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Advanced Asymmetric Supercapacitors Based on Ni(OH)2/

Graphene and Porous Graphene Electrodes with High
Energy Density
Jun Yan, Zhuangjun Fan,* Wei Sun, Guoqing Ning, Tong Wei, Qiang Zhang,
Rufan Zhang, Linjie Zhi,* and Fei Wei*

1. Introduction
Hierarchical flowerlike nickel hydroxide decorated on graphene sheets has
Supercapacitors or electrochemical capaci-
been prepared by a facile and cost-effective microwave-assisted method. In
tors have attracted considerable attention
order to achieve high energy and power densities, a high-voltage asymmetric in recent years because they can provide
supercapacitor is successfully fabricated using Ni(OH)2/graphene and porous instantaneously a higher power density
graphene as the positive and negative electrodes, respectively. Because than batteries and higher energy density
of their unique structure, both of these materials exhibit excellent electro- than conventional dielectric capacitors.[1–6]
Therefore, they have been widely used in
chemical performances. The optimized asymmetric supercapacitor could be
portable electronics, power back-up, elec-
cycled reversibly in the high-voltage region of 0–1.6 V and displays intriguing trical vehicles and various microdevices,
performances with a maximum specific capacitance of 218.4 F g−1 where high power density and long cycle-
and high energy density of 77.8 Wh kg−1. Furthermore, the Ni(OH)2/ life are desirable, and are considered to
graphene//porous graphene supercapacitor device exhibits an excellent long be the most important in next-generation
cycle life along with 94.3% specific capacitance retained after 3000 cycles. energy storage devices.[7,8]
Although supercapacitors have a high
These fascinating performances can be attributed to the high capacitance and
power density, they usually suffer from a
the positive synergistic effects of the two electrodes. The impressive results lower energy density than rechargeable
presented here may pave the way for promising applications in high energy batteries.[9] Advanced supercapacitors must
density storage systems. be developed with higher operating voltage
and higher energy without sacrificing the
power delivery and cycle life to meet the
energy demands for practical applications in the future.[10] The
improvements of energy density (E) can be achieved by maxi-
Dr. J. Yan, Prof. Z. J. Fan, W. Sun, Prof. T. Wei mizing the specific capacitance (C) and/or the cell voltage (V)
Key Laboratory of Superlight Materials and Surface Technology according to the following equation:[11,12]
Ministry of Education
College of Material Science and Chemical Engineering
E = 0.5C V 2 (1)
Harbin Engineering University
Harbin 150001, P. R. China More recently, asymmetric supercapacitors have been found
E-mail: [email protected] to be an effective alternative approach to increase the energy
Dr. G. Q. Ning density of supercapacitors. These asymmetric supercapac-
State Key Laboratory of Heavy Oil Processing
China University of Petroleum
itors consist of a battery-type Faradaic electrode (as the energy
Beijing 102249, P. R. China source) and a capacitor-type electrode (as the power source),
Prof. L. J. Zhi simultaneously offering the advantages of both supercapac-
National Center for Nanoscience and Technology of China itors (rate, cycle life) and advanced batteries (energy density).[9]
Zhongguancun, Beiyitiao 11 Therefore, asymmetric supercapacitors can make full use of
Beijing 100190, P. R. China the different potential windows of the two electrodes to provide
E-mail: [email protected]
a maximum operation voltage in the cell system, accordingly
Dr. Q. Zhang, R. F. Zhang, Prof. F. Wei
Beijing Key Laboratory of Green Chemical Reaction resulting in a greatly enhanced specific capacitance and signifi-
Engineering and Technology cantly improved energy density.[13]
Department of Chemical Engineering Hitherto, various materials such as transition metal oxides,
Tsinghua University metal hydroxides, and electronically conducting polymer mate-
Beijing 100084, P. R. China
E-mail: [email protected]
rials have been investigated extensively for possible applica-
tions in asymmetric supercapacitors.[7,8] Among them, Ni(OH)2
DOI: 10.1002/adfm.201102839 is one of the most promising candidates for its high theoretical

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specific capacitance (2082 F g−1).[1] Recently, an asymmetric

FULL PAPER
supercapacitor with graphene/Ni(OH)2 as the positive elec-
trode and graphene/RuO2 as the negative electrode[14] has been
demonstrated to exhibit a high specific capacitance (ca. 153
F g−1) and high energy (ca. 48 Wh kg−1) at a voltage of 1.5 V in
1 M KOH aqueous solution. Inspired by the potential applica-
tions of Ni(OH)2, numerous efforts have been recently devoted
to the synthesis of Ni(OH)2 nanostructures with different
morphologies and structures, such as plateletlike,[15] flower-
like,[16,17] nanoparticles,[18] microspheres,[19] nanotubes,[20] and
nanorods.[21] Among these different morphologies, flowerlike
nanostructured Ni(OH)2 has attracted considerable attention
because of its short diffusion path lengths for both electrolyte
ions and electrons, favoring the diffusion and migration of
electrolyte ions during the rapid charge/discharge process and Figure 1. Schematic illustration of the as-fabricated asymmetric super-
consequently improving the effective electrochemical utiliza- capacitor device based on Ni(OH)2/graphene composite as the positive
tion of Ni(OH)2.[22] electrode and porous graphene as the negative electrode in 6 M aqueous
Herein, for the first time, we report a novel strategy to pre- KOH electrolyte.
pare hierarchical flowerlike Ni(OH)2 decorated on graphene
sheets using a fast, facile, and cost-effective microwave
heating method without the need for hard/soft templates or pattern of the Ni(OH)2/graphene composite, which is perhaps
precipitate-controlling agents. The Ni(OH)2/graphene hybrid related to a more disordered stacking and quite uniform disper-
material showed a high specific capacitance of 1735 F g−1 and sion of the graphene sheets in the resulting composite. In addi-
high rate capability compared to a pure Ni(OH)2 electrode. tion, no peaks from other phases were detected indicating that
Moreover, an asymmetric supercapacitor based on Ni(OH)2/ the product is of high purity. Moreover, the relative intensity of
graphene composite as the positive electrode and porous the corresponding diffraction peaks for the Ni(OH)2/graphene
graphene as the negative electrode was successfully fabri- composite is significantly decreased compared to those of
cated (Figure 1). Our optimized asymmetric supercapacitor the pure Ni(OH)2 sample, demonstrating a decrease in grain
showed a specific capacitance of 218.4 F g−1 and a maximum sizes of Ni(OH)2 particles after decoration onto the graphene
energy density of 77.8 Wh kg−1 based on the total mass of sheets. The average crystalline sizes of the synthesized samples
active materials at a voltage of 1.6 V.
(003)

Ni(OH)2
(a) (b)

Ni 2p3/2
Ni(OH)2/graphene

Ni 2p1/2
Ni LMM2
2. Results and Discussion

Ni LMM1
Ni LMM
Intensity (a. u.)

