Journal of Power Sources 333 (2016) 118e124

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

High-performance MgCo2O4 nanocone arrays grown on three-

dimensional nickel foams: Preparation and application as binder-free
electrode for pseudo-supercapacitor
Lifeng Cui**, Lihua Huang, Min Ji, Yangang Wang, Huancong Shi, Yuanhui Zuo, Shifei Kang*
Department of Environmental Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Uniform MgCo2O4 nanocone arrays

(NCAs) grown on 3D nickel foams
were fabricated.

The MgCo2O4 NCAs were directly
used as a binder-free electrode for
pseudocapacitors.

The MgCo2O4 NCAs achieved excel-
lent electrochemical performance
over power sample.

The enhancement is attributed com-
bination of mesoporous MgCo2O4
NCAs with nickel foam.

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

Article history: Uniform MgCo2O4 nanocone arrays (NCAs) grown radially on three-dimensional (3D) nickel foams were
Received 15 June 2016 fabricated through a facile hydrothermal process. These MgCo2O4 NCAs were characterized by X-ray
Received in revised form diffractometry, X-ray photoelectron spectroscopy, N2 adsorption Brunauer-Emmett-Teller method,
19 September 2016
scanning electron microscopy and transmission electron microscopy. The MgCo2O4 NCAs were directly
Accepted 22 September 2016
Available online 2 October 2016
used as a binder-free integrated electrode for electrochemical pseudocapacitors. The electrode yielded a
high specific capacitance of 750 F g1 with high cycling ability at a charge-discharge current density of
1 A g1 (84.0% of initial specific capacitance was remained after 1000cycles) and it was much higher
Keywords:
MgCo2O4 nanocone arrays
compared with the powder MgCo2O4 (320 F g1 at 0.5 A g1). Evidently, MgCo2O4 NCAs achieved
3D nickel foam excellent electrochemical performance owing to the unique 3D nickel-foam-based in-situ self-assembly,
Binder-free electrode which accelerated electron transport and diffusion as well as intimate electrode/electrolyte contact. The
Supercapacitor remarkable performance of the aqueous symmetric supercapacitor device without addition of binders or
conductive additive is attributed to the close-knit combination of MgCo2O4 nanocone with highly-
conductive origin nickel foam, as well as the enlarged specific surface area (335.8 m2 g-1). This study
approves the future applications of the MgCo2O4 NCAs inspired large-scale supercapacitor grown on low-
cost nickel foams.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction

The rapid technological development and accelerated natural

* Corresponding author.
resource consumption have largely raised the demand for high-
** Corresponding author.
E-mail addresses: lifeng.cui@gmail.com (L. Cui), sfkang@usst.edu.cn (S. Kang).
efficiency, environmental-friendly and safe energy storage

