Electrochimica Acta 190 (2016) 57–63

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Synergistic effect of Ni and Co ions on molybdates for superior

electrochemical performance
Haichao Chen* , Si Chen, Yuying Zhu, Chao Li, Meiqiang Fan, Da Chen, Guanglei Tian,
Kangying Shu*
College of Materials Science & Engineering, China Jiliang University (CJLU), Hangzhou 310018, China

A R T I C L E I N F O A B S T R A C T

Article history: Nickel cobalt (Ni–Co) molybdates with different stoichiometric nickel and cobalt ratios have been
Received 1 December 2015 synthesized by a facile hydrothermal method. The hydrothermal method is robust enough to synthesis of
Received in revised form 26 December 2015 Ni–Co molybdates with same crystal structure and similar nanorods morphology at different ratios of Ni
Accepted 30 December 2015
and Co. The electrochemical performance of Ni–Co molybdates is measured as positive electroactive
Available online 3 January 2016
material in a three-electrode configuration, which demonstrates typical faradaic redox behaviors of Ni–
Co molybdates that consistent with battery-type materials. Owing to the synergistic effect of Ni and Co
Keywords:
ions, the electrochemical performance in terms of specific capacity, rate capability and cycling stability
Nickel cobalt molybdates
Electrochemical performance
can be readily tuned by varying the Ni and Co content. In particular, the Ni0.67Co0.33MoO4 demonstrates
Energy storage the highest specific capacity of 441C g
1 at 1 A g
1, superior rate capability of 71% capacity retention after
Hybrid supercapacitors 50 times increase in current density. In addition, the Ni0.67Co0.33MoO4 is used to assemble hybrid
supercapacitors with reduced graphene oxide, which shows high specific capacity (119C g
1 at 1 A g
1),
high specific energy (25.6 Wh kg
1 at 775 W kg
1) and high specific power (7750 W kg
1 at 13.2 Wh
kg
1).
ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction Recently, it is found that Ni and Co based battery-type materials

The ever-increasing energy and power demands in applications
such as electronics devices and electric vehicles have triggered
significant research interests in developing high performance
energy-storage devices. As one of the newly arisen electrical
energy storage devices, electrochemical capacitors (also called
supercapacitors) is considered to be the most promising power
sources owing to their high power density, short charge and
discharge time, long lifespan, environmental friendliness, and
excellent safety [1–6]. These significant qualities make super-
capacitors complementary to fuel cells and rechargeable batteries.
However, the energy density of supercapacitors is still much lower
than rechargeable batteries, which restricts them from various
important applications [7]. Therefore, it is urgent and desirable to
design energy-storage devices with both high energy density and
power density.
* Corresponding authors. Fax: +86 57186835738.
E-mail addresses: chenhc@cjlu.edu.cn (H. Chen), shukangying@cjlu.edu.cn
(K. Shu).
can achieve high electric charge storage while maintaining a high
power performance comparable to that of supercapacitive electro-
des [8–13]. Owing to their high power performance, such electrode
materials were once mistaken for pseudocapacitive materials.
However, the faradaic redox properties of Ni and Co based
materials, which characterize by redox CV peaks and flat charge/
discharge plateaus, definitely demonstrate their battery-type
nature, which is completely different from that of pseudocapaci-
tive electroactive materials [14,15]. When used as electrode
materials, Ni and Co based compounds in principle can offer
several-fold higher charge storage and energy densities than
typical carbonaceous materials with electric double layer capaci-
tance. So numerous Ni and Co based compounds (including their
oxides, hydroxides, and sulphides) have been explored to develop
electroactive materials with high electrochemical activity.
Compared to monometallic compounds, mixed transition metal
compounds are investigated to show higher electrochemical
activity, which can be attributed to their richer redox reactions
and improved electronic conductivity than the corresponding
monometallic systems. For example, NiCo2O4 shows higher

http://dx.doi.org/10.1016/j.electacta.2015.12.212
0013-4686/ ã 2015 Elsevier Ltd. All rights reserved.
