Journal of Materials Science: Materials in Electronics (2019) 30:7497–7506

https://doi.org/10.1007/s10854-019-01063-z

Hydrothermal synthesis of ­NiCo2O4–NiO nanorods for high

performance supercapacitors
M. Haripriya1 · R. Sivasubramanian1 · Anuradha M. Ashok2 · Shamima Hussain3 · G. Amarendra3

Received: 3 August 2018 / Accepted: 4 March 2019 / Published online: 11 March 2019
© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
In this work, spinel-metal oxide ­(NiCo2O4–NiO) nanorods based electrode was fabricated and tested for their efficacy as
supercapacitors. The ­NiCo2O4–NiO was synthesized by hydrothermal method and characterized using thermogravimetric
analysis/differential scanning calorimetry (TGA/DSC), X-ray diffraction (XRD), Fourier transform infrared spectroscopy
(FTIR), scanning electron microscope (SEM) and transmission electron microscope (TEM) respectively. The TEM images
reveal the morphology of the synthesized metal oxides in the form of nanorods with length of several micrometers and
diameter in the range of 60–70 nm. The XRD pattern confirmed the formation of cubic spinel structure. A three electrode
­ iCo2O4–NiO
cell set up was employed to estimate the electrochemical performance of the material. It is observed that the N
showed specific capacitance of 490 F/g at 0.5 A/g as compared to pure N ­ iCo2O4 which is around 216 F/g at 0.5 A/g. The
enhanced capacitance mainly arises from the incorporation of NiO secondary phases within the spinels which increases the
number of redox active sites. The present work proves to be a promising strategy to improve the performance of the electrode
material for supercapacitors.

1 Introduction storage takes place through Faradaic redox transition over

Supercapacitors have received increasing attention among
the research community due to its promising application
as an alternative energy source to the depleting fossil fuel
resources [1]. They are also known as ultracapacitors which
bridge the gap between conventional capacitors and batter-
ies. Unlike batteries, supercapacitors possess high power
density, low energy density and high cyclic stability [2]. It
is widely accepted that based on the energy storage mech-
anism, supercapacitors can be broadly classified into two
categories viz electrical double layer capacitor (EDLC)
and pseudocapacitor. EDLC store charge by non-Faradaic
adsorption/desorption of ions between the electrode–elec-
trolyte interface, whereas in pseudocapacitor the charge
* R. Sivasubramanian
rss@psgias.ac.in
1
Electrochemical Sensors & Energy Materials Laboratory,
Department of Chemistry, PSG College of Technology,
Coimbatore 641004, India
2
Functional Materials Laboratory, Department of Physics,
PSG College of Technology, Coimbatore 641004, India
3
Kalpakkam Center, UGC DAE CSR, Kokilamedu,
Tamil Nadu 603104, India
the electrode–electrolyte interface. Carbon based materials
like graphene [3], activated carbon [4], MWCNTs [5] con-
stitute suitable examples for EDLC and conducting polymers
like PANI [6] or PPy [7] and metal oxides such as ­RuO2 [8],
­Fe3O4 [9], ­Co3O4 [10, 11], NiO [12] ­Mn3O4 [13], ­MnO2
[14] exhibit pseudocapacitance behaviour. It is well known
that the pseudocapacitors show high specific capacitance and
cyclic stability than EDLC based materials.
Among the pseudocapacitor electrodes, metal oxides
show promising behaviour due to their high theoretical
capacitance. For instance NiO possess high theoretical
capacitance of 2573 F/g within the potential of 0–0.5 V
[15]. Recently, binary transition metal oxides have gained
increasing interest due to the presence of one or more metal
ions showing reversible multi- electron transfer. Metal
oxides such as ­MnFe2O4 [16], ­LaMnO3 [17–20], ­MnMoO4
[21] have been studied to a greater extent. Among them
­NiCo2O4 is a binary transition metal oxide with a spinel
structure wherein N ­ i2+ ions occupy the octahedral sites and
3+
­Co ions are present in both the octahedral and tetrahe-
dral sites respectively [22] (as shown in Fig. 1). Moreover
the tetrahedral sites are predominantly occupied by C ­ o3+
ions. Generally spinels are thermodynamically stable and
show improved electrochemical properties due to its high