http://dx.doi.org/10.1016/j.jpowsour.2016.09.159
0378-7753/© 2016 Elsevier B.V. All rights reserved.
 L. Cui et al. / Journal of Power Sources 333 (2016) 118e124
devices. So far, supercapacitor was widely recognized as one of the
most promising type of energy storage devices. Because of its fast
charge-discharge property, high power density and excellent cycle
performance, supercapacitor have attracted considerable attention
from various fields such as emergency power system, electric
vehicle and aerospace [1e4]. Particularly, the pseudocapacitor that
uses reversible faradaic redox reaction at the electrode surface
exhibits much larger specific capacitance compared with many
commercial double-layer supercapacitors made of carbonaceous
materials [5e9]. However, conventional pseudocapacitors based on
metal oxides (e.g. Co3O4, MnO2, NiO) are limited by large costs and
low recycling stability. It is well recognized that the major problem
in fabricating a preeminent supercapacitor is to develop novel
electrode materials with higher specific capacitance and broader
cell voltage range [10e13]. Moreover, the binding state is also a
major influence factor on the performance and stability of pseu-
docapacitors as it promotes the combination between electrode
materials and the current collector [14e18].
In recent years, the introduction of nanostructured ternary
transition metal oxides (TTMOs), especially cobalt-based MCo2O4
(M ¼ Zn, Ni, Mn, Cu, Mg etc.) TTMOs, is inspiring as high-
performance electrode materials for pseudocapacitors. The main
advantage of TTMOs (e.g. ZnCo2O4 [19,20], NiCo2O4 [21,22],
MnCo2O4 [23,24], and CuCo2O4 [25,26]) electrode is the
extremely high theoretical capacitance (~3000 F g1) because
their unique physiochemical properties facilitate mass transport,
ion diffusion and electron transfer, thus dramatically boosting the
electrochemical performance [27e29]. An additional advantage of
cobalt-based TTMOs is the cost reduction of rare cobalt by
partially substituting it with other TMOs [30]. Furthermore, the
capacitance of TTMOs can be improved by controlling the size
and structure of TTMOs electrodes [31]. A series of NiCo2O4
electrodes with different nanostructures on nickel foam were
prepared for supercapacitor and the electrochemical properties
are affected by morphologies significantly [32]. Compared with
ZnCo2O4 acicular nanocones [20], urchin-like ZnCo2O4 micro-
spheres [33] show higher specific capacitance and long-term
capacity retention at the same test condition of 1841.8 F g1
and 95.8%.
Among all the MCo2O4 TTMOs electrode materials for pseu-
docapacitors, MgCo2O4 with a superior theoretical capacitance
(~3122 F g1) is one promising candidate and has shown
excellent performance as electrode materials in lithium ion
battery [34,35]. However, the practical capacitance of MgCo2O4
electrode for pseudocapacitors is only 320 F g1 at 1 A g1 [15]
by powder spheroidal MgCo2O4 up to now, which is much lower
than the theoretical capacitance. This low specific capacitance is
attributed to the simple structures, poor electric conductivity
and small surface area. In order to break this limitation, we have
to find a novel method that can further improve the capacity of
MgCo2O4. To the best of our knowledge, there is no report on
the nanostructured MgCo2O4 directly supported on a conductive
current collector and used as binder-free electrode for
supercapacitors.
In this work, we fabricated MgCo2O4 nanocone arrays (NCAs)
grown on nickel foam by using a simple hydrothermal method and
used them as binder-free electrode for three-electrode electro-
chemical evaluation. The electrochemical performance and recy-
cling stability of MgCo2O4 NCAs electrode were studied to
investigate the practicability of this binder-free electrode material.
The MgCo2O4 NCAs placed in direct contact with the nickel col-
lector were expected to increase active sites for insertion/extraction
reactions, form numerous efficient transport pathways for ions and
electrons and break the low capacitance limitation of MgCo2O4 for
efficient energy storage.
119
2. Experimental
2.1. Materials
All reagents (analytical purity, Sinopharm Chemical Reagent Co.
Ltd. China) in the present work were used without further purifi-
cation. Nickel foam (pore density ¼ 110 PPI; mass per unit
area ¼ 320 g m2) and nickel power (mesh number 1000) were
purchased from Taiyuan Lizhiyuan Battery Sales Company. Nickel
foam and nickel power was used fresh exactly right after acid
surface treatment (6 M HCl, 30 min) and ethyl alcohol wash to
exclude NiO.
2.2. Synthesis of MgCo2O4 NCAs on a nickel foam
MgCo2O4 NCAs were fabricated by a simple hydrothermal
method. In a typical process, 1.5 mmol of magnesium nitrate
(Mg(NO3)2)$6H2O, 3 mmol of cobalt nitrate (Co(NO3)2)$6H2O,
2 mmol of ammonium fluoride (NH4F) and 6 mmol of urea
(CO(NH2)2) were dissolved in 40.0 ml of deionized water and stir-
red for 30 min to form a clear pink solution. Nickel foam (2  4 cm2)
was carefully cleaned with a 6.0 M HCl solution in an ultrasound
bath for 30 min to remove the NiO layer from the surface, then
rinsed with deionized water and absolute ethanol for several times,
and finally dried in a vacuum oven at 50  C. The aqueous solution
and the Ni foam were transferred into a 50 ml Teflon-lined stain-
less-steel autoclave which was maintained at 130  C for 5 h. The
samples were rinsed with deionized water several times and dried
at 60  C after the autoclave naturally cooled down to room tem-
perature. Finally, the products were calcinated at 400  C for 3 h to
form MgCo2O4 NCAs deposited on the nickel foam. For comparison,
powder MgCo2O4 was also prepared following the same procedure
except that metallic nickel power was introduced instead of Ni
foam.
2.3. Characterization of materials
The crystal structure and textural properties of the products
were investigated on a Bruker D8 Advance X-ray diffractometer