58 H. Chen et al. / Electrochimica Acta 190 (2016) 57–63
capacity than the corresponding single component oxides of NiO
and Co3O4 owing to its at least two orders of magnitude higher
electronic conductivity and much higher electrochemical activity
[16–19]. Our group has synthesized Ni–Co sulphides, which
exhibits improved electrochemical performance than single
component sulphides of Co sulphide and Ni sulphide [20,21]. In
addition, metal molybdates also show high electrochemical
activity and are recently intensely researched [22–26]. Owing to
the high electrochemical activity of Ni ion [27], NiMoO4 is
considered to show much higher capacity than other molybdates
including CoMoO4 and MnMoO4. However, the cycling stability of
NiMoO4 is still unsatisfactory. Conversely, most reports demon-
strated that CoMoO4 show excellent cycling stability, but low
charge storage capacity. The idea comes that whether partial
replacement of Ni ions with Co ions in their molybdates can inherit
the high capacity of NiMoO4 and the excellent cycling stability of
CoMoO4. Similar to NiCo2O4 and Ni–Co sulphides, the coexistence
of Ni and Co ions can provide multiple redox reactions for the
electrochemical process, which is beneficial for high electrochem-
ical activity. Consequently, superior capacitive performance can be
anticipated for Ni–Co molybdates owing to the synergistic effect of
Ni and Co ions.
To date, a few works have been reported about the synergistic
effect of NiMoO4 and CoMoO4. For example, Liu et al. synthesized
CoMoO4–NiMoO4 hierarchical bundles, which demonstrate high
capacity than both NiMoO4 and CoMoO4 [27]. Senthilkumar et al.
synthesized NiMoO4–CoMoO4 composites and attains a specific
capacity of 883C g
1 [28]. However, in all these reports, the
molybdates are a complex of CoMoO4 and NiMoO4. The partial
replacement between Ni and Co ions but still maintains the same
crystal structure is seldom found owing to the lack of efficient
synthesis method.
In this study, we developed a facile hydrothermal method to
synthesize Ni–Co molybdates with different Ni and Co ratios. All of
the Ni–Co molybdates show the same crystal structure owing to
mutual replacement of Ni and Co ions in molybdates. The
synergistic effect of Ni and Co ions contributes higher specific
capacity, superior rate capability combined with improved cycling
stability of the Ni–Co molybdates.
2. Experimental
2.1. Synthetic procedures
The NixCo1-xMoO4 is synthesized by a simple hydrothermal
method. Briefly, Ni(NO3)26H2O and Co(NO3)26H2O altogether
3 mmol was dissolved into 60 ml of deionized water under
stirring. Then, 3 mmol of Na2MoO42H2O was added and stirred
to form a transparent solution. The solution was transferred into
a Teflon-lined stainless steel autoclave and heated at 160  C for
6 h. After the autoclave had cooled down to room temperature
naturally, the precipitate was separated by centrifugation, and
was washed repeatedly with deionized water and ethanol, then
the nickel cobalt molybdate is dried at 60  C. The Ni and Co
content in the Ni–Co molybdate is stoichiometric determined by
Ni(NO3)26H2O and Co(NO3)26H2O. The chemical formula of the
Ni–Co molybdates are expressed as NixCo1-xMoO4, where x = 0,
0.33, 0.5, 0.67, 0.83, 1 correspond to the molar rations between
Ni(NO3)26H2O and Co(NO3)26H2O are 0:6, 2:4, 3:3, 4:2, 5:1 and
6:0, respectively.
The reduced graphene oxides (RGO) nanosheets were prepared
by the hydrothermal reduction of the graphene oxide (GO)
nanosheets. The detailed synthesis process can be found in our
previously reported study [11].
2.2. Materials characterization
The Ni–Co molybdates is characterized by X-ray diffraction
(XRD, AXS D2 Phaser), field emission scanning electron microscopy
(SEM, HITACHI SU8010), and transmission electron microscopy
(TEM, JEM-2100). The elemental distribution was tested by SEM
(HITACHI SU8010) equipped with elemental mapping.
