradaic pseudocapacitance from electrolyte.
additional pseudocapacitance in specific potential window, It is important to design high-performance electrode materials,
and the problem of electrochemical stability for the choose the suitable electrolyte, solve well matching problem. With
composite electrode system should to be paid more attention the high resistance and low charge–discharge stability resolved,
further. such asymmetric supercapacitor is expected to be a highly promis-
(2) Widen the potential window. The strategy of developing and ing candidate for application in high-performance energy-storage
matching asymmetric capacitors can make use of the differ- systems.
ent potential windows of the two electrodes to increase the
operation voltage in the cell system. However, the matching Acknowledgments
problem appears between positive and negative electrode. If
the electrodes are matched well, the overall performance of The support from National Natural Science Foundation of China
the supercapacitor will be improved. Otherwise, its perfor- (Grant Nos. 50525204 and 50832001), the special Ph.D. program
mance may drop or the supercapacitor may be damaged. (Grant No. 200801830025) from MOE, Major science and tech-
nology project of Jilin Province (Grant No. 11ZDGG010), NSF
Solid-state supercapacitors (SSCs) are emerging as energy- of China (grant no. 51372095), program for Changjiang Scholars
storage devices due to excellent stability, light weight, and easy to and Innovative Research Team in University, the “211” and “985”
handle, however, suffer from poor rate capability due to limited project of Jilin University, China, is highly appreciated.

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doi:10.1039/c2nr32040a Copyright © 2015 Zhao and Zheng. This is an open-access article distributed under the
Zhou, C., Zhang, Y., Li, Y., and Liu, J. (2013). Construction of high-capacitance 3D terms of the Creative Commons Attribution License (CC BY). The use, distribution or
CoO@polypyrrole nanowire array electrode for aqueous asymmetric superca- reproduction in other forums is permitted, provided the original author(s) or licensor
pacitor. Nano Lett. 13, 2078–2085. doi:10.1021/nl400378j are credited and that the original publication in this journal is cited, in accordance with
Zhu, X., Dai, H., Hu, J., Ding, L., and Jiang, L. (2012). Reduced graphene accepted academic practice. No use, distribution or reproduction is permitted which
oxide-nickel oxide composite as high performance electrode materials does not comply with these terms.

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