(XRD, Bruker Optics, Ettlingen, Germany) with Cu-Ka radiation,
operated at 40 kV and 40 mA (scanning step: 0.02 /s) in 2q ¼ 10-
80 . The MgCo2O4 NCAs layer was scraped from the nickel foam and
grinded to powder for XRD characterization to avoid the strong
interference signal of nickel substrate. Nitrogen adsorption-
desorption isotherms were measured at 77 K on a NOVA2000e
automated volumetric apparatus (Quantachrome Instruments,
USA) to determine the BrunauereEmmetteTeller (BET) surface
area, BarreteJoynereHalenda (BJH) pore size and size distribution.
The micro-morphologies were characterized on a Zeiss Ultra 55
scanning electron microscope (SEM) and a JEM-2010 transmission
electron microscope (TEM, JEOL Ltd., Japan) at an acceleration
voltage of 200 kV. The X-ray photoelectron spectra (XPS) were
recorded on an ESCALAB 250 XPS meter (Thermo Scientific) with Al
Ka monochromatization at 250 W.
2.4. Electrochemical measurements
The electrochemical properties of the MgCo2O4 NCAs were
examined by cyclic voltammetry (CV), galvanostatic charge/
discharge (GCD) test and electrochemical impedance spectroscopy
(EIS) in 6 M KOH aqueous solutions on a VSP three-electrode
electrochemical analysis system (Bio-logic Science Instruments,
France). The Ni-foam-supported MgCo2O4 NCAs (1  1 cm2, mass
loading of MgCo2O4 NCAs was~ 2 mg cm1) were directly used as
the working electrode without any binder or conductive additive, A
120 L. Cui et al. / Journal of Power Sources 333 (2016) 118e124
Pt plate (2  2 cm2) and an Ag/AgCl electrode were used as the
counter electrode and reference electrode, respectively. The mag-
nesium oxide herein is typical alkaline oxide so that it is stable in
the solution at high pH value. The CV tests were carried out within
the potential window of 0e0.5 V at the scan rates of 5e100 mV s1.
The GCD tests were conducted at the voltage from 0 to 0.4 V and at
the current density from 1 to 20 A g1. The EIS was obtained at the
frequency from 0.01 Hz to 100 KHz with amplitude of 5 mV. The
specific capacitance (Cs, F$g1) of a supercapacitor was calculated as
follows:
It
Cs ¼
DV  m
where I is the applied GCD current (A), t is the time of discharge
stage (s), V is the potential range of GCD test (V), and m is the active
mass of the working electrode. The mass of the NCAs working
electrode was calculated simply by weighing the electrodes care-
fully before and after NCAs deposition. Since the state of metal Ni
show no change after NCAs deposition, the weight difference can
accurately represent for the mass loading of NCAS on nickel
substrate.
3. Results and discussion
3.1. Morphology and structure of MgCo2O4 NCAs
As shown in Fig. 1, the fabrication process of MgCo2O4 NCAs
mainly involves two steps. In the first step, after the removal of
potential NiO layer from the surface by acid treatment, the skeleton
of the bare nickel foam is surrounded by parent ions and then light
purple mesoporous MgCo-precuosor NCAs are formed by a simple
surfactant-assisted hydrothermal process. In the second step, the
MgCo-precuosor is thermally transformed to dark MgCo2O4 NCAs
supported on the nickel foam, as can be described by the simple
dehydration reaction. The inset shows the physical map of bare
nickel foam (NF) and the black product MgCo2O4.
The XRD patterns in Fig. 2a reveal the well-defined diffraction
peaks attributed to the single-phase cubic spinel structure of
Fig. 1. Schematic illustration of the growth of MgCo2O4 NCAs on nickel foam.
MgCo2O4. The seven main peaks at about 31.0, 36.8, 38.3, 44.6, 55.2,
58.9 and 65.0 correspond to (220), (311), (222), (400), (422), (511)
and (440) crystal planes respectively, and are assigned to MgCo2O4
(JCPDS No. 02-1073). No additional diffraction peak other than
MgCo2O4 is detected, indicating the high purity of the product.
Small variation of XRD patterns among these two graphs is prob-
ably due to the different ratios of Mg, Co and O elements. Fig. 2b
shows the N2 adsorption-desorption isotherms and the corre-
sponding BJH pore size distributions of MgCo2O4 NCAs, MgCo2O4
powder and bare nickel foam. All the isotherms except that of
nickel foam can be classified as type IV isotherms, indicating the
mesoporous structures of MgCo2O4 NCAs and MgCo2O4 powder.
(1)
The BET surface area of MgCo2O4 NCAs is up to 335.8 m2 g1, much
larger than those of MgCo2O4 powder (45.2 m2 g1) and bare nickel
foam (5.1 m2 g1), indicating that the bare nickel foam almost did
not contribute to the large surface area. According to the BJH pore
size distributions, the average adsorption pore size is 7.8 nm for
MgCo2O4 NCAs and 17.4 nm for MgCo2O4 powder, which prove
again the mesoporosity of both substances. Theoretically, the large
increase in surface area after modification on the nickel foam as
well as the mesoporosity accelerated electrolyte-electrode
connection and ion migration in the electrochemical interaction.
XPS was adopted to investigate the oxidation states of elements
and the chemical compositions of MgCo2O4 NCAs. Except the C1s
peaks for calibration, the XPS spectra in Fig. 2c shows distinct peaks
and two weak peaks, which are on account of the existence of Mg,
Co, Ni and O elements in the MgCo2O4 NCAs. The atomic ratio of Mg
to Co is close to 1:5 in the MgCo2O4 NCAs. The binding energy of Mg
1s is around 1302.8 eV (Fig. 2d), which indicates the existence of Mg
element in the composite as previously reported [36]. The two
peaks of Co 2p at 780.0 and 795.5 eV (Fig. 2e) correspond to Co 2p1/2
and Co 2p3/2 respectively, suggesting the oxidation state of Co3þ
[37]. The O 1s spectrum in Fig. 2f consists of two oxygen contri-
butions at 529.5 and 531.1eV, which are attributed to the metal-
eoxygen bonds and numerous defect sites with low oxygen
coordination, respectively [38].
The surface morphologies of the NF-supported MgCo2O4 NCAs
examined by SEM are showed in Fig. 3. The nickel foam has smooth
 L. Cui et al. / Journal of Power Sources 333 (2016) 118e124 121