2.3. Electrochemical measurements
To prepare the work electrode, the Ni–Co molybdates, acetylene
black and poly(tetrafluoroethylene) in a mass ratio of 8: 1: 1 were
dispersed in ethanol to form a suspension. The suspension was
drop dried into nickel foam and dried at 60  C overnight. Then the
Ni foam was pressed at 10 MPa. The mass loading of electroactive
materials on each electrode is 23 mg. A three-electrode
configuration was used to measure electrochemical performance
of the Ni–Co molybdates, and platinum foil (1 1 cm2) was used as
the counter electrode, Hg/HgO electrode was used as the reference
electrode, 6 M KOH was used as the electrolyte. The electrochemi-
cal performance was measured by cyclic voltammetry (CV) and
galvanostatic charge and discharge (GCD) tests. The specific
capacity is calculated according to the following equation:
It
C¼ ð1Þ
m
where, C (in C g
1) represents the specific capacity of the electrode;
I represents the discharge current; t represents the discharge time;
m represents the mass of the electroactive material.
The hybrid supercapacitor is assembled by using as-synthe-
sized Ni–Co molybdates as positive electrode materials, and using
RGO as the negative material, where the Ni–Co molybdate are
battery-type material and the RGO is the electric double layer type
material. The mass loading of RGO is determined by balancing the
charge storage in positive and negative electrodes, which can be
expressed as:
Qþ ¼ Q
ð2Þ
The charge stored in positive electrode and negative electrode
can be calculated by the respective equation below:
Q þ ¼ C þ mþ ð3Þ
Q
¼ C 0
m
V
ð4Þ

1
Where, C+ (in C g ) represents the specific capacity of the positive
electrode, and C 0
(in F g
1) represents the specific capacitance of
RGO; m+ and m– represent the mass of the electroactive materials
on positive and negative electrodes, respectively; V– is the
potential window of the negative electrode. The mass ratio of
electroactive materials in positive electrode and negative is:
mþ C 0
V

¼ ð5Þ
m
Cþ
So the mass loading of RGO can be determined by the specific
capacity of Ni–Co molybdate material, specific capacitance and
potential window of RGO.
3. Results and discussion
Fig. 1 shows the XRD patterns of Ni–Co molybdates with
different Ni and Co ratios. When no Ni(NO3)26H2O is used as
precursor, all of the diffraction peaks can be assigned to CoMoO4
(JCPDS no. 15–0439), so CoMoO4 has been successfully synthe-
sized. After different amount of Ni(NO3)26H2O are added to
 H. Chen et al. / Electrochimica Acta 190 (2016) 57–63
Fig. 1. XRD patterns of the Ni–Co molybdates with different Ni to Co ratios.
provides Ni2+, the XRD patterns are not significantly varied
compared to CoMoO4, so NixCo1-xMoO4 (x = 0, 0.33, 0.5, 0.67,
0.83, 1) with different Ni and Co ratios but the same crystal
structure have been successfully synthesized. Ni2+ and Co2+ are
simultaneous precipitated to form NixCo1-xMoO4 (x = 0.33, 0.5,
0.67, 0.83, 1), and the reaction can be described according to the
following equation:
2þ
xNi þ ð1
xÞCo2þ þ MoO4 2
¼ Nix Co1
x MoO4
where, x = 0, 0.33, 0.5, 0.67, 0.83, 1. The atomic numbers of Co and Ni
are 27 and 28, respectively. This means that Ni locates adjacent to
Co in the Periodic Table, and thereby the atom radii of the Ni and
the Co atom are close. So the replacement of Co atom by Ni atom in
Ni–Co molybdates only brings about a small change in crystal
structure, giving rise to similar XRD patterns of Ni–Co molybdates
with different Ni and Co ratios, as shown in Fig. 1. With the increase
of Ni to Co ratio, all the diffraction peaks of Ni–Co molybdates
slightly shift to high diffraction angle direction. Take the
310 diffraction peaks for example, the diffraction peaks locates
at 29.45 , 29.55 , 29.57, 29.59 , 29.83 and 29.90 for the NixCo1-
xMoO4 with x = 0, 0.33, 0.5, 0.67, 0.83 and 1, respectively. The shift
of diffraction peaks to high angle direction can be attributed to the
gradually decrease in lattice parameters owing to the gradual
replace of Co with Ni ions.
Fig. 2. SEM images of the NixCo1-xMoO4, where (a) x = 0, (b) x = 0.33, (c) x = 0.5, (d) x = 0.67, (e) x = 0.87 and (f) x = 1.
