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Hydrothermal Reaction Combined with a Post

Anion-Exchange Reaction of Hierarchically
Nanostructured NiCo2S4 ....

Article in New Journal of Chemistry · August 2017

DOI: 10.1039/C7NJ02379K

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A hydrothermal reaction combined with a post

anion-exchange reaction of hierarchically
Cite this: New J. Chem., 2017,
41, 10037 nanostructured NiCo2S4 for high-performance
QDSSCs and supercapacitors†
S. Srinivasa Rao, a Ikkurthi Kanaka Durga,a Nagabhushanam Kundakarla,b
Dinah Punnoose,a Chandu V. V. M. Gopi, a Araveeti Eswar Reddy,a M. Jagadeeshc
and Hee-Je Kim *a

Received 3rd July 2017,
Accepted 7th August 2017
DOI: 10.1039/c7nj02379k
rsc.li/njc
This paper proposes a novel and facile strategy to synthesize hierarchical nanostructured NiCo2S4 via a
simple hydrothermal reaction combined with a post anion-exchange reaction that was used directly as
an electrode in supercapacitor and quantum-dot sensitized solar cells. By applying the appropriate
material concentration, deposition temperature, and time, the NiCo2S4 was densely deposited over the
entire surface of the Ni foam with good adhesion. The NiCo2S4 electrode exhibited outstanding
electrochemical performance in both the applications with a high specific capacitance of 1612.95 F g1,
energy density of 56 W h kg1 at 5 A g1, good cycling stability, power conversion efficiency of 3.94%,
and Jsc of 12.27 mA cm2. The NiCo2S4 electrode exhibited almost double the output values compared
to NiCo2O4 (693.6 F g1 at 6.66 A g1 and efficiency of 1.81%) and NiCo2Se (1401.4 F g1 at 10 A g1
and efficiency of 3.86%), resulting from the excellent electrochemical performance of the NiCo2S4.
Overall the excellent performance of the fabricated electrode was attributed mainly to the highly
electrocatalytic activity, large surface area and decent conductivity of the hierarchical nanostructures of
the NiCo2S4. This study shows that the NiCo2S4 nanostructures can be applied not only in high energy
density fields, but also in high power density and energy harvesting applications.

1. Introduction magnetic, pumped hydro, flywheels, and supercapacitors (SCs).3

The detrimental long-term effects of greenhouse gas emissions
into the atmosphere, industrialization at an enormous pace,
increasing global population, and the finite supply of fossil
fuels underscore the urgency of exploring renewable energy
resources as well as energy storage, generation, and conservation
technologies.1,2 In this fast growing world, lightweight, high-
performance, environmentally friendly, safe, and long lifespan
energy storage devices are needed urgently for sustainable and
renewable power sources in the modern electronics industry. Until
now, a number of electrical energy storage (EES) technologies have
been developed for use in daily life (batteries and fuel cells) and for
industrial applications, such as compressed air, superconducting
a
School of Electrical Engineering, Pusan National University,
Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan, 46241, Republic of Korea.
E-mail: heeje@pusan.ac.kr; Fax: +82 51 513 0212; Tel: +82 51 510 2364
b
Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201,
USA
c
Department of Chemistry, Indian Institute of Technology-Tirupati,
Andhra Pradesh, 517506, India
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c7nj02379k
Li-ion batteries can be rechargeable or non-rechargeable
depending on the specific battery chemistry and both can produce
electricity from chemical energy. Typically, Li-ion batteries have
low power density, high energy densities and limited cycle lives
because of the lack of a fully reversible redox reaction during the
charge and discharge process.4,5
SCs, which are often referred to as ultracapacitors or electro-
chemical capacitors, demonstrate outstanding power density
compared to batteries, and have a higher energy density than
conventional dielectric capacitors. In addition, they have a very
long cycle life (41 000 000 cycles), ease of integration into
electronics, and simple mode of operation.6 SCs are considered
to be the ideal storage device and they generate less thermo-
chemical heat because of the simpler charge storage mechanisms
associated with them. Owing to the multiple advantages listed
above, these SCs have been used widely in memory back-up
systems, consumer electronics, energy management and industrial
power, and are expected to be found in more niche markets in the
near future.7,8 On the other hand, there are certain areas where
SCs have shortcomings or fail to meet various needs, such as low
energy density, compared to batteries. Therefore, the central issue