Fig. 2. (a) XRD pattern of MgCo2O4 NCAs; (b) Nitrogen adsorption-desorption isotherms and pore size distribution of MgCo2O4 NCAs, MgCo2O4 powder and bare nickel foam; (c)
XPS general spectrum of MgCo2O4 NCAs; XPS survey scans of (d) Mg 1s, (e) Co 2p and (f) O1s.

surfaces and an average grain size of 80e100 mm (Fig. 3a). The
macroporous nickel foam skeleton is directly coated by large-scale,
dense and directional MgCo2O4 nanocones to form an electrode
(Fig. 3bec). This electrode would facilitate the trap and access of
electrolyte ions to the porous structures and shorten the transport
pathway for electrolyte ions and electrons during the super-
capacitor charge/discharge. These MgCo2O4 nanocones have an
edge length of 1e5 mm (Fig. 3d).
TEM was employed to probe into the morphology and structure
of MgCo2O4 NCAs. As showed in Fig. 4a and b, the MgCo2O4
nanocones has an inconspicuous tip, its length is about 2.1 mm, and
its diameter decreases from 90.8 to 46.8 nm, confirming the cone-
shape of MgCo2O4, which are consistent with the SEM images. The
MgCo2O4 nanocones are composed of plentiful small nanoparticles
(5e10 nm in diameter, Fig. 4c). These nanoparticles with different
sizes accumulate together to form a porous architecture, thus
improving the surface area and electrochemical performance of the
material. The high-resolution TEM image in Fig. 4d shows that the
MgCo2O4 nanocones are crystalline with a lattice spacing of
0.286 nm, which agrees well with the theoretical interplane
spacing of MgCo2O4 (220) planes [39].
3.2. Electrochemical properties
The characterization results above suggest that the large-scale
porous and dense MgCo2O4 nanocones covering the nickel foam
can be fabricated through a facile hydrothermal process and may be
an ideal electrode material for supercapacitors (theoretical
122 L. Cui et al. / Journal of Power Sources 333 (2016) 118e124