Intensity (a.u.)

O 1s
(101)

O KLL
Ni 2s
(110)

2.1. Positive Electrode Materials

(006)

C 1s

N 1s

Typical X-ray diffraction (XRD) patterns of the

Ni 3p
Ni 3s

as-prepared hierarchical flowerlike Ni(OH)2/

graphene composite and free Ni(OH)2 are
shown in Figure 2a. It can be seen that the 10 20 30 40 50 60 70 80 0 200 400 600 800 1000 1200
XRD pattern of the Ni(OH)2/graphene com- 2θ (degree) Binding energy (eV)
posite is similar to that of free Ni(OH)2, indi- Ni(OH)2/graphene
cating that the Ni(OH)2/graphene composite
(c) (d)
Transmittance (a. u.)

484

has been well synthesized. All of the reflec-

Intensity (a. u.)

tions in the XRD pattern in Figure 2a can be

1200

D G

indexed to rhombohedral α-Ni(OH)2 with lat-

1385
1637
1583

tice parameters of a = b = 3.08 Å and c = 23.41 graphene

641

Å (JCPDS 38-715), which is in good agreement

with the reported pattern for α-Ni(OH)2.[23]
3435

2255

The four characteristic peaks at 12.1°, 24.6°,

33.3°, and 59.4° correspond to the (003), (006),
800 1000 1200 1400 1600 1800 4000 3500 3000 2500 2000 1500 1000 500
(101), and (110) diffraction planes, respec- -1 -1
Raman shift (cm ) Wavenumber (cm )
tively. According to the Bragg formula, the cal-
culated basal spacing is 0.73 nm, which is in
Figure 2. a) XRD patterns of pure Ni(OH)2 and Ni(OH)2/graphene composite. b) XPS
accordance with the reported values.[23,24] It is spectrum of the prepared Ni(OH)2/graphene composite. c) Raman spectra of the pristine
noteworthy that the diffraction peaks of C for graphene sheets and Ni(OH)2/graphene composite. d) FTIR spectrum of the prepared
graphene could not be observed in the XRD Ni(OH)2/graphene composite.

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calculated from the (003) diffraction peak

using Scherrer’s formula are 14.2 and
11.5 nm for the pure Ni(OH)2 sample and
the Ni(OH)2/graphene composite, respec-
tively, which is consistent with the above
XRD analysis.
In order to further understand the sur-
face information of the obtained samples,
X-ray photoelectron spectroscopy (XPS) was
also carried out to analyze the composition
of the particle surface (Figure 2b). It can be
clearly seen that the survey spectrum of the
Ni(OH)2/graphene composite mainly shows
carbon, oxygen, and nickel species as well as
a small quantity of nitrogen, which comes
from the precursor nickel nitrate hexahy-
drate. The peak located at 284.6 eV can be
assigned to the characteristic peak of C 1s
and a detailed analysis of the C 1s region
indicates that there are still some residual
oxygen-containing functionalities on the
reduced graphene oxide sheets because of
incomplete reduction (Figure 2b and Sup-
porting Information Figure S1a). The Ni 2p Figure 3. TEM images of a,b) Ni(OH) and c,d) Ni(OH) /graphene composite. b) and d) are
2 2
XPS spectrum shows two major peaks with higher magnifications of the square frame regions in (a) and (c), respectively.
binding energies at 873.5 and 855.9 eV, cor-
responding to Ni 2p1/2 and Ni 2p3/2, respec-
tively, with a spin-energy separation of 17.6 eV (Supporting skeletal vibration of the carbon ring in the graphene sheets,
Information Figure S1b), which is the characteristic of a respectively.[27] Additionally, the absorption band located at
Ni(OH)2 phase and in good agreement with previously reported 1200 cm−1 is probably related to the presence of carbonate ions
[ 23]
data. This result is also consistent with the XRD analysis as derived from the adsorption of atmospheric CO2 or hydrolysis
mentioned above. It is worth noting that there are some extra of urea.[16] Moreover, the band at 1385 cm−1 can be attributed to
lines marked as satellite peaks around the expected Ni 2p1/2 the interlayer nitrate anion,[16] whereas the two bands around
and Ni 2p3/2 signals in the Ni 2p region as shown in Figure S1b 641 and 484 cm−1 are ascribed to the δOH and νNi-OH vibrations,
(Supporting Information). respectively.[17,28]
The Raman spectra of pristine graphene and the Ni(OH)2/ The morphology and structure of the as-prepared samples
graphene composite are shown in Figure 2c. It can be clearly were observed by transmission electron microscopy (TEM).
seen that there are two broad peaks at 1361 and 1583 cm−1 Figure 3a clearly shows that the as-prepared Ni(OH)2 sample
in both samples, corresponding to the D and G bands of is composed of many well-defined flowerlike architectures with
graphene, respectively. In the Raman spectrum, the G band diameters of 300 to 400 nm. It can also be observed that each
represents the in-plane bond-stretching motion of the pairs flower is assembled by dozens of interconnected flake-like nan-
of C sp2 atoms (the E2g phonons); whereas the D band cor- opetals with thicknesses of around 7 nm (Figure 3a, b). The
responds to the breathing modes of rings or κ-point phonons distances between the lattice fringes is around 0.7 nm, corre-
of A1g symmetry.[25] In addition, for the Ni(OH)2/graphene sponding to the d-spacing of the (003) plane of α-Ni(OH)2, which
composite, there is an additional broad peak centered around is consistent with the XRD results. By incorporating graphene
1077 cm−1, which may be attributed to the vibration of interca- sheets, the flowerlike Ni(OH)2 are well inherited and decorate
lated nitrate ions.[26] homogeneously on the graphene sheets (Figure 3c). Interest-
To further confirm the XRD and Raman results, the com- ingly, the diameters of these flowerlike structures decrease
position of the as-prepared Ni(OH)2/graphene composite was to 200–250 nm and the thickness of the nanoplatelets also
examined by Fourier transform infrared (FTIR) spectroscopy decreases from 7 to 5 nm, indicating a homogeneous nuclea-
in the range of 400–4000 cm−1 and the results are shown in tion of Ni(OH)2 on the graphene sheets.
Figure 2d. The broad band at 3435 cm−1 corresponds to the To explain the formation of hierarchical flowerlike Ni(OH)2
O-H vibration of hydrogen-bonded hydroxyl groups and inter- grown on graphene sheets, a possible formation mechanism
calated water molecules located in the interlamellar space of based on experimental results is proposed, which is speculated
α-Ni(OH)2.[16,23] The very strong absorption band at 2255 cm−1 to follow an adsorption-nucleation-coalescence-anisotropic
is the typical vibration of C≡N triple bonds in the OCN− growth-self-assembly mechanism (Figure 4). The main reac-
anions, which are the byproducts of urea hydrolysis.[16] The tions in the system are as follows:[16]
weak bands around 1637 and 1583 cm−1 can be assigned to
the bending mode of the interlayer water molecule and the CO (NH2 )2 + H2 O ↔ 2NH3 + CO2 (2)

