Journal of Alloys and Compounds 684 (2016) 707e713

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

A promising supercapacitor electrode material of CuBi2O4 hierarchical

microspheres synthesized via a coprecipitation route
Y.C. Zhang a, H. Yang a, *, W.P. Wang b, H.M. Zhang a, R.S. Li a, X.X. Wang a, R.C. Yu b
a
School of Science, Lanzhou University of Technology, Lanzhou 730050, China
b
Beijing National Laboratory of Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

a r t i c l e i n f o a b s t r a c t

Article history: CuBi2O4 hierarchical microspheres are synthesized via a coprecipitation method, where the effect of the
Received 1 March 2016 NaOH concentration in precursor solution on the product morphology is investigated. At n(NaOH) ¼ 1 M,
Received in revised form irregular microspheres of 0.5e1 mm are produced. With increase in the concentration of NaOH, the
5 May 2016
microspheres grow bigger in size and more regular in morphology. When the NaOH concentration is
Accepted 18 May 2016
Available online 20 May 2016
increased up to 6 M, regular microspheres of 4e6 mm in diameter are obtained. These microspheres are
constructed from nanorods with 30e60 nm in diameter and 200e400 nm in length via the hierarchical
self-assembly process. The electrochemical performances of the as-prepared samples are investigated by
Keywords:
CuBi2O4 hierarchical microspheres
cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge. It is
Coprecipitation method demonstrated that the sample composed of 0.5e1 mm microspheres exhibits the highest specific ca-
Electrode material pacity, reaching about 1895 F g1 in a 2 M KOH electrolyte at a measured current density of 1 A g1. This
Supercapacitor value is larger than the specific capacity for most transition metal oxides. Due to its excellent electro-
chemical performance, CuBi2O4 could find a promising application as the supercapacitor electrode
material.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction have been extensively studied as electrode materials for EDLC-

With the rapid development of economy and society, the
depletion of non-renewable fossil fuels such as oil and coal has
become one of the most serious problems facing mankind today.
The ever-increasing energy crisis has greatly stimulated the
development of new energy sources as well as energy storage
technologies. Electrochemical supercapacitors are a promising class
of electrical energy storage devices because they exhibit many
advantages such as high power density, fast charge-discharge
capability, good cyclic stability, excellent reversibility, and long
lifespan [1e3]. For supercapacitors, electrical energy is stored based
on two mechanisms, i.e., electric double-layer capacitance (EDLC)
and faradic pseudocapacitance [2,3]. The EDLC arises from the
physical accumulation of charges at electrode/electrolyte interfaces
under the action of electric field, which is highly dependent on the
effective surface area of the electrode material. Various carbon
nanomaterials such as activated carbon [4], templated carbon [5],
carbon nanotubes/nanofibers [6,7], and reduced graphene oxide [8]
* Corresponding author.
E-mail address: hyang@lut.cn (H. Yang).
based supercapacitors. However, the specific capacitance of these
carbon nanomaterials is generally low (100e350 F g1) due to the
limitation in the effective double-layer area, which restricts their
commercial application as electrode materials of supercapacitors.
On the other hand, the production of faradic pseudocapacitance is
due to fast and reversible redox reaction at the surface of the active
electrode material such as transition metal oxides and conducting
polymers. Examples of these transition metal oxides include RuO2
[9], MnO2 [10], V2O5 [11], NiO [12], Bi2O3 [13], Fe2O3 [14], Co3O4
[15], MoS2 [16], Ni3S2 [17] and CuS [18]. Among them, RuO2 has
been considered as one of the most promising electrode materials
since it can deliver a high energy density and specific capacitance
(1300 F g1) with excellent cycling stability [9]. However, the
commercial application of RuO2 is still restricted due to its high cost
and toxicity. It is desirable and challenging to develop promising
electrode materials with high specific capacitance, superior rate
capability, excellent cyclic stability, low cost and environmental
benignity. Recently research has been particularly concerned with
transition metal hydroxides and ternary transition metal oxides
such as Ni(OH)2 [19], Co(OH)2 [20], NiCo2O4 [21], MnMoO4 [22],
CoMoO4 [23] and NiMoO4 [24] due to their superior

http://dx.doi.org/10.1016/j.jallcom.2016.05.201
0925-8388/© 2016 Elsevier B.V. All rights reserved.