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017 New J. Chem., 2017, 41, 10037--10047 | 10037

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in the development of practical SCs is to identify new materials
and fabricate high energy SCs without losing the above-mentioned
benefits. Therefore, there is increasing focus on identifying a
single electrode system for both SC and quantum-dot sensitized
solar cells (QDSSCs) that would be beneficial for compact electronic
devices and smart energy storage.
In general, typical QDSSCs are composed of quantum dot
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semiconductor materials, such as CdS and CdSe sensitized as a
photoanode, a redox electrolyte consisting of the polysulfide redox
couple, and a counter electrode (CE).9,10 These QDSSCs are attractive
owing to their high absorption coefficient, hot-carrier transfer, larger
intrinsic dipole moments leading to charge separation, size-
dependent tunable band gap with quantum confinement to suit
the solar spectrum, and the generation of multiple electron carriers
under high energy excitation. Although QDSSCs have tremendous
advantages, the power conversion efficiency (PCE) is still behind
that of dye-sensitized solar cells (DSSCs) because of the high charge
transfer resistance between the CE/electrolyte and high electron
recombination occurring at the photoanode/electrolyte. In QDSSCs,
the CE plays a vital role because the bifunctional CE collects
electrons from the external circuit and reduction occurs at the CE.
Platinum has been a successful candidate for the CE in DSSC
because of its higher electron catalytic activity for the organic iodide/
triode redox electrolyte. On the other hand, in conjunction with the
polysulfide redox electrolyte, Pt and other metals, such as Au, are
not effective CEs because the physical adsorption of sulfur-
containing groups on the surface of Pt limits the surface activity
and conductivity of the electrode.11 To overcome this problem,
other efficient CE materials in conjunction of the polysulfide
electrolyte have been investigated to achieve a higher PCE and
low charge transfer resistance.
Two charge storage processes occur in SCs: a Faradaic charge
transfer process introduced by Trasatti et al. (i.e. pseudocapacitors
that employ electroactive materials of transition metal hydroxides/
oxides and their composites) and a non-Faradaic charge storage
accumulation process developed accurately by the Gouy–Chapman–
Stern model.12 Electric double layer capacitors (EDLCs) use
graphene, activated carbon, carbon nanotubes (CNTs), and carbon
aerogels to prepare active materials in SCs. Currently pseudo-
capacitors have attracted considerable attention owing to their
high specific capacitance, enhanced working potential window,
and ability to store more charge than EDLCs because of the
continuous reversible redox reactions in electroactive materials.13
Until now, numerous materials, including conducting polymers,
transition metal compounds, carbon-based materials, and single
transition metal oxides/hydroxides, have been studied extensively in
SC and QDSSC applications. Previous studies have shown that
electrodes with the appropriate network microstructures and
porosity can improve the power density and cycling stability for
SCs. Unfortunately, the inferior performance of electrode materials,
such as the meager cycling stability in conducting polymers, low
specific capacitance in carbon-based materials, high cost of RuO2,
and very low electrical conductivity in transition metal oxides, limits
their practical applications.14,15