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7498
Fig. 1  Pictorial representation of unit cell of ­NiCo2O4
conductivity. It is seen that the conductivity of ­NiCo2O4 is
two orders higher in magnitude than the individual oxides of
Ni and Co. The electronic conductivity can further enhance
the electron transfer rate giving rise to Faradaic reaction
eventually increasing the specific capacitance. In this context
­NiCo2O4 has shown to be a promising material for superca-
pacitor applications [23–31]. In addition various structural
modifications like inducing porosity [32], increasing the
surface area [33] and using carbon based support materials
[34–36] for enhancing the capacitance has been reported in
the recent past. For instance Hu et al., reported a mesoporous
­NiCo2O4 nanoparticles with high specific area of 438.3 m2/g
and specific capacitance of 1157.7 F/g [25]. The electrode
material showed a long term cyclic stability with capac-
ity retention of 97.1% upto 5000 cycles. In a similar work
Yamauchi [37] in 2017 reported ­NiCo2O4 nanosheets on
nanoporous carbon composites with a specific capacitance
of 310 F/g at a scan rate of 5 mV/s. Interestingly symmetric
and asymmetric supercapacitors based on ­NiCo2O4 having
large areal capacitance was reported by Cao et al. [23].
In addition to the above modifications binary metal
oxides of nickel & cobalt were also studied for their pseu-
docapacitance [38–40]. For example Zhu et al. prepared
­ o3O4–NiO using electrodeposition method and
flower like C
showed a specific capacitance of 607.5 F/g at a current den-
sity of 0.5 A/g [41]. Although NiO and C ­ o3O4 are known
to have high theoretical specific capacitance, their poor rate
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Journal of Materials Science: Materials in Electronics (2019) 30:7497–7506
of electron transfer capability limits their practical applica-
tion. But a combination of both metal oxides could increase
the conductivity and can also exhibit high rate of capaci-
tance due to the synergetic effect. For instance Liu et al.
in [42], prepared a one dimensional porous NiO decorated
on ­Co3O4 composite for supercapacitor applications. The
nanocomposite showed a capacitance of 1112 F/g at a high
current density of 2 A/g. Similarly studies on binary metal
oxide-metal oxide nanocomposite were also carried out for
its good pseudocapacitive behaviour. Hao et al. [43] reported
NiO anchored ­NiCo2O4 composite on carbon cloth elec-
trode which showed a capacitance of 709 F/g. Further Liu
et al. [44] showed an improved capacitive behaviour with
­NiCo2O4@NiO nanowire arrays in a two step approach. The
composite in a three electrode set up showed a capacitance
of 2220 F/g with a capacitance retention of 93.1% after 3000
cycles. Further kalaiselvan et al. [45] fabricated an asym-
metric supercapacitor with ­NiCo2O4–NiO composite as a
positive electrode and ­Fe2O3 as negative electrode instead of
activated carbon. The cell showed a capacitance of 417 F/g
at a scan rate of 1 mV/s with a cyclic stability of 97%.
The large surface area, porosity, short diffusion path, good
electrolyte accessibility along with fast Faradaic reaction
lead to increased performance in the material [46]. In addi-
tion the construction of composites with different phases,
induces extra charge at the interface leading to synergistic
effect and rapid charge transport [47, 48]. Zhao et al. [47]
reported a core–shell ammonium nickel cobalt phosphate
with unique interfacial structure providing extra charges and
thereby enhancing the capacitance. Similarly improving the
charge storage mechanism by altering the interface struc-
tures in a nanocomposite was reported by Maier et al. [49].
In this context, secondary phases induced binary metal oxide
structures can provide a rich interface which may further
increase the pseudocapacitance of the material. In this work,
NiO phase was induced in ­NiCo2O4 nanostructures through
a simple one-step hydrothermal method and their perfor-
mance in the energy storage application were analysed. The
formation of rich interface by inducing NiO was noticed
leading to high capacitance contribution.
2 Experimental details
2.1 Materials
Cobalt chloride (Loba ≥ 98%), nickel chloride (Loba ≥ 98%),
urea (Loba ≥ 98%), nickel foil (Alfa Aesar ≥ 99.5%),
potassium hydroxide (Loba ≥ 85%), ACETYLENE black
(Alfa Aesar ≥ 99.9%), POLYVINYLIDENE fluoride
(Alfa Aesar ≥ 99%) and N-methyl-2-pyrrolidone (Alfa
Aesar ≥ 99.9%) were purchased and used without further
purification. Millipore water of conductivity (18 mΩ) was
Journal of Materials Science: Materials in Electronics (2019) 30:7497–7506 7499
used for the preparation of all the solutions throughout the
work.
3 Synthesis of ­NiCo2O4–NiO
Initially, ­NiCo2O4 powder was prepared using hydrothermal
synthesis method. Stoichiometric amount of C ­ oCl2.6H2O
(1.33 g), ­NiCl2.6H2O (0.66 g) and urea (0.48 g) were dis-
solved in 100 mL deionized water and stirred for 30 min
using a magnetic stirrer. A transparent pink coloured solu-
tion was obtained. The solution was then transferred into a
100 ml Teflon–lined stainless steel autoclave and heated at
120 °C for 16 h. The obtained solution was centrifuged and
rinsed with deionised water and ethanol for several times.