708 Y.C. Zhang et al. / Journal of Alloys and Compounds 684 (2016) 707e713
electrochemical properties. In particular, electrodeposited Ni(OH)2
was reported to exhibit a specific capacitance up to 3152 F g1 in a
KOH electrolyte [19]. This is the highest capacitance value reported
to date. However, it is disadvantaged by poor cycling stability as a
supercapacitor electrode.
In recent years, copper bismuth oxide (CuBi2O4) with a spinel-
type structure has been investigated for its magnetic, dielectric,
conductive, optical and photocatalytic properties [25e33].
Furthermore, it was reported that CuBi2O4-doped MnO2 thin films
exhibited enhanced specific capacitance compared to bare MnO2
thin films [34], implying possible redox reaction occurring on
CuBi2O4. In fact, bismuth oxide and bismuth-based oxides (like
Bi2WO6) are expected to exhibit good pseudocapacitive behavior
due to the reversible redox reaction between Bi(III) oxidation state
and Bi0 metallic state [35,36]. Unfortunately, there has been no
attention paid to the electrochemical properties of bare CuBi2O4. In
this work, we demonstrate that CuBi2O4 particles prepared via a
coprecipitation method can deliver a specific capacitance up to
1895 F g1 in a KOH electrolyte, which is larger than the specific
capacitance for most transition metal oxides.
It is noted that the faradic reaction dominantly occurs at the
surface of the pseudocapacitive materials, implying that the
morphology and microstructure of the pseudocapacitive materials
has an important influence on their electrochemical properties;
especially the creation of nanostructures offers great potential to
achieve excellent specific capacitance. Hydrothermal process
[28e32], electrodeposition [33], solid state reaction method [27]
and sol-gel route [37] have been used to fabricate CuBi2O4 parti-
cles or thin films. Among these methods, the hydrothermal process
offers the advantage of tailoring particle morphology and size;
however, it requires power consumption to drive the hydrothermal
reaction. Coprecipitation method is an alternative method exhib-
iting the capability of particle morphology control, and further-
more, this method consumes no any external energy source during
the particle preparation. Herein, we introduce a coprecipitation
method to synthesize CuBi2O4 particles, where the particle
morphology and size is tailored by varying the NaOH concentration.
The electrochemical properties of the as-prepared samples were
systematically investigated.
2. Experimental
CuBi2O4 particles were synthesized by a coprecipitation method
as described in the literature [38]. Bismuth nitrate pentahydrate
(Bi(NO3)3$5H2O, 99%) was purchased from Chengdu Gray West
Chemistry Technology Limited Company. Copper nitrate trihydrate
(Cu(NO3)2$3H2O, 99e102%) was purchased from Tianjinshi Guang
Fu Fine Chemical Institute. Sodium hydroxide (NaOH, 96%) was
purchased from Tianjinshi TianXin Fine Chemical Industry Devel-
opment Center. Nitric acid (HNO3, 65e68%) was purchased from
Baiyin LiangYou Chemical Reagent Limited Company. All raw ma-
terials and chemical reagents used in this study are of analytical
grade without further purification. 0.004 mol (1.9402 g) of
Bi(NO3)3$5H2O was dissolved in 10 mL of distilled water containing
2 mL of nitric acid under magnetic stirring. To the above solution
was dissolved 0.002 mol (0.4832 g) of Cu(NO3)2$3H2O, and the
resultant solution was designated as solution A. A certain amount of
NaOH was weighed out and dissolved in 70 mL of distilled water,
which was designated as solution B. Then solution B was slowly
added dropwise to solution A under constant stirring, and imme-
diately a suspension solution was formed. The obtained suspension
was continuously magnetically stirred for 12 h at room tempera-
ture (~25  C), during which a brown precipitate was gradually
formed. The precipitate was collected and washed using distilled
water and ethanol for several times, and then submitted to drying
in a thermostatic drying oven at 60  C for 12 h to obtain final
CuBi2O4 products. By varying the NaOH concentration in final re-
action solution from 1 to 6 mol L1 (M), we prepared several
CuBi2O4 samples.