Fig. 3. SEM images of (a) Ni foam, and (b, c, d) MgCo2O4 NCAs at different magnifications. Inset in 3d is the cross section of MgCo2O4 NCAs layer.

Fig. 4. Low- and high-magnification TEM images of MgCo2O4 NCAs.

capacitance ~3122 F g1). The electrochemical performances of
MgCo2O4 NCAs tested by CV, GCD and EIS in a three-electrode
system in 6 M KOH aqueous solutions are illustrated in Fig. 5aef.
Fig. 5a displays the CV curves of the MgCo2O4 NCA electrode and
the neat Ni foam electrode (vs. Ag/AgCl) at a scan rate of 5 mV s1
and within the potential of 0e0.5 V. A pair of broad redox peaks
appear during the charge-discharge process, which are typical of
faradic reaction in an alkaline electrolyte. The large integrated area
on the CV curve of MgCo2O4 NCAs suggests the charge storage and
high capacitance. In comparison, the integrated area of MgCo2O4
NCAs is much larger than that of nickel foam, indicating the
contribution from nickel foam can be ignored. The CV curves of the
MgCo2O4 NCA electrode at different scan rates are showed in
Fig. 5b. A pair of redox peaks are visible at low scan rate, but
migrate to negative and positive potentials respectively at high scan
rate because of the polarization in the electrode [40e42] with the
rise of peak currents. The possible redox peaks can be explained by
the following reactions [5]:
MgCo2 O4 þ H2 O%MgO þ 2CoOOH (2)
2CoOOH þ 2H2 O þ 2e %2CoðOHÞ2 þ 2ðOHÞ (3)
 L. Cui et al. / Journal of Power Sources 333 (2016) 118e124 123

Fig. 5. (a) CV curves of the MgCo2O4 NCA electrode and Ni foam electrode at a scan rate of 5 mV s1 in 6 M KOH solutions; (b)e(f): only the MgCo2O4 NCA electrode; (b) CV curves at
different scan rates; (c) GCD curves at different current densities; (d) specific capacitance as a function of current density; (e) cycle performance at a current density of 1 A g1 (inset
shows GCD curves of the first 10 and last 10 cycles from 1000 cycles); (f) EIS and equivalent circuit.