59
The morphology and structure of Ni–Co molybdates are
measured by SEM test, as shown in Fig. 2. Obviously, all the Ni–
Co molybdates show similar morphology and structure even at
different Ni and Co contents. The NixCo1-xMoO4 (x = 0, 0.33, 0.5,
0.67, 0.83, 1) all exhibit rod-like morphology. With increasing the
content of Ni, the lengths of those nanorods gradually increase, and
their diameters gradually decrease. So Ni contributes the
longitudinal growth of the Ni–Co molybdates. To further demon-
strate the detailed morphology and structure of Ni–Co molybdates,
as a representative, Ni0.67Co0.33MoO4 is measured by TEM test, as
shown in Fig. 3a and b. Apparently, the Ni0.67Co0.33MoO4 is
composed of numerous nanorods, which is in good agreement
with the SEM measurement. To ensure the uniform distribution of
the Ni and Co ions in the Ni–Co molybdates, the Ni0.67Co0.33MoO4
sample was also measured using a SEM equipped with elemental
mapping. Fig. 3c shows the elemental mapping of the Ni, Co and
Mo elements of the Ni0.67Co0.33MoO4. Evidently, the Ni, Co and Mo
elements are uniformly distributed in the Ni0.67Co0.33MoO4,
demonstrating the coexistence of the Ni and Co ions in the Ni–
Co molybdates. So, different from various reports with respect to
CoMoO4–NiMoO4 [27,28], the Ni–Co molybdates in this study is
constituted by inter-substitution of both Ni and Co ions, which is in
good agreement with the XRD measurement.
Owing to the same crystal structure and similar morphology of
NixCo1-xMoO4 (x = 0, 0.33, 0.5, 0.67, 0.83, 1), the effect of Ni and Co
ð6Þ ratio on electrochemical performance of Ni–Co molybdates can be
well investigated. The Ni–Co molybdates with different Ni and Co
ratios were used as electroactive materials, and a three-electrode
glass configuration is used to measure their electrochemical
performance; wherein, 6 M KOH is used as the aqueous electrolyte,
a Hg/HgO electrode is used as the reference electrode, and a Pt
electrode (1 1 cm) is used as the counter electrode. Fig. 4a shows
CV curves at 5 mV s
1 of the Ni–Co molybdates with different Ni
and Co ratios. All of the CV curves are distinct from a true
pseudocapacitive electrode (such as MnO2, RuO2) characterized by
nearly rectangular CV curves [14,15]. A pair of strong redox peaks
can be definitely observed in the CV curves of the Ni–Co
molybdates with different Ni and Co ratios. The obvious redox
peaks in CV curves is a typical feature of faradaic behaviour of
battery-type electrodes, so it is concluded that all of the Ni–Co
molybdates are battery-type materials. The redox peaks of the CV
curves can be ascribed to the faradaic reactions of Ni and Co ions
60 H. Chen et al. / Electrochimica Acta 190 (2016) 57–63

Fig. 3. (a,b) TEM images of the Ni0.67Co0.33MoO4. (c) The elemental mapping measurement of Ni0.67Co0.33MoO4 sample.

associated with OH

anions, which can be described by the

following equations [22]:
CoOOH þ OH
$CoO2 þ H2 O þ e
ð8Þ
 

3 MðOHÞ3 $3MOOH þ 3H2 O þ 3e
ð7Þ
Where, M represent Ni ions and Co ions. From Fig. 4a, it is found
that the integrated area of the Ni–Co molybdates varies as the Ni
and Co ratios changes. Generally, the integrated area of an

Fig. 4. (a) CV curves of the Ni–Co molybdates at 5 mV s
1. (b) CV curves and (c) GCD curves at different rates. (d) Specific capacity and (e) rate capability of Ni–Co molybdates at
different current densities. (f) cycling stability of the Ni–Co molybdates.
 H. Chen et al. / Electrochimica Acta 190 (2016) 57–63
electrode is in direct proportion to its capacity. So our study
provides an effective method to optimize the electrochemical
performance of molybdates by tuning the transition-metal
compositions. In particular, Ni–Co molybdates with a Ni and Co
ratio of 2:1 show the maximum integrated area, demonstrating its
highest specific capacity.