The phase purity of the as-prepared CuBi2O4 samples was
examined by using powder X-ray diffraction (XRD) with Cu Ka
radiation. The morphology of the samples was investigated by us-
ing a field-emission scanning electron microscope (SEM) and a
field-emission transmission electron microscope (TEM). The
Brunauer-Emmett-Teller (BET) specific surface area of the samples
was measured by the N2 adsorptionedesorption technique on an
ASAP2020M system.
The working electrode used for the electrochemical perfor-
mance study was prepared as follows. CuBi2O4, carbon black and
polyvinylidene fluoride (PVDF) were mixed in a weight ratio of
8:1:1 using ethyl alcohol as solvent to form slurry. The slurry was
uniformly coated onto a Ni foam electrode with an area of 1 cm2.
The mass of CuBi2O4 on the Ni foam electrode was 2 mg cm2. The
electrochemical tests were carried out on a CST 350 electro-
chemical workstation using a three-electrode cell, where a plat-
inum foil served as the counter electrode and a standard calomel
electrode (SCE) served as the reference electrode. KOH, Na2SO4 and
H2SO4 aqueous solutions with a concentration of 2 M were sepa-
rately used as the electrolyte. The electrochemical properties of
CuBi2O4 samples were investigated by cyclic voltammetry (CV),
electrochemical impedance spectroscopy (EIS) and galvanostatic
charge-discharge. The specific capacity (C) of the Ni foam-
supported CuBi2O4 electrodes was calculated using the following
equation
It
C¼ (12)
mDV
where C, I, t, m, and DV are the specific capacity (F g1) of the
electrodes, discharging current (A), discharging time (s), mass of
CuBi2O4 (g), and discharging potential range (V), respectively.
3. Results and discussion
Fig. 1 shows the XRD patterns of CuBi2O4 samples prepared at
different NaOH concentrations (S1 / 1 M, S2 / 2 M, S3 / 4 M,
S4 / 6 M), along with the standard XRD line pattern for CuBi2O4
Fig. 1. XRD patterns of CuBi2O4 samples prepared at different NaOH concentrations,
along with the standard XRD line pattern for CuBi2O4 tetragonal structure (PDF card
No. 42-0334). S1 / 1 M, S2 / 2 M, S3 / 4 M, S4 / 6 M.
 Y.C. Zhang et al. / Journal of Alloys and Compounds 684 (2016) 707e713 709

tetragonal structure (PDF card No. 42-0334). It is seen that the
diffraction peaks of the samples are in good agreement with those
in the PDF standard card, and no diffraction peaks assignable to
other secondary phases are detected. This indicates that the four
samples crystallize in a pure tetragonal phase.
Fig. 2(a)e(d) show the SEM images of samples S1eS4, respec-
tively. It is seen that the sample prepared at the NaOH concentra-
tion of 1 M is mainly composed of irregular microspheres in the size
range of 0.5e1 mm. With increasing the NaOH concentration, the
microspheres grow bigger in size and more regular in morphology.
When the NaOH concentration is increased up to 6 M, regular
microspheres of 4e6 mm in diameter are obtained. The higher-
magnification SEM images inserted in the figures reveal that
these microspheres are constructed from nanorods with 30e60 nm
in diameter and 200e400 nm in length via the hierarchical self-
assembly process. Fig. 2(e) shows, as an example, the high-
resolution TEM image of sample S1, revealing that the nanorods
are well crystalized and exhibit a single-crystal feature. The BET
specific surface areas of samples S1eS4 are 18.7, 16.2, 5.3 and
3.9 m2 g1, respectively.
The crystallization process of CuBi2O4 can be described by the
“dissolutionecrystallization” mechanism [39]. According to this
mechanism, the produced amorphous precipitates BiOOH and
Cu(OH)2 under the alkaline condition undergo an attack of the
mineralizer, NaOH, to dissolve and form ion groups. CuBi2O4 nuclei
are formed and grow into large nanorods in the region of super-
saturated fluid. The involved chemical reactions can be described
by Eqs. (1)e(4). It is noted that the crystal structure of Bi2CuO4 can
be described as the stacking of CuO4 square planar units with one
on the top of another in a staggered manner, forming chains along

Fig. 2. (a)e(d) SEM images of CuBi2O4 samples S1eS4. (e) High-resolution TEM image of sample S1.