The specific capacitance is measured by GCD within the potential of
0e0.4 V (vs. Ag/AgCl). The GCD curves at current density from 1 to
20 A g1 (Fig. 5c) show there are two stages of potential change with
time in the charge-discharge process. The curves in the first stage from
potential 0e0.15 V are basically vertical, which characterize the pure
double-layer capacitance resulting from the electrode/electrolyte
interface charge isolation. The majority of the capacitance is generated
in the second stage from potential 0.15e0.4 V, where the curves
characterize a typical pseudocapacitance. The capacitance increase
may result from electrochemical adsorption-desorption or reduction-
oxidation on the electrode-electrolyte interface. The specific capaci-
tance calculated by Eq. (1) is plotted in Fig. 5c. Compared with the
reported value of powder MgCo2O4 (320 F g1) at current density of
1 A g1, the specific capacitances of MgCo2O4 NCAs at current density
of 1, 2, 5, 10, 20 A g1 are improved to 750, 557.4, 516.9, 484.4 and
445.7 F g1, respectively. Clearly, 59.4% of capacitance is remained
when the current density varies from 1 to 20 A g1, which suggests an
excellent rate capability. Such high performance of the MgCo2O4 NCAs
is attributed to the independence on binder, flexible conduction along
nanocones, and direct connection with the current collector.
To further investigate the superiority of the MgCo2O4 NCA
electrode, we carried out another critical test of long-term cycling
performance for practical application. Fig. 5e presents the cycling
stability through GCD tests for 1000 cycles at a current density of
1 A g1. About 84.0% (630 F g1) of initial capacitance is remained
after 1000 cycles, which indicates the high cycling stability of
MgCo2O4 NCAs. This result is at the same level as other similar
mesoporous structured metal oxide electrodes [20,21,43]. The inset
124 L. Cui et al. / Journal of Power Sources 333 (2016) 118e124
in Fig. 5e shows no difference between the GCD curves of the first
10 and last 10 cycles, which indicates that no significant structural
variation of MgCo2O4 NCAs during the GCD experiment.
The influence and mechanism of the Mg addition on the elec-
trochemical properties of the new MgCo2O4 type electrode was
further studied by EIS. Fig. 5f illustrates the EIS spectra and
impedance data analyzed on basis of the equivalent circuit of each
electrode. The intersection of the curve at real part Z0 shows the
internal resistance (Rs), which is the sum of the ionic resistance of
electrolyte, the intrinsic resistance of active materials and the
contact resistance at the active material-collector interface [44]. It
is evident that the MgCo2O4 NCAs have lower Rs (Fig. 5f). The
diameter of Nyquist plot semicircle, which characterizes Faradic
reactions, reflects the double layer capacitance (CL) and interfacial
charge transfer resistance (Rct). It is clear that the semicircle of the
MgCo2O4 NCA electrode has a much smaller diameter compared
with the MgCo2O4 powder electrode, demonstrating that the nickel
foam substrate promoted the charge-transfer compared to pure
powder materials. These results indicate that the nickel foam
substrate enhances the conductivity of pure binary metal oxide
materials. The curve slope at lower frequency reveals the Warburg
impedance Zw which characterizes the electrolyte migration in the
porous electrode and the proton spread in the host. The MgCo2O4