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50
(a) 5 mV s
-1

Current density (A g )
40

-1
-1
10 mV s
-1
30 15 mV s
-1
20 20 mV s
-1
25 mV s
10
0
-10
-20
Figure 4. Schematic illustration for the possible formation of the flower- -30
like Ni(OH)2 nanostructures decorated on graphene sheets.
-0.1 0.0 0.1 0.2 0.3 0.4 0.5
Potential (V vs. Hg/HgO)
 2+
Ni2+ + xNH3 ↔ Ni(NH3 )x (3)
2000

Specific capacitance (F g )
(b) Ni(OH)2/graphene

-1
Ni(OH)2
NH3 + H2 O ↔ OH− + NH+
4 (4) 1600

Ni2+ + 2OH− ↔ Ni(OH)2 (5) 1200

2+
Initially, the Ni ions in the solution are adsorbed on the sur-
face of graphene sheets because of the electrostatic attraction.
800
Then, urea decomposes to NH3 and CO2 according to Equa-
tion 2. NH3 can form a complex with Ni2+, which decreases the
concentration of free Ni2+ and accordingly reduces the growth 400
rate of the crystals.[29,30] During the microwave heating process,
urea can provide a steady OH− ion supply through hydrolysis
(Equation 2 and 4), which is favorable for the nucleation and 0
0 10 20 30 40 50
the formation of ultrathin Ni(OH)2 platelets based on the coa- -1
lescence mechanism. From a thermodynamics perspective, Scan rate (mV s )
the surface energy of an individual nanoplatelet is extraordi-
Figure 5. a) CV curves of Ni(OH)2/graphene composite at various scan
nary high. In order to minimize the overall surface energy, the rates in 6 M KOH. b) Specific capacitance of pure Ni(OH)2 and Ni(OH)2/
ultrathin platelets tend to self-assemble spontaneously to form graphene composite as a function of the scan rates based on the CV
3D flowerlike Ni(OH)2 architectures on the graphene sheets as curves.
the reaction continues further.[29]
Cyclic voltammetry (CV) is generally used to characterize the
capacitive behavior of an electrode material. Figure 5a shows
scan rates increase from 5 to 50 mV s−1, implying the improved
the typical CV curves of the as-prepared Ni(OH)2/graphene
mass transportation, excellent electron conduction within the
composite at different scan rates in 6 M KOH aqueous solution.
nanoparticles, and small equivalent series resistance. With
All the CV curves consist of a pair of strong redox peaks, indi-
increasing scan rates the potential of the oxidation peak shifts
cating that the capacitance characteristics are mainly governed
in the positive direction and that of the reduction peak shifts in
by Faradaic redox reactions, which is very distinct from that of
the negative direction, which is mainly related to the internal
electric double layer capacitors that usually produce a CV curve
resistance of the electrode.
close to an ideal rectangular shape. The anodic peak (positive
The specific capacitance of the electrode can be calculated
current density) occurred around 0.27 V (vs. Hg/HgO) indicates
from the CV curves according to the following equation:
an oxidation process related to the oxidation of α-Ni(OH)2 to
γ-NiOOH, whereas the cathodic peak (negative current density)  
observed around 0.10 V (vs. Hg/HgO) corresponds to a reduc- C= IdV / (υmV ) (7)
tion process following the Faradaic reactions of Ni(OH)2:
where C is the specific capacitance (F g−1) based on the mass
α ¯ Ni(OH)2 + OH  γ ¯ NiOOH + H2 O + e
− − of the electroactive materials, I is the response current den-
(6)
sity (A cm−2), V is the potential (V), υ is the potential scan rate
The symmetric characteristic of the anodic and cathodic (mV s−1), and m is the mass of the electroactive materials in
peaks indicates the excellent reversibility of the Ni(OH)2/ the electrodes (g cm−2). The specific capacitance of our as-pre-
graphene electrode. In addition, it can be seen that the shapes pared pure Ni(OH)2 and Ni(OH)2/graphene electrodes at dif-
of these CV curves show almost no significant change as the ferent scan rates in 6 M KOH is presented in Figure 5b. It can

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be seen that the specific capacitance of the Ni(OH)2/graphene

electrode is always higher than that of the pure Ni(OH)2
electrode at different scan rates. A high specific capacitance
of 1735 F g−1 can be obtained at 1 mV s−1 for the Ni(OH)2/
graphene electrode, which is comparable to those of previously
reported values.[1,23,28,29] When the scan rate is increased to
50 mV s−1, the specific capacitance of the Ni(OH)2/graphene
electrode is still 523 F g−1, and retain 30% of its initial value
with a scan-rate increase of 50 times, indicating the positive
synergistic effect of graphene and Ni(OH)2 in the composite.
Moreover, the specific capacitance decreases gradually with
increasing scan rate, which can be attributed to the diffusion
effect limiting the diffusion and migration of the electrolyte ions
within the electrode at high scan rates, resulting in low elec-
trochemical utilization of the Ni(OH)2 particles.[29] Therefore,
the high capacitance of the Ni(OH)2/graphene electrode can
be ascribed to the synergistic effect of graphene and Ni(OH)2.
Firstly, the Ni(OH)2 nanoplatelets on graphene sheets can effec-
tively utilize their high pseudo-capacitance. Secondly, 3D inter-
connected nanoplatelets can form plenty of macropores, which
is beneficial for the transport of electrolyte ions and charge
transfer reactions. Finally, the graphene sheets in the compos-
ites can not only buffer the volume change of Ni(OH)2 during
the charging and discharging processes, but also preserve the
high electrical conductivity of the overall electrode thanks to
the excellent conductivity of graphene.[31] Because of the high
performances of the Ni(OH)2/graphene composite, it is highly
desirable to develop a negative electrode material with superior
electrochemical performance to assemble asymmetric superca-
pacitors with a wider voltage range and thus higher energy den-
sity than each of the components. Figure 6. a) TEM and b) high-magnification TEM image of the porous
graphene. The arrows indicate the existence of pores in the graphene
sheets.
2.2. Negative Electrode Materials