710 Y.C. Zhang et al. / Journal of Alloys and Compounds 684 (2016) 707e713
the c axis inter-connected through BiO2 chains [40]. Therefore, the
growth of nanorods might be due to the intrinsic crystal structure
of Bi2CuO4. The freshly produced CuBi2O4 nanorods simultaneously
self-assemble into superstructured microspheres. It is expected
that the NaOH concentration in precursor solution has an impor-
tant effect not only on the nucleation and growth process of
CuBi2O4 nanorods, but also on their surface energy and hence the
hierarchical self-assembly process. The increase in the NaOH con-
centration could lead to the increase in the nanorod surface energy.
As a result, with increasing the NaOH concentration, the freshly
produced CuBi2O4 nanorods tend to self-assemble into larger-sized
superstructured microspheres.
Bi3þ þ 3OH / Bi(OH)3
Cu2þ þ 2OH / Cu(OH)2
Bi(OH)3 / BiOOH þ H2O
2BiOOH þ Cu(OH)2 / CuBi2O4 þ 2H2O
In order to select an appropriate electrolyte, 2 M KOH, 2 M
Na2SO4 and 2 M H2SO4 aqueous solutions, which are representa-
tives of alkaline, neutral and acidic electrolytes, were separately
used as the electrolyte to investigate the electrochemical perfor-
mance of CuBi2O4. Fig. 3(a) shows the CV curves of CuBi2O4 (sample
S1) measured in the three different types of electrolytes at a scan
rate of 10 mV s1. It is noted that the CV curves are obtained after
stability, and the open circuit voltage (OCV) is measured to be
0.28 V. In the KOH electrolyte, the CV curve presents two oxida-
tion peaks at 0.67 and 0.5 V and a sharp reduction peak at
0.86 V, which arise from the oxidation and reduction reactions
occurring in the material. The CV curve elucidates an obvious
pseudo capacitive behavior. In the Na2SO4 electrolyte, the obtained
CV curve exhibits a quasi-rectangular shape and its area is very
small. This indicates that no redox reaction occurs at the CuBi2O4
electrode in the Na2SO4 electrolyte. The CV curve in the H2SO4
electrolyte was measured at the voltage window between 0.2 and
0.6 V because the working electrode undergoes vigorous reaction
at other potentials. This CV curve also encloses a very small area
and no redox peaks are visible, indicating that the CuBi2O4 elec-
trode is not suitable for use in the acidic electrolyte. Fig. 3(b) shows
the charge-discharge voltage profiles of CuBi2O4 (sample S1) in
KOH, Na2SO4 and H2SO4 electrolytes at a current density of 2 A g1.
Fig. 3. (a) CV curves of CuBi2O4 particles (S1) measured in 2 M KOH, 2 M Na2SO4 and 2 M H2SO4 electrolytes at a scan rate of 10 mV s1. (b) Charge-discharge voltage profiles of
CuBi2O4 particles (S1) in 2 M KOH, 2 M Na2SO4 and 2 M H2SO4 electrolytes at a current density of 2 A g1.
It is quite obvious that the charge-discharge time in the KOH
electrolyte is much longer than that in Na2SO4 and H2SO4 electro-
lytes. According to Eq. (1), we get the specific capacity of 1605, 12
and 20 F g1 in KOH, Na2SO4 and H2SO4 electrolytes, respectively.
Among the three types of electrolyte systems, CuBi2O4 shows an
excellent capacitive performance in the alkaline electrolyte and
hence the further electrochemical investigation of CuBi2O4 samples
is performed by using 2 M KOH aqueous solution as the electrolyte.
Fig. 4(a) shows the CV curves of CuBi2O4 samples S1eS4 in the
2 M KOH electrolyte at a scan rate of 10 mV s1. It is seen that the
samples have similar CV curves with a reduction peak at about
0.86 V and two oxidation peaks at about 0.67 and 0.5 V. For
sample S2, the oxidation peak at 0.64 V exhibits a slight shift
(1) toward positive potential compared with the other three samples.