It was then dried at 80 °C for 6 h and calcined at 400 °C
for 2 h. For the preparation of N
­ iCo2O4–NiO similar proce-
dure was followed by changing the amount of N ­ iCl2.6H2O
to 1.2 g. A schematic illustration of the preparation of the
composite was shown in Scheme 1.
4 Characterization methods
The phase formation was identified using thermo gravimet-
ric analysis/differential scanning calorimetry (TGA/DSC;
Netzsch STA Jupiter 4429) with a heating rate of 20 °C/
min. The structural patterns of the as-synthesized powders
were characterized by X-ray diffraction (XRD; Rigaku D/M
ax-2400, Japan) at a scanning speed of 20° min− 1 over a 2θ
range of 10°–80°. The surface morphology was recorded
using scanning electron microscope (SEM; CARL ZEISS
EVO 18) and high resolution transmission electron micro-
scope (HRTEM; JEOL JEM 2100). Fourier transform
infrared spectroscopy (FTIR) was used to identify func-
tional groups using IR Affinity 1 spectrometer. The Brau-
nauer–Emmett–Teller (BET) measurement was carried out
from Quanta Chrome Autosorb 1C analyser.
Scheme 1  Illustration of the preparation of N
­ iCo2O4–NiO composite
5 Electrochemical measurements
The electrochemical techniques such as cyclic voltammetry
(CV), galvanostatic charge–discharge (GCD) and impedance
analysis were performed from Biologic VMP3B-20 worksta-
tion at room temperature. A three-electrode cell set up was
employed with Ni foil as the working electrode, platinum
wire as counter electrode and Ag/AgCl (3M KCl) as ref-
erence electrode respectively. The working electrode was
prepared by coating the homogeneous slurry of N ­ iCo2O4/
NiCo2O4–NiO, acetylene black and polyvinylidene fluoride
(PVDF) in a weight ratio of 80:10:10 in N-methyl-2-pyr-
rolidone (NMP) onto 1 cm × 1 cm Ni foil as the current
collector. The coated samples were dried under vaccum at
80 °C for 2 h. All the electrochemical measurements were
performed in 1M KOH aqueous solution. The CV studies
were carried out within the potential range of 0 V-0.5 V at
different scan rates. Similarly the GCD studies were car-
ried out at different current densities per unit weight in the
potential range of 0 V-0.4 V and the specific capacitance was
computed from the following equation.
Cs = It∕mΔV (1)
where Cs is the specific capacitance in (F/g), I is the cur-
rent in (A), t is the discharging time (s), m is the mass of the
active material loaded (g) and ΔV is the potential window
(V). The cyclic stability was performed on the electrode
materials using GCD for 2000 charge–discharge cycles at
a current density of 5 A/g. The electrochemical impedance
analysis was performed for the electrodes in the frequency
range of ­102 to 1­ 0− 2 Hz with an amplitude of 5 mV at their
open circuit potentials.
6 Results and discussion
The TGA/DSC analysis was performed in the temperature
range of 0–800 °C. Figure 2a, b shows the TGA/DSC curve
of ­NiCo2O4 and ­NiCo2O4–NiO respectively. The first stage
of weight loss at 320 °C was due to the removal of vola-
tile components and moisture in the material. After 400 °C,
no significant weight loss was observed which indicates
the formation of final phase in both the compounds. The
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7500
Fig. 2  TGA and DSC curves for a ­NiCo2O4 and b ­NiCo2O4–NiO
DSC curve shows the clear evidence of exothermic reac-
tions occurring in the material which is in comparison with
the TGA results. Upto 300 °C dehydration and release of
volatile compounds takes place. At 400 °C there is a melt-
ing peak indicating the sudden phase transition of the sam-
ple. Beyond 400 °C crystallisation occurs in the material.
Hence both the materials were calcined separately at a tem-
perature of 400 °C for 2 h at a heating rate of 4 °C ­min− 1.
Figure 3a shows the XRD patterns of the calcined N ­ iCo2O4
and ­NiCo2O4–NiO. The diffraction peaks are comparatively
strong and sharp which suggests that the powders are highly
crystalline in nature. For N­ iCo2O4, the peaks obtained at
18.6°, 31.1°, 36.4°, 38.2°, 44.6°, 55.3°, 58.9°and 64.7° cor-
responds to (111), (220), (311), (222), (400), (422), (511)
and (440) planes respectively. As the ratio of Nickel pre-
cursor was varied, secondary phases of NiO was noticed
Fig. 3  a XRD pattern and b FTIR spectrum of ­NiCo2O4 and ­NiCo2O4–NiO
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Journal of Materials Science: Materials in Electronics (2019) 30:7497–7506
along with the peaks corresponding to N ­ iCo2O4. The peaks
obtained at 16.6°, 21.3°, 33.3°, 42.2°, 61.8° and 26.0° corre-
sponds to (111), (200), (311), (400), (440) of NiO and (101)
planes of N­ i2O4 respectively. The XRD pattern indicates the
presence of cubic spinel structure and the values of the cell
parameters are in agreement with JCPDS database number
73-1702 and 89-5881 respectively. In addition the crystal-
lite size of N
­ iCo2O4 and N
­ iCo2O4–NiO was estimated using
Debye–Scherrer equation
D = 0.9𝜆∕𝛽cos𝜃 (2)
where D is the crystallite size (nm), λ the wavelength of
the X-ray (1.54 Å), β is Full width half maximum of the
peak and θ the angle of diffraction. The crystallite size of
­NiCo2O4 and ­NiCo2O4–NiO was found to be 28.17 nm and
16.30 nm respectively. Figure 3b shows the FTIR image of
Journal of Materials Science: Materials in Electronics (2019) 30:7497–7506 7501