Compared with carbon nanomaterials, the transition-metal
sulfides, such as NiSx and CoSx have received extra attention
10038 | New J. Chem., 2017, 41, 10037--10047 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
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due to their higher theoretical capacitance and multiple redox
reactions in SCs. Unfortunately, poor electrochemical performance
was observed due to their low surface area and non-porosity. In
order to address this problem, many researchers have been working
on the synthesis and design of metal sulfides with a higher surface
area to enhance the performance of SCs. Mixing metal sulfides with
low cost elements (Ni, Mn, Fe and Sn) are another interesting way of
enhancing the surface area and specific capacitance because the
introduction of mixing can lead to superior electrical conductivity.15
Among the emerging electrode materials for SCs, NiCo2O3, NiCo2Se,
and NiCo2S4 are the most promising electrode materials owing to
their high specific capacitance from the rapid and reversible redox
reactions on the active electrode surface. In particular, NiCo2S4 has
attracted recent interest due to its richer redox reactions than the
corresponding binary NiSx and CoSx, low-cost, natural abundance,
and environmental benignity. In addition, it has a major advantage
over NiCo2O4 in terms of its higher conductivity. NiCo2S4 powder is
generally synthesized by using a hydrothermal method and a slurry
is coated directly on the substrate, which seriously limits the
capacitive performance due to the increased ‘‘dead surface’’.16 An
effective way to improve the utilization of NiCo2S4 is to grow the
material directly on a conductive substrate to form an integrated
electrode for electrochemical evaluations. NiCo2S4 nanostructures
can be directly synthesized on a conductive substrate using different
growth methods, such as chemical bath deposition, solvothermal
methods, microwave-assisted methods, hydrothermal synthesis,
and the electrochemical deposition method (EDM).17–20 Among
these methods, the EDM is relatively attractive because it can grow
functional materials through complex 3D masks and be performed
at room temperature for a short growth time from water-based
electrolytes. The EDM is carried out using a three electrode system
with a counter electrode (i.e. Pt wire) and reference electrodes, such
as the standard calomel and Ag/AgCl electrode. On the other hand,
these reference electrodes are quite sensitive and expensive. More-
over, the tip of the reference electrode might be broken during the
EDM process under increased temperature.6
Based on the above consideration, this paper reports a
facile, cost-effective, and eco-friendly metal source to obtain
well-assembled porous NiCo2O4, NiCo2S4, and NiCoSe on Ni
foam using a simple hydrothermal method followed by thermal
treatment. The as-fabricated NiCo2S4 electrode produced efficient
performance in a SC and also good CE performance in a QDSSC.
Assembled in QDSSCs, the hierarchical nanostructured electrode
showed a good PCE, fill factor, Voc, and Jsc of 3.94%, 0.54, 0.58 V,
and 12.27 mA cm2, respectively. Moreover, the NiCo2S4 possessed
an enhanced specific capacitance of 1612.95 F g1 at 5 A g1 and
energy density of 56 W h kg1 and excellent cycling performance.
2. Experimental methods
2.1 Preparation of the Ni foam substrate
Prior to synthesis, the Ni foam substrate (1 cm  1 cm in
rectangular shape) was cleaned by sonication in acetone for
15 min and immersed into an HCl solution for 15 min to
remove the surface oxide layer. Finally, the Ni foam was washed