NCAs show more ideal straight lines along the imaginary axis and
thereby lower diffusion resistance compared with powder
MgCo2O4. All above causes contribute greatly to the large specific
capacitance of the MgCo2O4 NCAs.
Based on the above results, we propose a mechanism to explain
the good capacitance performance of the MgCo2O4 NCAs. First,
MgCo2O4 nanocones are grown on the nickel foam to form a highly-
porous structure, which promotes the ions migration in the elec-
trolyte as well as the electrolyte-material interaction. Second, the
highly-conductive nickel foam creates a highway for electrons and
thereby accelerates the charge transfer. Thirdly, the growth on the
mechano chemically-stable nickel foam substrate prevents the
stacking of MgCo2O4 nanocones during the electrochemical reac-
tion. Thus, the stability of the MgCo2O4 nanocone structure is
maintained after a number of cycles. The addition of Mg in MCo2O4
TTMOs materials was proved successful in constructing high-
performance MCo2O4 type electrode for pseudocapacitors.
4. Conclusions
MgCo2O4 NCAs on 3D nickel foam substrate were synthesized by
a facial hydrothermal method and used as electrode material for
supercapacitors. The MgCo2O4 NCAs have a BET surface area up to
335.8 m2 g1 and an ideal pore size of 7.8 nm. The MgCo2O4 NCA
electrode exhibits an electrochemical capacitance up to 750 F g1 at
a current density of 1 A$g1, which is significantly higher than the
MgCo2O4 power electrode (320 F g1). After 1000 cycles at current
density of 1 A g1, the long-term capacity retention of the material
is about 84.0%. All these improvements of MgCo2O4 NCAs can be
ascribed to the unique 3D nickel-foam-supported mesoporous
structure, which provides large electric contact surfaces of the
active material, and also completely reduces the dependence on
binder or conductive additive, thus significantly accelerating the
ion-electron migration and shortening the transport pathway.
Undoubtedly, this work as well as the superior theoretical capaci-
tance of MgCo2O4 shows the huge potential for MgCo2O4 to be used
as a high-performance electrode for supercapacitors.
Acknowledgments
This work was supported by National Natural Science Founda-
tion of China (Grant No. 51528202, 51502172 and 21606150),
Capacity-Building of Local University Project by Science and Tech-
nology of Shanghai Municipality (Grant No. 12160502400) and
Program of Shanghai Pujiang Talent Plan (Grant No. 14PJ1406800).
References
[1] J.R. Miller, P. Simon, Science 321 (2008) 651e652.
[2] M. Winter, R.J. Brodd, Chem. Rev. 35 (2004) 4245e4269.
[3] N.S. Choi, Z.H. Chen, S.A. Freunberger, X.L. Ji, S.Y. Kook, A. Khalil, Y. Gleb,
L.F. Nazar, C. Jaephil, P.G. Bruce, Angew. Chem. Int. Ed. 51 (2012) 9994e10024.
[4] C. Liu, F. Li, L.P. Ma, H.M. Cheng, Adv. Mater. 22 (2010) 23e26.
[5] G.P. Wang, L. Zhang, J.J. Zhang, Chem. Soc. Rev. 41 (2012) 797e828.
[6] S. Chu, A. Majumdar, Nature 488 (2012) 294e303.
[7] R. Ko € tz, M. Carlen, Electrochim. Acta 45 (2000) 2483e2498.
[8] X.M. Zhang, Y.Q. Jiao, L. Sun, L. Wang, A.P. Wu, H.J. Yan, M.C. Meng, C.G. Tian,
B.J. Jiang, H.G. Fu, Nanoscale 8 (2016) 2418e2427.
[9] S. Biswas, L.T. Drzal, ACS Appl. Mat. Interfaces 2 (2010) 2293e2300.
[10] F. Du, D.S. Yu, L.M. Dai, S. Ganguli, V. Varshney, A.K. Roy, Chem. Mater. 23
(2011) 4810e4816.
[11] C.X. Guo, C.M. Li, Energy Environ. Sci. 4 (2011) 4504e4507.
[12] D.N. Futaba, H. Kenji, Y. Takeo, H. Tatsuki, H. Yuhei, K. Yozo, T. Osamu,