­NiCo2O4 and ­NiCo2O4–NiO. The prominent bands observed
in the spectrum for N ­ iCo2O4 at 3495 cm− 1 due to O–H
stretching vibrations and the band at 2922 cm− 1 due to bend-
ing vibration of water molecules. The bands at 1509 cm− 1 &
1376 cm− 1 indicates the presence of H–O–H bending vibra-
tion mode. The weak bands at 662 cm− 1 and 567 cm− 1 were
attributed to the metal oxide vibrations which were shifted
to 755 cm− 1 and 834 cm− 1 as in case of ­NiCo2O4–NiO. The
broad absorption band in the region 410 cm− 1 & 490 cm− 1
was assigned to Ni–O stretching vibration mode [50].
Figure  4a, b shows the SEM images of ­NiCo2O4 and
­NiCo2O4–NiO respectively. Bundles of nanorods intercon-
nected with each other were observed for ­NiCo2O4 as shown in
Fig. 4a. In the case of N
­ iCo2O4–NiO, flower like morphology
formed by conjoined bundles of nanorods were observed. TEM
images in Fig. 4 c, d show the presence of distinct nanorods
with length of several micrometers and diameter in the range
of 60–70 nm. In the case of ­NiCo2O4–NiO nanorods, nano-
particles of size ~ 20–50 nm are found attached on the surface
of the rods. These particles could possibly be the secondary
phase (NiO) in the sample. The selected area electron diffrac-
tion (SAED) pattern shows the polycrystalline nature in both
the cases and the concentric rings can be assigned to the cor-
responding planes of N­ iCo2O4 and ­NiCo2O4–NiO respectively.
The indexed patterns are consistent with the XRD analysis.
The energy dispersive X-ray (EDX) analysis shows the pres-
ence of the constituent elements of the composite (Fig. 4e).
The specific surface area of N ­ iCo2O4 and N ­ iCo2O4–NiO
were estimated using ­N2 adsorption–desorption isotherms at
77 K. Figure 5 depicts the BET isotherms of N ­ iCo2O4 and
­NiCo2O4–NiO. All the adsorption and desorption isotherms
fall under the characteristics of type II isotherm. The specific
surface area was estimated to be 14.3 m2/g and 13.6 m2/g for
­NiCo2O4 and ­NiCo2O4–NiO respectively. Hence no obvious
change in surface area was observed with the incorporation of
NiO. Typically the formation of ­NiCo2O4–NiO can be viewed
as follows. The hydrothermal synthesis yield the nickel and
cobalt oxide precursors and the addition of urea act as the