Graphene has emerged as a promising material for applications densities from 1 to 25 A g−1, which is another typical character-
in energy storage and conversion devices because of its high istic of an ideal capacitor. No obvious iR drop is observed for any
surface area and excellent electrical conductivity.[31,32] Recently, of the curves, meaning that the electrode has low internal resist-
a KOH-activated graphene electrode has exhibited high spe- ance. The specific capacitance of porous graphene and chemi-
cific capacitance (200 F g−1) and rate performance in 1-butyl- cally reduced graphene at different charge/discharge current
3-methyl-imidazolium tetrafluoroborate/acetonitrile electrolyte, densities is compared in Figure 7c. It can be seen that porous
suggesting excellent electrochemical properties compared to graphene not only exhibits high specific capacitance values but
chemically reduced graphene.[33] In our previous work, porous also maintains these high values much better at high current
graphene was successfully synthesized using porous MgO density compared to chemically reduced graphene. The porous
sheets as the template using a chemical vapor deposition (CVD) graphene electrode shows a specific capacitance of 245, 236,
approach.[34] TEM images of this porous graphene show that 231, 220, and 209 F g−1 at different densities of 1, 2.5, 5, 10, and
numerous wrinkled and folded regions and considerable mes- 25 A g−1, respectively. Moreover, the porous graphene electrode
opores (3-8 nm) with a Brunauer-Emmett-Teller surface area of exhibits an excellent long cycle life with only 5.9% capacitance
1654 m2 g−1 are observed on the sheets (Figure 6a,b). Based on loss after 2000 cycles (Figure 7d). These interesting results dem-
its unique structure, it is highly expected that porous graphene onstrate that porous graphene delivers a high specific capaci-
will exhibit an excellent electrochemical performance compared tance and superior rate performance compared to chemically
to chemically reduced graphene. reduced graphene because of its narrow mesopore distribution
Compared to reduced graphene oxide, the CV curve of porous and open flat layer with high surface area.[34]
graphene measured in 6 M KOH solution still exhibits the typical
rectangular shapes without obvious distortion even at a scan rate
of 500 mV s−1 (Figure 7a), indicating an excellent capacitance
behavior and fast diffusion of electrolyte ions into the electrode. 2.3. Asymmetric Supercapacitors
Figure 7b shows the galvanostatic charge/discharge curves of
the as-prepared sample. It can be clearly observed that all the The high capacitance of the redox character of the Ni(OH)2/
curves are highly linear and symmetrical at various current graphene composite and the fast ion-transport property of the

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0.0 -1 graphene electrode. As a consequence, if the
(b)

Potential (V vs. Hg/HgO)

80 (a) 1: 1.0 A g
total cell voltage is expressed as the sum of
Current density (A g )

-1
-1

2: 2.5 A g
-0.2
40
3: 5.0 A g
-1

-1
the potential range for the Ni(OH)2/graphene
4: 10 A g
-0.4 -1 composite and that for the porous graphene
5: 25 A g
0 material, the cell voltage could be extended up
-0.6 to 1.6 V in 6 M KOH aqueous solution for an
-40
asymmetric supercapacitor.[35–37] For superca-
Chemically reduced graphene
pacitors, it is well-known that the charge bal-
-1
100 mV s
-80 -1 -1
-0.8
10 mV s 200 mV s
20 mV s
-1

-1
500 mV s
-1

-1
ance between the two electrodes will follow
50 mV s 500 mV s 5 4 3 2 1
-120
-1.0 -0.8 -0.6 -0.4 -0.2 0.0
-1.0
0 40 80 120 160 200
the relationship q+ = q-, where the charge
Potential (V vs. Hg/HgO) Time (s) stored by each electrode usually depends on
the specific capacitance (C), the potential
Specific Capacitance (F g )

(c) Capacitance retention (%)

(d)
-1

250
porous graphene
100 range for the charge/discharge process (ΔE),
200 80
and the mass of the electrode (m) following
Equation 8:[38]
150 chemically reduced graphene 60
q = C × E × m (8)
100 40

50 20 and in order to obtain q+ = q-, the mass bal-

ancing will be expressed as follows:[38]
0 0
0 5 10 15 20 25 0 400 800 1200 1600 2000
-1 Cycle number m+ C− × E −
Current density (A g ) = (9)
m− C+ × E +
Figure 7. a) CV curves of porous graphene at different scan rates in 6 M KOH. b) Galva-
nostatic charge/discharge curves of porous graphene at different constant current densities. Based on the above analysis of the spe-
c) Specific capacitance of porous graphene and chemically reduced graphene as a function of
cific capacitance values and potential ranges
the current densities calculated from the corresponding discharge curve for each current density.
d) Cycle performance of the porous graphene electrode at a scan rate of 200 mV s−1 in 6 M found for the Ni(OH)2/graphene composite
KOH aqueous solution. and porous graphene, the optimal mass
ratio between the two electrodes should be
m(Ni(OH)2/graphene)/m(graphene) = 0.44 in
electric double-layer storage of the porous graphene led to the the asymmetric supercapacitor cell.
successful fabrication of an asymmetric capacitor using them Figure S3a (Supporting Information) exhibits the CV curves
as the positive and negative electrodes, respectively (Figure 1). at different voltage windows for an asymmetric two-electrode
To further evaluate the electrochemical properties and esti- cell assembled with the optimal mass ratio between the two
mate the stable potential windows of the as-prepared Ni(OH)2/ electrodes in 6 M KOH aqueous electrolyte at a scan rate of
graphene composite and porous graphene, we performed CV 10 mV s−1. It can be clearly seen that the fabricated asymmetric
measurements on these two electrode materials in 6 M KOH supercapacitor shows a good capacitive behavior with quasi-rec-
using a three-electrode system at 20 mV s−1 before evaluating tangular CV curves, even at voltages up to 1.6 V. When the oper-
the asymmetric cell (Supporting Information Figure S2). The ation voltage window is 1.0 V, the presence of the redox peaks
CV curve of the porous graphene electrode exhibited a relatively indicate the pseudo-capacitive property of the supercapacitor
ideal rectangular shape and near mirror-image current response because of the Faradaic reaction of Ni(OH)2. Further increasing
on voltage reversal, and no obvious redox peaks were observed, the operation voltage window to values as high as 1.6 V, more
indicating a typical characteristic of a electric double-layer severe Faradaic reactions occur at the Ni(OH)2/graphene elec-
capacitor and excellent electrochemical reversibility. As for the trode. Figure S3b (Supporting Information) depicts the specific
CV curve for the Ni(OH)2/graphene electrode, its shape is more capacitance of the fabricated asymmetric supercapacitor as a
complicated and very distinguished from that of the porous function of the operation voltage window. It was found that the
graphene, indicating that its capacitance mainly originates from specific capacitance greatly increases from 28.8 to 88.1 F g−1 as
the redox pseudo-capacitance of Ni(OH)2. A pair of redox peaks the operation voltage window range is increased from 1.0 to
could be clearly observed with the cathodic peaks at 0.10 V and 1.6 V, which means that the stored energy and delivered power
anodic peaks around 0.27 V. The specific capacitance calculated could be improved at least by 783% according to Equation 1.
from the CV curves using Equation 7 under these conditions is As a consequence, the overall performance of the supercapac-
816 F g−1 for the Ni(OH)2/graphene composite, which is much itor could also be remarkably improved. As is generally known,
higher than that of the porous graphene electrode (217 F g−1). operating at higher voltage will be favorable for reducing the
This significant difference can be explained by the fact that the number of devices in series required to reach the desired output
overall capacitance of the Ni(OH)2/graphene composite derives voltage in practical applications.[10] Thus, we chose an operation
from the combined contribution of the primary redox pseudo- voltage window of 1.6 V in 6 M KOH aqueous electrolyte to fur-
capacitance of Ni(OH)2 and the electrical double-layer capaci- ther investigate the superior electrochemical performance of
tance of graphene in the composite, whereas only the electrical the as-fabricated asymmetric supercapacitor in our subsequent
double layer contributes toward the capacitance of the porous research.