As a representative example, CV curves and GCD curves at
different rates of the Ni0.67Co0.33MoO4 are presented in Fig. 4b and
c, respectively. The definite redox peaks and charge/discharge
plateaus in the CV and GCD curves, respectively, can also
demonstrate the faradaic behaviour of the Ni–Co molybdates,
which can further demonstrate the battery-type charge storage
mechanism of Ni–Co molybdates. The specific capacity at different
rates of the Ni–Co molybdates can be calculated from the GCD
curves at different current densities, and the result is plotted in
Fig. 4d. In good agreement with the CV curves in Fig. 4a, the
Ni0.67Co0.33MoO4 show the highest specific capacity in NixCo1-
xMoO4 (x = 0, 0.33, 0.5, 0.83, 1), indicating its superior
Fig. 5. (a–d) TEM images of the Ni0.67Co0.33MoO4 after 1000 charge and discharge cycles. (e) Schematic illustration of the morphology evolution of the Ni–Co molybdate
nanorods during long-term cycling test.
61
electrochemical activity. A specific capacity up to 441C g
1 has
been achieved at a current density of 1 A g
1, which is much higher
than various reports about metallic molybdates, such as CoMoO4
[24,29], MnMoO4/CoMoO4 [22]. From Fig. 4d, it is found that both
of the bimetallic Ni–Co molybdates and NiMoO4 show much higher
specific capacity than CoMoO4, which can be ascribed to the
relatively higher electrochemical activity of Ni ions in charge
storage than Co ions. After all, most of the Ni based compound
show higher charge storage performance than Co based compound
at similar preparation condition. Therefore, increasing the Ni
content in Ni–Co molybdates will give rise to an increase in active
mass of electroactive materials. So the specific capacities of Ni–Co
molybdates gradually increase as the Ni and Co ratio increasing.
The order of specific capacity of the NixCo1-xMoO4 (x = 0, 0.33, 0.5,
0.67) is: CoMoO4 < Ni0.33Co0.67MoO4 < Ni0.5Co0.5MoO4 <
Ni0.67Co0.33MoO4. However, owing to the synergistic effect of Ni
and Co ions on the Ni–Co molybdates, a certain amount of Co is
essential for superior capability. So, when the Ni and Co ratio is
62 H. Chen et al. / Electrochimica Acta 190 (2016) 57–63
higher than 2:1, the specific capacity gradually decreases with the
increase of Ni and Co ratio. The order of specific capacity of the
NixCo1-xMoO4 (x = 0.67, 0.83, 1) is: Ni0.67Co0.33MoO4 > Ni0.83Co0.17-
MoO4 > NiMoO4. Therefore, our study provides a facile and robust
method to tuning the electrochemical activity of molybdates. The
improved capability of bimetallic Ni–Co molybdates NixCo1-xMoO4
(x = 0.5, 0.67, 0.83) than monometallic molybdates can be
attributed to the combined contributions from both of Ni ions
and Co ions. The coexistence of Ni ions and Co ions provides richer
redox reactions for the electrochemical process, which is beneficial
for higher electrochemical activity. Especially, Ni0.67Co0.33MoO4
shows highest capability, indicating the highest electrochemical
activity of Ni–Co molybdates at a Ni and Co ratio of 2:1.
The rate capability of as-synthesized Ni–Co molybdates is also
used to evaluate the high-power performance. The specific
capacities of NixCo1-xMoO4 (x = 0, 0.33, 0.5, 0.67, 0.83, 1) are all
normalized relative to their specific capacities at 1 A g
1, respec-
tively. Fig. 4e shows the capacity retention versus current density
curves of Ni–Co molybdates. After 50 times increase in current
density, the capacity retentions of NixCo1-xMoO4 at x = 0, 0.33, 0.5,
0.67, 0.83, 1 are 34%, 50%, 72%, 71%, 51% and 33%, respectively.
Apparently, bimetallic Ni–Co molybdates NixCo1-xMoO4 (x = 0.33,
0.5, 0.67, 0.83) show much higher capacity retention than
monometallic molybdates NiMoO4 and CoMoO4, which can be
attributed to the combined contributions of Ni ions and Co ions.