We speculate that a possible reason for this is that the transfer
(2) speed of the ions into the sample could become relatively slow due
to its morphology. The reduction and oxidation peak potentials of
(3) CuBi2O4 samples are similar to those of Bi2O3 in hydroxide elec-
trolyte [35]. According to the redox mechanism described by Vivier
(4) et al. [41], the reduction and oxidation processes involve a partial
dissolution of CuBi2O4 into the ionic species BiO 2 . The reduction
peak at 0.86 V arises from the reduction of Bi(III) to Bi metal
through the following reaction pathway.
BiO  2
2 þ e / BiO2 (5)
disproportionation
2H2 O þ 3BiO2 2 ƒƒƒƒƒƒƒƒƒ! 2BiO2  þ4OH þ Bi0 (6)
Bi(0) / Bi(metal) (7)
The oxidation peaks at 0.67 and 0.5 V are due to the oxida-
tion of Bi metal to Bi(III). The involved reaction process can be
described as follow.
Bi(metal) / Biþ þ e (8)
disproportionation
3Biþ ƒƒƒƒƒƒƒƒƒ! Bi3þ þ2BiðmetalÞ (9)
3OH þ Bi3þ / Bi(OH)3 (10)
Bi(OH)3 / BiOOH þ H2O (11)
To further understand the electrochemical performance of
 Y.C. Zhang et al. / Journal of Alloys and Compounds 684 (2016) 707e713
Fig. 4. (a) CV curves of CuBi2O4 samples S1eS4 in the 2 M KOH electrolyte at a scan rate of 10 mV s1. (b) Nyquist spectra of CuBi2O4 samples, with the insets showing the enlarged
high frequency region of the spectra and the equivalent circuit. (c) Charge-discharge curves of CuBi2O4 samples at a current density of 2 A g1. (d) Calculated specific capacities of
CuBi2O4 samples according to the data in (c).
CuBi2O4 samples, EIS measurements were carried out in the fre-
quency range from 0.01 Hz to 100 kHz. Fig. 4(b) shows the obtained
Nyquist spectra and the inset shows the enlarged high frequency
region of the spectra. Generally Nyquist spectra are expected to
exhibit a shape with a semicircle at the high frequency region and a
straight line in the low frequency region. The semicircle at the high
frequency region is related to the charge-transfer resistance at the
electrode/electrolyte interface (i.e., faradic resistance), and the
straight line is ascribed to the diffusion of the electrolyte ions into/
from the electrode pores [42]. On the Nyquist spectra of CuBi2O4
samples, small semicircle is observed at the high frequency region,
indicating that the charge-transfer resistance is very small. A small
charge-transfer resistance suggests that the faradic reaction is easy
to proceed with a high reversibility. In the mid frequency region,
the phase angle for the Nyquist spectra of CuBi2O4 samples is
observed to be higher than 45 as seen from the inset to Fig. 4(b);
especially samples S1 and S2 have a Nyquist plot nearly parallel to
the imaginary axis Z00 . This suggests an important capacitive
behavior for CuBi2O4 samples. The EIS data can be fitted by an
equivalent circuit as shown in Fig. 4(b), which includes the solution
resistance (Rs), double layer capacity (Cd), charge-transfer resis-
tance (Rct) and Warburg impedance (W). The intercept on the real
axis Z0 corresponds to Rs, which is 1.02, 1.06, 1.20 and 1.32 U for
samples S1eS4, respectively. The semicircle corresponds to Rct and
its value for samples S1eS4 is obtained to be 0.38, 0.40, 0.42 and
0.62 U, respectively. The Cd value of samples S1eS4 is calculated to
be 138  106, 131  106, 125  106 and 85  106 F, respectively.
Fig. 4(c) shows the charge-discharge curves of CuBi2O4 samples
in the voltage window between 0.3 and 0.9 V at a current
711
density of 2 A g1. It is seen that these curves resemble each other
quite closely with a charge voltage plateau at 0.68 ~ 0.62 V and a
discharge voltage plateau at 0.79 ~ 0.75 V. The non-linear
characteristic of the charge-discharge curves suggests that the
electrochemical reaction takes place due to the redox mechanism,
and this result is concordant with the CV results shown in Fig. 3(a).