H. Hiroaki, Y. Motoo, I. Sumio, Nat. Mater. 5 (2006) 987e994.
[13] J. Gamby, P.L. Taberna, P. Simon, J.F. Fauvarque, M. Chesneau, J. Power Sources
101 (2001) 109e116.
[14] C. Wu, X.Y. Wang, B.W. Ju, X.Y. Zhang, L.L. Jiang, W. Hao, Int. J. Hydrogen
Energy 37 (2012) 14365e14372.
[15] S.G. Krishnan, M.V. Reddy, M. Harilal, B. Vidyadharan, I.I. Misnon,
M.H.A. Rahim, J. Ismail, R. Jose, Electrochim. Acta 161 (2015) 312e321.
[16] K.W. Qiu, Y. Lu, J.B. Cheng, H.L. Yan, X.Y. Hou, D.Y. Zhang, M. Lu, X.M. Liu,
Y.S. Luo, Electrochim. Acta 157 (2015) 62e68.
[17] X.L. Wang, X.Y. Fan, G. Li, M. Li, X.C. Xiao, A.P. Yu, Z.W. Chen, Carbon 93 (2015)
258e265.
[18] X.Y. Wang, X.Y. Wang, L.H. Yi, L. Liu, Y.Z. Dai, H. Wu, J. Power Sources 224
(2013) 317e323.
[19] Y. Sharma, N. Sharma, G.V.S. Rao, B.V.R. Chowdari, Adv. Funct. Mater. 17
(2007) 2855e2861.
[20] K.W. Qiu, D.Y. Zhang, J.B. Cheng, H.L. Yan, J.Y. Xu, X.M. Liu, J.K. Kim, Y.S. Luo,
Nano Energy 11 (2015) 687e696.
[21] D.P. Cai, D.D. Wang, C.X. Wang, B. Liu, L.L. Wang, Y. Liu, Q.H. Li, T.H. Wang,
Electrochim. Acta 151 (2015) 35e41.
[22] X.Y. Zhou, G.H. Chen, J.J. Tang, Y.P. Ren, J. Yang, J. Power Sources 299 (2015)
97e103.
[23] Y.W. Zhang, X.Y. Wang, Q.L. Zhao, Y.Q. Fu, H. Wang, H.B. Shu, Electrochim. Acta
180 (2015) 866e872.
[24] L. Li, Y.Q. Zhang, X.Y. Liu, S.J. Shi, X.Y. Zhao, H. Zhang, X. Ge, G.F. Cai, C.D. Gu,
X.L. Wang, J.P. Tu, Electrochim. Acta 116 (2014) 467e474.
[25] S.J. Sun, Z.Y. Wen, J. Jin, Y.M. Cui, Y. Lu, Microporous Mesoporous Mater. 169
(2013) 242e247.
[26] S.D. Liu, K.S. Hui, K.N. Hui, ACS Appl. Mater. Interfaces 8 (2016) 3258e3267.
[27] M.D. Stoller, R.S. Ruoff, Energy Environ. Sci. 3 (2010) 1294e1301.
[28] G. Lota, K. Fic, E. Frackowiak, Energy Environ. Sci. 4 (2011) 1592e1605.
[29] E. Kang, Y.S. Jung, A.S. Cavanagh, G.H. Kim, S.M. George, A.C. Dillon, K.K. Jin,
J. Lee, Adv. Funct. Mater. 21 (2011) 2430e2438.
[30] M.V. Reddy, B.C. Zhang, K.P. Loh, B.V.R. Chowdari, Crystengcomm 15 (2013)
3568e3574.
[31] W.Z. Ya, W.F. Ping, L. Yan, H.J. Lin, L.Y. Zhen, X. Mei, Nanoscale 8 (2016)
7309e7317.
[32] D.P. Cai, S.H. Xiao, D.D. Wang, B. Liu, L.L. Wang, Y. Liu, H. Li, Y.R. Wang, Q.H. Li,
T.H. Wang, Electrochim. Acta 142 (2014) 118e124.
[33] C. Wu, J.J. Cai, Q.B. Zhang, X. Zhou, Y. Zhu, L.J. Li, P.K. Shen, K.L. Zhang, Elec-
trochim. Acta 169 (2015) 202e209.
[34] Y. Sharma, N. Sharma, G. Subbarao, B. Chowdari, Solid State Ionics 179 (2008)
587e597.
[35] D. Darbar, M.V. Reddy, S. Sundarrajan, R. Pattabiraman, S. Ramakrishna,
B.V.R. Chowdari, Mater. Res. Bull. 73 (2016) 369e376.
[36] Z.J. Huang, Z.X. Wang, X.B. Zheng, H.J. Guo, X.H. Li, Q. Jing, Z.H. Yang, Elec-
trochim. Acta 182 (2015) 795e802.
[37] R.C. Ambare, S.R. Bharadwaj, B.J. Lokhande, Appl. Surf. Sci. 349 (2015)
887e896.
[38] C.Z. Yuan, J.Y. Li, L.R. Hou, X.G. Zhang, L.F. Shen, W.L. Xiong, Adv. Funct. Mater.
22 (2012) 4592e4597.
[39] X.J. Wang, G.H. Zhai, H. Wang, J. Nanopart. Res. 17 (2015).
[40] Y.G. Li, B. Tan, Y.Y. Wu, J. Am. Chem. Soc. 128 (2006) 14258e14259.
[41] D.D. Han, P.C. Xu, X.Y. Jing, J. Wang, P.P. Yang, Q.H. Shen, J.Y. Liu, D.L. Song,
Z. Gao, M.L. Zhang, J. Power Sources 235 (2013) 45e53.
[42] W.K. Hu, X.P. Gao, M.M. Geng, Z.X. Gong, D. Noreus, J. Phys. Chem. B 109
(2005) 5392e5394.
[43] M. Yu, J.P. Chen, J.H. Liu, S.M. Li, Y.X. Ma, J.D. Zhang, J.W. An, Electrochim. Acta
151 (2015) 99e108.
[44] B. Zhang, Y.S. Liu, Z.D. Huang, S. Oh, Y. Yu, Y.W. Mai, H.Y. Kim, J. Mater. Chem.
24 (2012) 12133e12140.