The coexistence of Ni and Co ions is beneficial for high rate
capability, which can be generally found in Ni–Co based
compounds, such as Ni–Co oxides [17], Ni–Co hydroxides
[12,13], Ni–Co sulphides [21]. However, a systematic study of Ni
and Co content on the rate capability of Ni–Co molybdates is
seldom found. The Ni0.5Co0.5MoO4 and Ni0.67Co0.33MoO4 show the
much higher rate capability than Ni–Co molybdates at other Ni and
Co ratios; so they can be used as high-rate electroactive materials
for high-power supercapacitors.
As long-term cycling stability is vital for high-performance
charge storage device, the cycling stability of Ni–Co molybdates is
measured by repeated charge and discharge measurement. Fig. 4f
Fig. 6. (a) CV curves of the Ni0.67Co0.33MoO4 and RGO at 5 mV s
1. (b) GCD curves and (c) specific capacity at different current densities, and (d) Ragone plot of the
Ni0.67Co0.33MoO4//RGO hybrid supercapacitors.
shows the calculated specific capacity as a function of cycle
number curves of the Ni–Co molybdates. For the NiMoO4 sample,
the specific capacity gradually decreased with cycling. After
1000 charge and discharge cycles, only 54% of the specific capacity
can be retained. So NiMoO4 show poor cycling stability during
repeated charge and discharge, which is commonly found in the
reports about NiMoO4 [30,31]. However, when introducing Co ions
to partial replace Ni ions, improved cycling stability can be
attained. The NixCo1-xMoO4 at x = 0.83, 0.67, 0.5, 0.33 retain 64%,
80%, 84%, 98% and 100% of the capacity, which are all much higher
than NiMoO4. So Co ions contribute higher cycling stability in Ni–
Co molybdates. After 1000 charge and discharge cycles, the specific
capacity of Ni0.67Co0.33MoO4 still retains 336C g
1. This specific
capacity is still higher than Ni–Co molybdates with other Ni and Co
ratios, demonstrating its superior capability.
To unveil the evolution of Ni–Co molybdates during repeated
charge and discharge process, TEM test is used to measure the
morphology of Ni0.67Co0.33MoO4 after 1000 charge and discharge
cycles, as shown in Fig. 5. The Ni0.67Co0.33MoO4 after 1000 cycles is
ultrasonic treated in ethanol to separate from Ni foam, and used for
TEM measurment. Obviously, the Ni0.67Co0.33MoO4 still maintains
the rod-like morphology (Fig. 5a and b). However, the solid
nanorod becomes ultra-loosen, which is completely different from
the sample before long-term cycling test. The Ni0.67Co0.33MoO4 is
composed of numerous connected nanosheets, as shown in Fig. 5c
and d. Therefore, there is a gradually corrosion of electroactive
material during repeated charge and discharge process, matching
well with various electroactive materials, including NiCo2O4 [32],
Co9S8 [33], NixCo4-xS4 [21]. This is the first attempt to investigate
the morphology evolution of Ni–Co molybdates during long-term
cycling test. Owing to the corrosion of electroactive material, the
diameter of Ni0.67Co0.33MoO4 nanorods becomes much larger, and
some of them even bend due to the morphology change of the
electroactive material, as shown in Fig. 5b. Based on the above
analysis, the mechanism for morphology change during long-term
cycling can be proposed. During the repeated charge and discharge
process, the Ni–Co molybdates are gradually corroded owing to the
 H. Chen et al. / Electrochimica Acta 190 (2016) 57–63
repeated faradic redox reaction of both Ni and Co ions with the
electrolyte ions OH
. The Ni–Co molybdate nanorods are recrystal-
lized to form numerous nanosheets. Owing to the continuous
corrosion of the electroactive materials in repeated charge and
discharge process, the Ni–Co molybdate nanorods are completely
converted to nanosheets structure. However, the interconnection
of those nanosheets ensures the Ni–Co molybdate not cracked and
pulverized, excellently maintaining the nanorod-like morphology.
Therefore, the Ni–Co molybdate nanorods are converted to
nanosheets constituted ultra-loosen nanorods structure, as shown
in Fig. 5e.