Fig. 4  SEM (a, b) and TEM (c, d) images of ­NiCo2O4 and ­NiCo2O4–NiO prepared from a simple hydrothermal method. The inset of (c, d)
depicts the SAED pattern of the nanomaterials. e Shows the EDX image of N
­ iCo2O4–NiO

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NH3 + H2 O → NH4 + + OH− (4)

Ni2+ + 2Co2+ + 6 OH− → NiCo2 (OH)6 (5)

NiCo2 (OH)6 + 1∕2O2 → NiCo2 O4 + 3H2 O (6)

Fig. 5  Nitrogen adsorption and desorption isotherm of ­NiCo2O4 and
­NiCo2O4–NiO
reducing agent as well as the structure directing agent. The
excess ­Ni2+ was reduced to Ni upon addition of urea. Further
on calcination the nickel–cobalt oxide precursors get converted
to ­NiCo2O4 and the metallic Ni reacts with O ­ 2 to form NiO.
The reaction mechanism is given as [51]
(3)
( )
6CO NH2 2 → C3 H6 N6 + 6NH3 + 3CO2
Ni + O2 → 2NiO. (7)
The electrochemical performance N ­ iCo 2 O 4 and
­NiCo2O4–NiO was evaluated using CV and GCD tech-
niques. Figure 6a, b shows typical CV curves of ­NiCo2O4
and ­NiCo2O4–NiO in 1M KOH at the scan rate of 5 mV/s
to 80 mV/s within the potential range of 0 V–0.5 V. A pair
of well defined peaks was clearly observed at ~ 0.35 V and
~ 0.29 V during anodic and cathodic sweeps respectively
indicating the pseudocapacitance behaviour of the electrode.
The pseudocapacitance behaviour arises through the Fara-
daic redox transition of nickel and cobalt hydroxides and
oxides. The mechanism for the redox transition is given as
[39]
NiCo2 O4 + OH− ↔ NiOOH + 2CoOOH + e− (8)
CoOOH + OH− ↔ CoO2 + H2 O + e− (9)
NiO + OH− ↔ NiOOH + e− (10)
From the CV curves it is clear that the peak current of the
­NiCo2O4–NiO is much higher than ­NiCo2O4 under identical
condition. This indicates the role of secondary structure in