NJC
sequentially in ethanol and deionized (DI) water for 10 min
each, and dried with a hair dryer.
2.2 Fabrication of Hierarchical NiCo2O4 nanowire arrays
All the chemicals used in the experiment were of analytical
grade and used without any further purification. Hierarchical
NiCo2O4/Ni foam nanowire arrays were synthesized from a
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simple hydrothermal method, according to similar procedures
reported elsewhere. In a typical procedure, the growth solution
was prepared by mixing 8 mmol of CoCl26H2O, 4 mmol of
NiCl26H2O, and 12 mmol of urea in 60 mL of DI water to form
a clear pink solution at room temperature. Sequentially, the
mixed solution was transferred to an 80 mL Teflon-lined
stainless steel autoclave with cleaned Ni foam substrates and
heated to 120 1C for 6 h and cooled naturally to room tempera-
ture. After the Teflon-lined stainless steel autoclave was cooled
to room temperature, the NiCo2(CO3)1.5(OH)3 nanowire arrays
supported on the Ni foam were collected, washed several times
with DI water and ethanol, and treated thermally at 400 1C for
2 h to convert them to NiCo2O4.
2.3 Fabrication of NiCo2S4 nanotube arrays
The NiCo2(CO3)1.5(OH)3 nanowire arrays supported on the Ni
foam were used to prepare the NiCo2S4 nanotube arrays by an
anion-exchange reaction and used directly as the electrode for
supercapacitors. In a typical procedure, 8 mmol of Na2S was
dissolved in 60 mL of DI water and stirred for 20 min. The
solution was then transferred to an 80 mL Teflon-lined stainless
steel autoclave, followed by the addition of NiCo2(CO3)1.5(OH)3
supported on Ni foam. After cooling naturally to room temperature,
the NiCo2S4 nanotube arrays were collected and washed with DI
water and ethanol, and the sample was dried at 60 1C for 10 h.
2.4 Fabrication of NiCo2Se nanoparticles
The NiCo2Se nanoparticles on the Ni foam substrates were prepared
by hydrothermally treating the as-collected NiCo2(CO3)1.5(OH)3
nanowire arrays with Se and sodium sulfite. The selenium solution
was prepared by mixing Se (4 mmol) and sodium sulfite (8 mmol) in
60 mL of DI water. The resulting mixture with NiCo2(CO3)1.5(OH)3
was kept in an 80 mL stainless steel autoclave at 120 1C for 6 h and
dried at 60 1C for 10 h.
2.5 Electrochemical measurements
The electrochemical measurements, including electrochemical
impedance spectroscopy (EIS), cyclic voltammetry (CV), and
galvanic charge–discharge were taken using a BioLogic potentio-
stat/galvanostat/EIS analyzer (SP-150, France) at room temperature.
EIS was performed in a three-electrode glass cell setup and the
frequency range was 500 kHz to 0.1 Hz at the open-circuit potential
with an amplitude of 10 mV. The weight of the active material
on the Ni foam was acquired by measuring the electrode with a
microbalance with an accuracy of 0.01 mg and the weight was
approximately 3 to 3.5 mg cm2 for all electrodes. The galvano-
static charge–discharge was performed at 25 1C in 1 M KOH
with different current densities, such as 5, 8.3, 11.6, 15, 20 and
23.3 A g1. The specific capacitance of the electrode was
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calculated from the CV and galvanostatic discharge curves using
eqn (1) and (2).
ð vc
IðvÞdv
C¼ (1)
va mV ðVa  Vc Þ
where I(A) is the charge or discharge current, C is the specific
capacitance (F g1), V is the scan rate of the CV curve (V s1), m
is the mass of the electrode, and (Va  Vc) represents the voltage
change after a full charge or discharge.
IDt
C¼ (2)
mDV
where Dt (s) is the time for a full charge or discharge, DV is the
potential drop (V), C is the specific capacitance (F g1), and m is
the mass of the electrode. The energy density (E) and power
density (P) were calculated from the CV curves using the
following well-known formulae:
1 1000
E¼  (3)
2CðDVÞ2 3600
E iDV
P¼ ¼  1000 (4)
t 2m
where C is the capacitance (F g1), DV is the potential window
(V), and t is the discharge time (s).
2.6 Material characterization
The product was characterized by X-ray diffraction (XRD,
D/Maz-2400, Rigaku), X-ray photoelectron spectroscopy (XPS),
high-resolution scanning electron microscopy (HR-SEM) and
transmission electron microscopy (TEM) at the Busan KBSI to
identify the microstructure, surface morphology and chemical
composition. The powder XRD patterns were obtained using Cu
Ka radiation at 40 kV and 30 mA. Photocurrent density–voltage
( J–V) and EIS were performed using an ABET technology (USA)
solar simulator under 1 Sun illumination (100 mW cm2, AM
1.5G). Tafel polarization measurements were analyzed using
symmetric dummy cells under dark conditions; the detailed
method for the fabrication of this symmetrical cell is reported
elsewhere. The surface roughness of the prepared products was
explored using atomic force microscopy (JPK NanoWizard II
AFM, JPK Instruments, Berlin, Germany) with a scan rate of
0.8 Hz in contact mode.
3. Results and discussion
3.1 Synthesis and characterization of the active material
electrodes
Fig. 1 presents a schematic diagram of the synthesis process
of NiCo2O4, NiCo2S4, and NiCo2Se on Ni foam via a one-step
and/or two-step process. The Ni foam substrate was suitable for
growing the active material electrodes using a hydrothermal
method owing to its high conductivity and flexible. First, the
NiCo2(CO3)1.5(OH)3 nanowire arrays were fabricated on an Ni
foam substrate via a hydrothermal method. After thermal
treatment of the grown NiCo2(CO3)1.5(OH)3 at 400 1C for 2 h,
New J. Chem., 2017, 41, 10037--10047 | 10039