During the charge process, the potential exhibits an initial rise and
then a slight decrease, followed by another rise; at the beginning of
the discharge cycle, it brings about a very high potential drop of
about 0.5 V. This unusual electrochemical behavior upon charge-
discharge is likely due to the phase nucleation. From their charge-
discharge curves, the specific capacity of the samples is obtained as
shown in Fig. 4(d). Among the four samples, the highest specific
capacity is observed for sample S1, reaching about 1605 F g1 at a
measured current density of 2 A g1. This can be explained by the
fact that sample S1 has a relatively higher BET surface area and thus
can provide more available surface active sites for the electro-
chemical reaction.
Fig. 5(a) shows the CV curves of sample S1 at various scan rates
ranging from 5 to 40 mV s1 in the 2 M KOH electrolyte. The redox
peaks are observed at all scan rates and furthermore their positions
undergo only a slight shift. This observation implies a fast and
reversible redox reaction and a good capacitive behavior of the
CuBi2O4 electrode. Fig. 5(b) show the charge-discharge curves of
sample S1 at various current densities ranging from 1 to 10 A g1 in
the 2 M KOH electrolyte. The calculated specific capacity values at
various current densities are shown in Fig. 5(c). At the current
density of 1 A g1, the specific capacity is obtained to be 1895 F g1.
With increase in the current density, the specific capacity exhibits a
712 Y.C. Zhang et al. / Journal of Alloys and Compounds 684 (2016) 707e713
Fig. 5. (a) CV curves of sample S1 at various scan rates in the 2 M KOH electrolyte. (b) Charge-discharge curves of sample S1 at various current densities in the 2 M KOH electrolyte.
(c) Calculated specific capacity values at various current densities. (d) Specific capacity retention of sample S1 as a function of the charge-discharge cycling number at a constant
current density of 6 A g1 in the 2 M KOH electrolyte.
decreasing trend, which could be due to an increase in ionic re-
sistivity and a decrease in charge diffusion to the inner active sites
and the redox reaction rate [43,44]. Even so the specific capacity
still reaches 1408 F g1 at a high current density of 10 A g1. This
suggests that the CuBi2O4 electrode maintains an excellent elec-
trochemical performance under high charge-discharge current
densities.
The electrochemical cycling stability of the CuBi2O4 electrode
(sample S1) was evaluated by the repeated charge-discharge
measurement at a constant current density of 6 A g1 in the 2 M
KOH electrolyte. Fig. 5(d) shows the specific capacity retention as a
function of the charge-discharge cycling number. At the initial
stage, the specific capacity undergoes a slight decrease with
increasing the cycle number. After 600 cycles, the specific capacity
is about 1300 F g1, maintaining 82% of the initial value. However,
further increase in the cycle number leads to almost no lose of the
specific capacity. The inset showed in Fig. 5(d) describes the first
and last (1200th cycle) charge-discharge curves, demonstrating
that the CuBi2O4 electrode material keeps good charge-discharge
performance after 1200 cycles. Due to its excellent electro-
chemical performance, CuBi2O4 could find a promising application
as supercapacitor electrode material.
4. Conclusions
In this study, a series of CuBi2O4 microspheres are synthesized
via a coprecipitation route by varying the NaOH concentration from
1 to 6 M. The sample prepared at n(NaOH) ¼ 1 M presents irregular
microspheres in the size range of 0.5e1 mm. With increase in the
NaOH concentration, the prepared microspheres become bigger in
size and more regular in morphology. When raising the NaOH
concentration up to 6 M, regular microspheres of 4e6 mm in
diameter are prepared. These microspheres are constructed from
nanorods by the self-assembly process to form hierarchical archi-
tectures. The results of electrochemical tests reveal that the as-
prepared CuBi2O4 samples exhibit excellent pseudocapacitive
behavior. In particular, the sample composed of 0.5e1 mm micro-
spheres can deliver a specific capacity up to 1895 F g1 in a 2 M KOH
electrolyte at a current density of 1 A g1. Furthermore, the CuBi2O4
electrode shows a good cycling stability. The excellent electro-
chemical performance makes CuBi2O4 attractive for the application
as supercapacitor electrode material.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Grant No. 51262018), the Fundamental
Research Funds for Universities of Gansu Province (Grant No.
056003) and the Hongliu Outstanding Talents Foundation of
Lanzhou University of Technology (Grant No. J201205).
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