Fig. 6  Cyclic voltammogramm of a ­NiCo2O4 and b ­NiCo2O4–NiO in 1 M KOH solution obtained at different scan rates; c plot of i/ν1/2 versus
ν1/2; d, e shows the capacitive and diffusion contribution of ­NiCo2O4 and ­NiCo2O4–NiO respectively

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Journal of Materials Science: Materials in Electronics (2019) 30:7497–7506 7503
increasing the capacitance of the material. With increasing
scan rate the cathodic and anodic peak potential shifts to
higher and lower end respectively. In order to investigate the
charge storage mechanism of ­NiCo2O4 and ­NiCo2O4–NiO,
the kinetic analysis was performed using the CV curves
obtained at different scan rate as shown in Fig. 6. The rela-
tion between current and scan rate is given as
i = 𝜈ab
taking log in Eq. (11)
log i = b log 𝜈 + log a (12)
where a and b are adjacent values. The b value of 0.5 indi-
cates that the charge storage is diffusion controlled process
and that the value near to 1 implies that the storage mecha-
nism is by capacitive process [52]. The capacitive behaviour
includes the contribution of a small part of EDLC and larger
Faradaic reaction or pseudocapacitance. Herein the plot of
log i vs log ν yields a slope of b = 0.72 and b = 0.92 for
­NiCo2O4 and N ­ iCo2O4–NiO respectively. This indicates that
the current rises predominantly from the capacitive process.
Further the ratio of capacitive and diffusion contribution at
constant potential can be quantitatively estimated using the
equation [53]
I(V) = k1 𝜈 + k2 𝜈 1∕2 (13)
where I(V) denotes the current at specific potential V, k1ν
and k2ν ½ belongs to the capacitive and diffusive process
respectively. The equation is modified further by dividing ν½
I∕ 𝜈 1∕2 (V) = k1 𝜈 1∕2 + k2 (14)
1/2 1/2
The plot between I/ν versus ν yielded a straight line
(as shown in Fig. 6c) with a slope of 0.33 for ­NiCo2O4 and
1.84 for ­NiCo2O4–NiO respectively. It is seen that the capac-
itive contribution is higher for N
­ iCo2O4–NiO than N ­ iCo2O4
with respect to scan rate. For example the capacitive con-
tribution of ­NiCo2O4–NiO is upto 82.4% at 40 mV/s while
Fig. 7  a, b Depicts the GCD curves of N
­ iCo2O4 and ­NiCo2O4–NiO obtained at different current density
that for N
­ iCo2O4 is 69.0% at the identical scan rate (Fig. 6d,
e). Thus high capacitance can be attributed to the presence
of NiO secondary phases which improves the charge stor-
age kinetics.
The GCD studies for the ­NiCo2O4 and ­NiCo2O4–NiO
electrode were conducted to compute the specific capaci-
tance and cycling stability of the material. The study was
performed within the potential range of 0 V–0.4 V and at
(11) different current densities of 5 A/g, 4 A/g, 2 A/g, 1 A/g,
0.5 A/g and 0.25 A/g. Figure 7a, b shows the charge–dis-
charge curves of N ­ iCo2O4 and N ­ iCo2O4–NiO obtained at
different current density. All the curves show a similar trend
with a nonlinear variation of the voltage as a function of
time during charge discharge which indicates pseudocapaci-
tive behaviour of the electrode. The specific capacitance of
the electrode obtained at different current density was cal-
culated and the results are shown in Fig. 8. The specific
capacitance of the ­NiCo2O4–NiO electrode was 380 F/g,
430 F/g, 448 F/g, 490 F/g at a current density of 4 A/g,
2 A/g, 1 A/g, 0.5 A/g respectively. Similarly the specific
capacitance of the N ­ iCo2O4 electrode was found to be
125 F/g, 200 F/g, 216 F/g, 227 F/g at a current density of
5 A/g, 1 A/g, 0.5 A/g, 0.25 A/g respectively. The maximum
specific capacitance of the electrode is 227 F/g at a current
density of 0.25 A/g. The specific capacitances of both the
samples decrease with the increase of current densities as
shown in Fig. 8. This may be due to the difficulty in the
penetration and diffusion of the electrolyte under a high cur-
rent density [54, 55]. The maximum specific capacitance
of the electrode is 490 F/g at a current density of 0.5 A/g.
Table 1 illustrates the comparison on the performance of
various ­NiCo2O4 nanostructures with the present work.
The capacitance of N ­ iCo2O4–NiO nanorods were found
to be higher than the nanoplatelets [56] or microspheres
[57] as reported in the literature. However 3D nanoflow-
ers [58] exhibited high capacitance than the present work
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7504 Journal of Materials Science: Materials in Electronics (2019) 30:7497–7506