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8 250 Figure 8c shows the typical galvanostatic

(b)

Specific capacitance (F g )
(a) 5 mV s
-1
1.6 V

-1
Current density (A g )

charging/discharging curves of our optimal

-1

6 10 mV s
-1 1.4 V
200 1.2 V
15 mV s
-1
asymmetric supercapacitor at a current den-
1.0 V
4
sity of 5 A g−1 in 6 M KOH aqueous solution.
-1
20 mV s
150
2
A good linear relation of the charge/discharge
0 100 potentials with time was found, indicating
-2
a rapid I–V response and small equivalent
50 series resistance.[3] Additionally, from the typ-
-4
ical isosceles triangular-shaped galvanostatic
0
-6
0 10 20 30 40 50 charge/discharge curve, it can be observed
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 -1
Voltage (V) Scan rate (mV s ) that the discharge curve is nearly symmetric
1.6 with its corresponding charging counterpart,
1.4 (c)
(d)
Capacitance retention (%)
100 demonstrating the excellent electrochemical
1.2 reversibility and good Coulombic efficiency.
80
As a long cycling life is an important
Voltage (V)

1.0
60 requirement for supercapacitor applica-
0.8
tions,[41] a cycling-life test was carried out for
0.6 40
the Ni(OH)2/graphene//porous graphene
0.4
20
asymmetric supercapacitor by repeating the
0.2 CV test between 0 and 1.6 V at a scan rate of
0.0 0 100 mV s−1 for 3000 cycles. Figure 6d shows
0 20 40 60 80 0 500 1000 1500 2000 2500 3000
Time (s) Cycle number the capacitance retention ratio of the asym-
metric capacitor charged at 1.6 V as a func-
Figure 8. a) CV curves of an optimized asymmetric supercapacitor in 6 M KOH electrolyte tion of the cycle number. It is worth noting
at different scan rates of 5, 10, 15, and 20 mV s−1. b) Variation of specific capacitance at dif- that the specific capacitance sharply decreases
ferent scan rates for the asymmetric supercapacitor operated within different voltage windows.
c) Galvanostatic charge/discharge curves of the asymmetric supercapacitor at a current density
after the initial 150 cycles (retained ca. 75.1%
of 5 A g−1. d) Cycle performance of the optimized Ni(OH)2/graphene//porous graphene asym- of its initial capacitance), which is probably
metric supercapacitor within a voltage window of 1.6 V at a scan rate of 100 mV s−1. related to pulverization and loss of electrical
contact between the active material and
the current as well as wettability issues.[42]
Figure 8a exhibits the CV curves of an optimized asym- The subsequent increase in capacitance can be related to an
metric supercapacitor at various scan rates of 5, 10, 15, and improvement in the surface wetting of the electrode by the
20 mV s−1 measured between 0 and 1.6 V in 6 M KOH aqueous electrolyte during extended cycling.[43] After 3000 cycles, the
electrolyte. The current-potential response is dependent on asymmetric supercapacitor displays an excellent long cycle life
the potential as opposed to the potential-independent cur- with only 5.7% deterioration of its initial specific capacitance,
rent response of an electrochemical capacitor based on a non- demonstrating superior long-term electrochemical stability.
faradaic process. The specific capacitance of the asymmetric In addition, such cycling performance is highly competitive
cell (based on the total mass of the active materials of the with those of some other asymmetric supercapacitors, such as
two electrodes) at different scan rates calculated from the CV Co(OH)2//activated carbon (93% retention after 1000 cycles),[44]
curves using Equation 7 is presented in Figure 8b. The spe- MnO2//activated carbon in organic electrolyte (96% reten-
cific capacitance decreases gradually with increasing scan rate tion after 1000 cycles),[45] graphene/MnO2//activated carbon
as diffusion limits the movement of electrolyte ions at high nanofiber (97% retention after 1000 cycles),[3] LiNi0.5Mn1.5O4//
scan rates because of the time constraint and only the outer activated carbon (95% retention after 1000 cycles),[46] Ni(OH)2//
active surface can be utilized for charge storage, resulting activated carbon (82% retention after 1000 cycles),[35] Ni(OH)2/
in a lower electrochemical utilization of electroactive mate- graphene//RuO2/graphene (ca. 92% retention after 5000
rials.[39] The higher specific capacitance could be obtained at cycles),[14] LiNi1/3Co1/3Mn1/3O2//AC (ca. 80% retention after
higher operation voltage windows thanks to the redox reac- 1000 cycles),[47] graphene/MnO2//graphene (79% retention after
tions of Ni(OH)2.[40] When the operation voltage window was 1000 cycles),[9] Li2MnO4//activated carbon (ca. 95% retention
1.6 V, a maximum specific capacitance of 218.4 F g−1 could be after 20000 cycles),[48] and MnO2//activated carbon in aqueous
obtained at a scan rate of 1 mV s−1, which is about 2.3, 3.6, electrolyte (87.5% retention after 19500 cycles).[49]
and 4.7 times the specific capacitances obtained when oper- The power density (P) and energy density (E) are generally
ated at 1.4, 1.2, and 1.0 V, respectively. Importantly, it should used as important parameters to characterize the electrochem-
be pointed out that the specific capacitance is calculated based ical performance of electrochemical cells.[3] The energy density
on the total mass of the active material on both electrodes. at different average power density (Pav) was calculated for our
The excellent performance of the Ni(OH)2/graphene//porous cells from the CV curves at different scan rates according to
graphene supercapacitor can thus be attributed to the high Equation 1 and 10:
capacitance and rate performance as well as the synergistic
effects of both the Ni(OH)2/graphene composite and porous E
Pav =
graphene electrodes. t (10)