To better demonstrate the excellent charge storage perfor-
mance of as-synthesized Ni–Co molybdates, Ni0.67Co0.33MoO4 is
used as the positive material to assemble hybrid supercapacitors
with RGO electrode. The potential windows of Ni0.67Co0.33MoO4
and RGO are 00.55 V and –10 V (vs. Hg/HgO), respectively.
Owing to the different potential windows of Ni0.67Co0.33MoO4 and
RGO, the voltage of Ni0.67Co0.33MoO4//RGO hybrid supercapacitors
can be extended to 1.55 V, as shown in Fig. 6a. Fig. 6b shows the
GCD curves of the hybrid supercapacitors, which is evidently
showing that the voltage of as-assembled hybrid supercapacitors
can be charged to 1.55 V. Based on the GCD curves at different
current densities, the specific capacity of the hybrid super-
capacitors can be calculated. Fig. 6c shows the specific capacity
vs. current density curves of the Ni0.67Co0.33MoO4//RGO hybrid
supercapacitor. A specific capacity up to 119C g
1 can be attained at
1 A g
1. The mass of electroactive refers to the total mass of both
Ni0.67Co0.33MoO4 and RGO, so the specific capacity is still
remarkable. The energy density and power density of the
Ni0.67Co0.33MoO4//RGO hybrid supercapacitor were calculated
based on the GCD curves to obtain the Ragone plot, as shown in
Fig. 6d. The hybrid supercapacitor shows an energy density of
25.6 Wh kg
1 at a power density of 775 W kg
1. The energy density
still retains 13.2 Wh kg
1 when the power density increased to
7750 W kg
1, demonstrating high power performance of the
hybrid supercapacitor. The Ni0.67Co0.33MoO4//RGO hybrid super-
capacitor shows much higher energy density than the previously
reported Ni-Co compounds or molybdates based hybrid super-
capacitors, such as AC//NiMoO4-CoMoO4 [27,28], Ni-Co oxides//AC
hybrid supercapacitors [34], demonstrating high energy density of
the Ni0.67Co0.33MoO4//RGO hybrid supercapacitor.
4. Conclusions
In summary, we have developed a facile hydrothermal method
to synthesize Ni–Co molybdates with the different Ni and Co ratios.
The method is robust enough to maintain the Ni–Co molybdates
with same crystal structure and similar nanorods morphology
even at different Ni and Co ratios. The electrochemical perfor-
mance of Ni–Co molybdates is tuned by the Ni and Co content. The
bimetallic molybdates, especially for Ni0.67Co0.33MoO4, show
superior capability than monometallic molybdates including
NiMoO4 and CoMoO4. This work demonstrates that the synergistic
effect of Ni and Co ions on molybdates contributes high specific
capacity and improved rate capability, and Co ions contribute high
63
cycling stability of Ni–Co molybdates. So it is feasible to design high
performance electroactive materials using the synergistic effect of
metallic components.
Acknowledgements
The authors acknowledge financial support from the National
Natural Science Foundation of China (no. 51501175) and the
Natural Science Foundation of Zhejiang Province (LQ16E010001).
References
[1] B.E. Conway, Electrochemical Supercapacitors: Scientific Fundamentals and
Technological Applications, Kluwer Academic/Plenum Publishers, New York,
1999.
[2] L.L. Zhang, X.S. Zhao, Chem. Soc. Rev. 38 (2009) 2520.
[3] H. Jiang, P.S. Lee, C. Li, Energy Environ. Sci. 6 (2013) 41.
[4] Z. Wu, Y. Zhu, X. Ji, J. Mater. Chem. A 2 (2014) 14759.
[5] J. Yan, Q. Wang, T. Wei, Z. Fan, Adv. Energy Mater. 4 (2014) 1300816.
[6] G. Wang, L. Zhang, J. Zhang, Chem. Soc. Rev. 41 (2012) 797.
[7] P. Simon, Y. Gogotsi, Nat. Mater. 7 (2008) 845.
[8] B.P. Bastakoti, H.S. Huang, L.C. Chen, K.C.W. Wu, Y. Yamauchi, Chem. Commun.
48 (2012) 9150.
[9] B. Wang, J.S. Chen, Z. Wang, S. Madhavi, X.W. Lou, Adv. Energy Mater. 2 (2012)
1188.