active sites leading efficient utilization of the material. Also

­NiCo2O4.Cyclic stability tests were conducted using GCD
Fig. 8  Depicts the change in specific capacitance of ­NiCo2O4 and
­NiCo2O4–NiO obtained at different current density
which may be due to the presence of three-dimensional
network providing high surface area. The incorporation of
NiO introduces impurity band effects thereby improving the
electronic conductivity resulting in effective charge transfer.
Further the nanorod like structure increases the number of
from the BET analysis, no significant change in the surface
area was observed. Hence the enhanced capacitance was
observed solely due to the presence of NiO which not only
improves the conductivity but also increases the reversible
electron transfer Faradaic reaction in the material. These
results imply that the N ­ iCo2O4–NiO electrode possesses a
high specific capacitance and a promising performance than
for both the electrodes at a current density of 5 A/g for 2000
cycles. Figure 9 shows the graph of specific capacitance
vs cycle number for both the electrodes. After 2000 cycles
the capacitance reduced from the initial value of 150 F/g to
110 F/g with a capacitance retention of 73% for ­NiCo2O4.
In the case of ­NiCo2O4–NiO the capacitance retention was
found to be 85% at the end of 2000 cycles. This indicates
the increased stability of N­ iCo2O4–NiO electrode. Also the
GCD values of the last 10 cycles was provided in the inset
of the Fig. 9 (a & b).The curves remain undistorted even
after the long period of GCD cycles. In order to understand
the charge transfer behaviour of the electrode, impedance
analysis was performed in the frequency range between 1­ 02
to ­10− 2 Hz at their open circuit potentials. Figure 10 shows
the typical Nyquist plot of N ­ iCo2O4–NiO recorded before

Table 1  Comparison on the Electrode Specific capaci- Current den- Electrolyte References

performance of ­NiCo2O4 tance (F/g) sity (A/g)
nanostructured based electrodes
NiCo2O4 nanoparticles 394 1 3 M KOH [60]
­ iCo2O4 microspheres
Dandelion Like N 372 1 2 M KOH [57]
Porous hexagonal ­NiCo2O4 nanoplates 294 1 1 M KOH [56]
3D ­NiCo2O4 nanoflowers 543 1 3 M KOH [58]
Mesoporous ­NiCo2O4 320* 0.5 6 M KOH [61]
NiCo2O4–NiO nanorods 448 1 1 M KOH This work

*Capacitance obtained after calcination at 400 °C

Fig. 9  Cyclic stability of a ­NiCo2O4 and b ­NiCo2O4 –NiO at 5 A/g and the inset shows the corresponding GCD curves of the last 10 cycles

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Journal of Materials Science: Materials in Electronics (2019) 30:7497–7506 7505

provided by the Management PSG Sons and Charities, Coimbatore

India.

Compliance with ethical standards 

Conflict of interest  The authors declare no conflict of interest.

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