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5
10 and power performances of this asymmetric supercapacitor are
highly competitive with Li-ion batteries and significantly supe-
Power density (W kg -1

rior to current electrochemical capacitors and Ni-MH batteries.

4
10 The superior electrochemical performance of the fabricated
Ni(OH)2/graphene//porous graphene asymmetric superca-
pacitor can be reasonably attributed to the synergistic effects
3
10 between the positive and negative electrodes. The energy
density of the asymmetric capacitor is significantly improved
because of the high specific capacitance of the electrodes and
2
10 the wide operation voltage window. On the other hand, the
graphene materials in both electrodes demonstrate their dis-
tinctive features for asymmetric supercapacitors. Because of its
1
10 excellent mechanical properties, good electrochemical stability,
and superior conductivity, the graphene nanosheets can not
only act as the support for the nanoscale flower-like Ni(OH)2
0
10 grown on the sheets, but also maintain the mechanical integ-
0 1 2
10 10 10 rity and high electrical conductivity of the overall electrode.
-1
Energy density (Wh kg ) On the other hand, using porous graphene with considerable
mesopores (ca. 10 nm) as the negative electrode facilitates the
Figure 9. Ragone plot related to energy and power densities of the transport of electrolyte ions and provides a larger surface area
Ni(OH)2/graphene//porous graphene asymmetric supercapacitor ()
for charge-transfer reactions, ensuring high power density and
operated at 1.6 V in comparison to symmetric capacitors from com-
mercial porous carbon (EC-600JD, )[50] and porous graphene (), and excellent rate performance. Thus, pairing up Ni(OH)2/graphene
several nickel-based asymmetric supercapacitors previously reported in and porous graphene hybrid materials for asymmetrical super-
the literature, namely NiO//carbon (, )[40,60] and Ni-Zn-Co oxide/ capacitors represents a new approach to high-performance
hydroxide//carbon ().[61] energy storage.

3. Conclusions
where t is indicating the discharge time (s). Figure 9 shows
the Ragone plots of the as-fabricated asymmetric supercapac- We have successfully developed an asymmetric supercapacitor
itors measured in the voltage window of 0–1.6 V at different using Ni(OH)2/graphene and porous graphene as the positive
scan rates. Although the specific energy density generally and negative electrodes, respectively. The asymmetrical super-
decreases with increasing specific power density, it is obvious capacitor shows high specific capacitance, high energy density,
that both the power density and energy density are signifi- and good cycling stability at an operating voltage of about 1.6 V
cantly enhanced upon increasing the operation voltage from in KOH aqueous electrolytes. It is shown that it is highly desir-
1.0 to 1.6 V (Supporting Information Figure S4) as the energy able to couple the Ni(OH)2/graphene composite with porous
density of a capacitor is governed by the specific capacitance graphene to produce supercapacitors with high energy and
and the maximum operational voltage.[5] It should be noted power densities. These encouraging findings can open up the
that the obtained maximum energy operated at 1.6 V is about possibility of graphene-based composites for numerous appli-
3, 6, and 12 times those of the cells operated at 1.4, 1.2, and cations in asymmetric supercapacitors with high voltage, high
1.0 V, respectively. According to Equation 1, the considerably energy, and high power densities to meet the diverse demands
improved energy density can probably be ascribed to the high where high power and energy storage systems are required.
voltage and the increased capacitance because of Faradaic reac-
tions. The Ni(OH)2/graphene//porous graphene asymmetric
supercapacitor with a cell voltage of 1.6 V can exhibit an energy 4. Experimental Section
of 77.8 Wh kg−1 at a power density of 174.7 W kg−1, and still
retains 13.5 Wh kg−1 at a power density of 15.2 kW kg−1. In Synthesis of Flowerlike Ni(OH)2/Graphene Composite: Graphene sheets
were prepared by chemical reduction of graphene oxide with hydrazine
addition, this high energy density is much higher than that hydrate according to the literature.[25] The flowerlike Ni(OH)2/graphene
of symmetrical supercapacitors, such as activated carbon// composite was synthesized using a microwave heating approach
activated carbon supercapacitors (<10 Wh kg−1),[50–55] carbon without any hard/soft templates or precipitate-controlling agents. In a
nanotubes(CNTs)//CNTs supercapacitors (<10 Wh kg−1),[56–59] typical synthesis, 0.1 g of graphene was added into 100 mL of distilled
graphene//graphene supercapacitors (ca. 9.1 Wh kg−1)[14] water and subjected to ultrasonic vibration to form a homogeneous
and porous graphene//porous graphene supercapacitors (ca. suspension. Then 3.28 g of nickel (II) nitrate hexahydrate and 13.54 g
of urea were added into the above graphene suspension and stirred
5.7 Wh kg−1) and some recently reported nickel-based asym-
for a while. Subsequently, the as-formed suspension was transferred
metric supercapacitors in aqueous electrolyte solutions, such into a microwave synthesis system (PreeKem, APEX) and subjected to
as Ni(OH)2/graphene//RuO2/graphene (48 Wh kg−1),[14] NiO// microwave heating for 7 min under ambient atmosphere with a power
carbon (15-20 Wh kg−1),[40,60] Ni-Zn-Co oxide/hydroxide//carbon of 700 W, and then cooled naturally to room temperature. Finally, the
(41.65 Wh kg−1),[61] and Ni(OH)2//activated carbon (42.3 Wh black deposit was filtered, washed several times with distilled water and
kg−1).[35] Furthermore, it is worth noting that both the energy alcohol, and dried at 100 °C for 12 h in a vacuum oven. For comparison,