[10] Y. Xiao, S. Liu, F. Li, A. Zhang, J. Zhao, S. Fang, D. Jia, Adv. Funct. Mater. 22 (2012)
4052.
[11] H.C. Chen, J.J. Jiang, L. Zhang, D.D. Xia, Y.D. Zhao, D.Q. Guo, T. Qi, H.Z. Wan, J.
Power Sources 254 (2014) 249.
[12] D.D. Xia, H.C. Chen, J.J. Jiang, L. Zhang, Y.D. Zhao, D.Q. Guo, J.W. Yu, Electrochim.
Acta 156 (2015) 108.
[13] H.C. Chen, J.J. Jiang, L. Zhang, Y.D. Zhao, D.Q. Guo, Y.J. Ruan, D.D. Xia,
ChemPlusChem 80 (2015) 181.
[14] P. Simon, Y. Gogotsi, B. Dunn, Science 343 (2014) 1210.
[15] T. Brousse, D. Belanger, J.W. Long, J. Electrochem. Soc. 162 (2015) A5185.
[16] T.Y. Wei, C.H. Chen, H.C. Chien, S.Y. Lu, C.C. Hu, Adv. Mater. 22 (2010) 347.
[17] H.C. Chen, J.J. Jiang, L. Zhang, T. Qi, D.D. Xia, H.Z. Wan, J. Power Sources 248
(2014) 28.
[18] C. Yuan, J. Li, L. Hou, X. Zhang, L. Shen, X.W. Lou, Adv. Funct. Mater. 22 (2012)
4592.
[19] H. Wang, Q. Gao, L. Jiang, small 7 (2011) 2454.
[20] H.C. Chen, J.J. Jiang, L. Zhang, H.Z. Wan, T. Qi, D.D. Xia, Nanoscale 5 (2013) 8879.
[21] H.C. Chen, J.J. Jiang, Y.D. Zhao, L. Zhang, D.Q. Guo, D.D. Xia, J. Mater. Chem. A 3
(2015) 428.
[22] L.Q. Mai, F. Yang, Y.L. Zhao, X. Xu, L. Xu, Y.Z. Luo, Nat. Commun. 2 (2011) 381.
[23] S. Peng, L. Li, H.B. Wu, S. Madhavi, X.W. Lou, Adv. Energy Mater. 5 (2014)
1401172.
[24] M.C. Liu, L.B. Kong, C. Lu, X.M. Li, Y.C. Luo, L. Kang, Mater. Lett. 94 (2013) 197.
[25] M.C. Liu, L. Kang, L.B. Kong, C. Lu, X.J. Ma, X.M. Li, Y.C. Luo, RSC Advances 3
(2013) 6472.
[26] D. Guo, P. Zhang, H. Zhang, X. Yu, J. Zhu, Q. Li, T. Wang, J. Mater. Chem. A 1 (2013)
9024.
[27] M.C. Liu, L.B. Kong, C. Lu, X.J. Ma, X.M. Li, Y.C. Luo, L. Kang, J. Mater. Chem. A 1
(2013) 1380.
[28] B. Senthilkumar, D. Meyrick, Y.S. Lee, R.K. Selvan, RSC Adv. 3 (2013) 16542.
[29] M.C. Liu, L.B. Kong, X.J. Ma, C. Lu, X.M. Li, Y.C. Luo, L. Kang, New J. Chem. 36
(2012) 1713.
[30] B. Senthilkumar, K.V. Sankar, R.K. Selvan, M. Danielle, M. Manickam, RSC Adv. 3
(2013) 352.
[31] D. Cai, D. Wang, B. Liu, Y. Wang, Y. Liu, L. Wang, H. Li, H. Huang, Q. Li, T. Wang,
ACS Appl. Mater. Interfaces 5 (2013) 12905.
[32] Y. Li, Y. Zhang, Y. Li, Z. Wang, H. Fu, X. Zhang, Y. Chen, H. Zhang, X. Li,
Electrochim. Acta 145 (2014) 177.
[33] J. Yu, H. Wan, J. Jiang, Y. Ruan, L. Miao, L. Zhang, D. Xia, K. Xu, J. Electrochem.
Soc. 161 (2014) A996.
[34] C. Tang, Z. Tang, H. Gong, J. Electrochem. Soc. 159 (2012) A651.