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pure Ni(OH)2 was also synthesized by the same procedure as described [1] H. Wang, H. S. Casalongue, Y. Liang, H. Dai, J. Am. Chem. Soc.
above in the absence of graphene. The mass fraction of Ni(OH)2 grown 2010, 132, 7472.
on graphene was 79 wt%, which was obtained by comparing the mass [2] Z. Chen, Y. Qin, D. Weng, Q. Xiao, Y. Peng, X. Wang, H. Li, F. Wei,
of the Ni(OH)2/graphene composite with the mass of graphene used in Y. Lu, Adv. Funct. Mater. 2009, 19, 3420.
the synthesis. [3] Z. Fan, J. Yan, T. Wei, L. Zhi, G. Ning, T. Li, F. Wei, Adv. Funct. Mater.
Synthesis of Porous Graphene: Porous graphene was prepared by a 2011, 21, 2366.
template CVD approach as described in our previous report.[34] Briefly, [4] L. H. Bao, J. F. Zang, X. D. Li, Nano Lett. 2011, 11, 1215.
the quartz reactor was heated to 900 °C in an argon flow of 1000 mL [5] Z. Chen, V. Augustyn, J. Wen, Y. W. Zhang, M. Q. Shen, B. Dunn,
min−1 at atmospheric pressure. When the reaction temperature was Y. F. Lu, Adv. Mater. 2011, 23, 791.
reached, CH4 was introduced into the reactor at a flow rate of 800 mL
[6] B. E. Conway, Electrochemical Supercapacitors: Scientific Funda-
min−1. Then, the MgO template (ca. 30 g) was fed into the reactor over
mentals and Technological Applications, Kluwer Academic/Plenum,
5 min from the top hopper. After 10 min of carbon deposition, the CH4
New York 1999.
stream was turned off and the reactor was cooled to room temperature
in an Ar atmosphere. The material obtained was purified by acid washing [7] P. Simon, Y. Gogotsi, Nat. Mater. 2008, 7, 845.
under reflux for 1 h to remove MgO. Finally, the resultant precipitate was [8] C. Liu, F. Li, L.-P. Ma, H.-M. Cheng, Adv. Mater. 2010, 22, E28.
filtered and dried overnight in an oven at 80 °C. [9] Z.-S. Wu, W. Ren, D.-W. Wang, F. Li, B. Liu, H.-M. Cheng, ACS Nano
Characterization: The crystallographic structures of the materials were 2010, 4, 5835.
determined by a powder XRD system (TTR-III) equipped with Cu Kα [10] A. Izadi-Najafabadi, S. Yasuda, K. Kobashi, T. Yamada, D. N. Futaba,
radiation (λ = 0.15406 nm). XPS measurements were performed using a H. Hatori, M. Yumura, S. Iijima, K. Hata, Adv. Mater. 2010, 22,
PHI 5700 ESCA spectrometer with a monochromated Al Kα radiation (hν = E235.
1486.6 eV). All XPS spectra were corrected using the C 1s line at 284.6 eV. [11] L. Demarconnay, E. Raymundo-Pinero, F. Beguin, J. Power Sources
Curve fitting and background substraction were accomplished using 2011, 196, 580.
Casa XPS version 2.3.13 software. The microstructure of the samples [12] W. G. Pell, B. E. Conway, J. Power Sources 2004, 136, 334.
was investigated by TEM (JEOL JEM2010). Raman spectra were obtained [13] P. C. Chen, G. Z. Shen, Y. Shi, H. T. Chen, C. W. Zhou, ACS Nano
on a Renishaw RM2000 Raman spectrometer with 457.9 nm wavelength 2010, 4, 4403.
incident laser light. FTIR spectroscopy was carried out on a Perkin Elmer [14] H. Wang, Y. Liang, T. Mirfakhrai, Z. Chen, H. S. Casalongue, H. Dai,
Spectrum 100 spectrometer in a range of 600-4000 cm−1. Nano Res. 2011, 4, 729.
Electrochemical Characterization: Electrodes used for the fabrication of [15] X. Y. Guan, J. C. Deng, Mater. Lett. 2007, 61, 621.
asymmetric supercapacitors were prepared by mixing the electroactive [16] L. P. Xu, Y. S. Ding, C. H. Chen, L. L. Zhao, C. Rimkus, R. Joesten,
material, carbon black, and poly(tetrafluoroethylene) with ethanol in a
S. L. Suib, Chem. Mater. 2008, 20, 308.
mass ratio of 75:20:5 to obtain a slurry. Then the slurry was pressed onto
[17] Y. Ren, L. Gao, J. Am. Ceram. Soc. 2010, 93, 3560.
the nickel foam current collector (1 cm × 1 cm) and dried at 100 °C for
[18] X. H. Liu, L. Yu, Mater. Lett. 2004, 58, 1327.
12 h. Each electrode contained about 3 mg cm−2 of electroactive material.
To fabricate an asymmetric supercapacitor, the loading mass ratio of [19] X. H. Kong, X. B. Liu, Y. D. He, D. S. Zhang, X. F. Wang, Y. D. Li,
active material (Ni(OH)2/graphene:porous graphene) was estimated to Mater. Chem. Phys. 2007, 106, 375.
be 0.44 from the specific capacitance calculated from their CV curves. [20] F. S. Cai, G. Y. Zhang, J. Chen, X. L. Gou, H. K. Liu, S. X. Dou,
The electrochemical tests of the individual electrode were performed in a Angew. Chem. Int. Ed. 2004, 43, 4212.
three-electrode cell, in which platinum foil and Hg/HgO electrodes were [21] K. Matsui, T. Kyotani, A. Tomita, Adv. Mater. 2002, 14, 1216.
used as the counter and reference electrodes, respectively. The Ni(OH)2/ [22] Q. Cheng, J. Tang, J. Ma, H. Zhang, N. Shinya, L.-C. Qin, Carbon
graphene cathode and porous graphene anode were pressed together and 2011, 49, 2917.
separated by a porous non-woven cloth separator. The electrochemical [23] J. W. Lee, T. Ahn, D. Soundararajan, J. M. Ko, J.-D. Kim, Chem.
measurements of the asymmetric supercapacitor were carried out in a Commun. 2011, 47, 6305.
two-electrode cell at room temperature in 6 M KOH aqueous electrolyte [24] P. Jeevanandam, Y. Koltypin, A. Gedanken, Nano Lett. 2001, 1,
solution (Figure 1). All of the above electrochemical measurements were 263.
carried out by a CHI 660C electrochemical workstation. [25] J. Yan, T. Wei, B. Shao, Z. J. Fan, W. Z. Qian, M. L. Zhang, F. Wei,
Carbon 2010, 48, 487.
[26] M. C. Bernard, P. Bernard, M. Keddam, S. Senyarich, H. Takenouti,
Electrochim. Acta 1996, 41, 91.
[27] C. Nethravathi, M. Rajamathi, Carbon 2008, 46, 1994.
Supporting Information [28] J. P. Liu, C. W. Cheng, W. W. Zhou, H. X. Li, H. J. Fan, Chem.
Supporting Information is available from the Wiley Online Library or Commun. 2011, 47, 3436.
from the author. [29] H. Jiang, T. Zhao, C. Z. Li, J. Ma, J. Mater. Chem. 2011, 21, 3818.
[30] C. Z. Yuan, X. G. Zhang, L. H. Su, B. Gao, L. F. Shen, J. Mater. Chem.
2009, 19, 5772.
[31] S. Park, R. S. Ruoff, Nat. Nanotechnol. 2009, 4, 217.
[32] Z. Fan, J. Yan, L. Zhi, Q. Zhang, T. Wei, J. Feng, M. Zhang, W. Qian,
Acknowledgements F. Wei, Adv. Mater. 2010, 22, 3723.
[33] Y. Zhu, S. Murali, M. D. Stoller, K. J. Ganesh, W. Cai, P. J. Ferreira,
The authors acknowledge financial support from the National Science
A. Pirkle, R. M. Wallace, K. A. Cychosz, M. Thommes, D. Su,
Foundation of China (51077014, 21003028), the China Postdoctoral
E. A. Stach, R. S. Ruoff, Science 2011, 332, 1537.
Science Foundation (20100480058, 201104411), the Heilongjiang
Postdoctoral Foundation (LBH-Z10205), Fundamental Research funds [34] G. Ning, Z. Fan, G. Wang, J. Gao, W. Qian, F. Wei, Chem. Commun.
for the Central Universities and Program for New Century Excellent 2011, 47, 5976.
Talents in University (NCET-10-0050). [35] J. W. Lang, L. B. Kong, M. Liu, Y. C. Luo, L. Kang, J. Solid State Elec-
tron. 2010, 14, 1533.
[36] C. L. Qin, X. D. Bai, G. P. Yin, Y. X. Liu, Z. Jin, H. J. Niu, Pigm. Resin
Received: November 23, 2011 Technol. 2009, 38, 230.
Published online: March 22, 2012 [37] J. P. Zheng, J. Electrochem. Soc. 2003, 150, A484.

2640 wileyonlinelibrary.com © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2012, 22, 2632–2641
 www.afm-journal.de
www.MaterialsViews.com

FULL PAPER
[38] V. Khomenko, E. Raymundo-Pinero, F. Beguin, J. Power Sources [50] C. Zheng, L. Qi, M. Yoshio, H. Y. Wang, J. Power Sources 2010, 195,
2006, 153, 183. 4406.
[39] Z. J. Lao, K. Konstantinov, Y. Tournaire, S. H. Ng, G. X. Wang, [51] D. W. Wang, F. Li, M. Liu, G. Q. Lu, H. M. Cheng, Angew. Chem. Int.
H. K. Liu, J. Power Sources 2006, 162, 1451. Ed. 2008, 47, 373.
[40] D. W. Wang, F. Li, H. M. Cheng, J. Power Sources 2008, 185, [52] Q. T. Qu, L. Li, S. Tian, W. L. Guo, Y. P. Wu, R. Holze, J. Power
1563. Sources 2010, 195, 2789.
[41] Y. Hou, Y. W. Cheng, T. Hobson, J. Liu, Nano Lett. 2010, 10, 2727. [53] V. Khomenko, E. Raymundo-Pinero, F. Beguin, J. Power Sources
[42] G. X. Hu, C. X. Li, H. Gong, J. Power Sources 2010, 195, 6977. 2010, 195, 4234.
[43] V. Ganesh, S. Pitchumani, V. Lakshminarayanan, J. Power Sources [54] Q. T. Qu, Y. Shi, S. Tian, Y. H. Chen, Y. P. Wu, R. Holze, J. Power
2006, 158, 1523. Sources 2009, 194, 1222.
[44] L. B. Kong, M. Liu, J. W. Lang, Y. C. Luo, L. Kang, J. Electrochem. Soc. [55] Q. T. Qu, Y. Shi, L. L. Li, W. L. Guo, Y. P. Wu, H. P. Zhang,
2009, 156, A1000. S. Y. Guan, R. Holze, Electrochem. Commun. 2009, 11, 1325.
[45] H. Q. Wang, Z. S. Li, Y. G. Huang, Q. Y. Li, X. Y. Wang, J. Mater. [56] C. Yu, C. Masarapu, J. Rong, B. Wei, H. Jiang, Adv. Mater. 2009, 21,
Chem. 2010, 20, 3883. 4793.
[46] H. M. Wu, C. V. Rao, B. Rambabu, Mater. Chem. Phys. 2009, 116, [57] K. H. An, W. S. Kim, Y. S. Park, J. M. Moon, D. J. Bae, S. C. Lim,
532. Y. S. Lee, Y. H. Lee, Adv. Funct. Mater. 2001, 11, 387.
[47] Y. Zhao, Y. Y. Wang, Q. Y. Lai, L. M. Chen, Y. J. Hao, X. Y. Ji, Synth. [58] Y. Honda, T. Haramoto, M. Takeshige, H. Shiozaki, T. Kitamura,
Met. 2009, 159, 331. M. Ishikawa, Electrochem. Solid-State Lett. 2007, 10, A106.
[48] Y. G. Wang, Y. Y. Xia, J. Electrochem. Soc. 2006, 153, A450. [59] M. Kaempgen, C. K. Chan, J. Ma, Y. Cui, G. Gruner, Nano Lett. 2009,
[49] T. Brousse, P. L. Taberna, O. Crosnier, R. Dugas, P. Guillemet, 9, 1872.
Y. Scudeller, Y. Zhou, F. Favier, D. Belanger, P. Simon, J. Power [60] H. Inoue, Y. Namba, E. Higuchi, J. Power Sources 2010, 195, 6239.
Sources 2007, 173, 633. [61] H. L. Wang, Q. M. Gao, J. Hu, J. Power Sources 2010, 195, 3017.

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