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the NiCo2(CO3)1.5(OH)3 was converted to NiCo2O4 by dehydration.
Under the next conditions, the initially prepared NiCo2(CO3)1.5(OH)3
nanowire arrays were converted hydrothermally to a NiCo2S4
hierarchical nanostructure and NiCo2Se nanotubes by reacting
with a Na2S and selenium solution. When Na2S reacts with
NiCo2(CO3)1.5(OH)3, the S2 ions in the solution exchange with
Co32 and OH anions to form a complete array structure of
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NiCo2S4 at the surface of the nanowire. The NiCo2O4 (NCO),
NiCo2Se (NCSe) and NiCo2S4 (NCS) were distributed uniformly on
the Ni foam without any gaps or voids, which led to a black color.
The as-synthesized NCS on the Ni foam was confirmed by
XRD and XPS. Fig. 2a shows the XRD patterns of pure NiCo2S4
and the diffraction peaks were indexed to the cubic type of
NiCo2S4 (JCPDS card no. 43-1477), indicating the successful
formation of the NiCo2S4 phase. The XRD patterns of NiCo2O4
and NiCo2Se are shown in the ESI† (Fig. S1). XPS was used to
examine the surface species, chemical composition, and surface
electronic states of NiCo2S4, and the results are presented in
Fig. 2(b)–(e). As shown in the XPS survey spectrum of Fig. 2b, the
S2p, C1s, O1s, Co2p, Ni2p3, and Na1s peaks originate from
NiCo2S4 and the following conclusions were drawn. (1) As shown
in Fig. 2e, the S2p spectrum can be divided into two main peaks,
where the components at 162.6 eV and 163.3 eV were assigned to
sulfur ion low coordination and a metal sulfur bond on the
surface. (2) Fig. 2c and d shows the XPS spectra of Ni2p and Co2p
of the NiCo2S4/Ni foam. In the Ni2p film, the two spectral curves
commonly exhibited two spin–orbit characteristics of Ni2+ and
Ni3+ with a shake-up satellite peak which is indicated by ‘‘Sat’’.
For the Ni2p curves of Fig. 2c, the peaks at 855.9 eV and 875.0 eV
were indexed to Ni3+ and Ni2+. (3) Two types of Co species were
observed in the high-resolution spectra of Co2p. The peak at
797.3 eV was assigned to Co2+ and Co2p1/2, whereas the peak at
781.3 eV was indexed to Co3+ and corresponds to the Co2p3/2
region.21 On the other hand, Co3+/Co2+ coexist in the NiCo2S4 film
and these values matched with the Co2p and Ni2p spectra in
NiCo2S4. In addition, the presence of Ni3+/Ni2+ and Co3+/Co2+
Fig. 1 Schematic illustration of the formation process of the NiCo2O4,
NiCo2Se, and NiCo2S4 films on the Ni foam substrate.
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cations in the NiCo2S4 provides abundant active sites for energy
storage.22,23
Fig. 3 shows HR-SEM images of the NCO, NCSe, and NCS
materials deposited on Ni foam substrates. A closer examination
of Fig. 3a–c showed that the NCO, NCSe, and NCS materials
covered the Ni foam substrate uniformly while comprehensively
perpetuating the 3D grid structure. The SEM images in Fig. 3a1
and a2 show that NCO consists of numerous slim nanowires
arranged vertically on the substrates with an extremely long
length of approximately 100–200 nm to form homogeneous
nanowire arrays. After adding Se into the mixture, the surface
morphology of NCO was altered considerably and commutated
from homogeneous nanowire arrays to a nanotube like morphology.
From a wide investigation, the NCSe nanowires were hollow
internally and abundant pores were located on the substrate,
confirming the fabrication of the nanotube arrays. The sulfide
particles reacted with NiCo2(CO3)1.5(OH)3 over the entire surface
(Fig. 3c1). Under the growth conditions, the NCS was entrapped
uniformly with a hierarchical nanostructure and showed higher
adhesion on the Ni foam substrate. The flexibility, strong adhesion
and inter connected arrangement of the NCS film will enhance the
electrochemical stability during charge/discharge cycling. In
addition, it can provide high accessibility for electrolyte ions
into the electrode to reduce the diffusive path length of the ions.
3.2 Electrochemical performances of the NCO, NCSe and NCS
nanoelectrodes
To test the feasibility for pseudocapacitors, the electrochemical
characteristics of the as-prepared NCO, NCSe, and NCS/Ni foam
were examined by cyclic voltammetry and galvanostatic charge–
discharge measurements in a three electrode cell using Pt and
Ag/AgCl as the counter and reference electrode, respectively, in
a freshly prepared 1 M KOH aqueous solution. In addition, the
electrochemical properties of the pure Ni foam without an
electroactive material were also observed and showed extremely
small area surrounded by CV curves at 50 mV s1. The results
for the pure Ni foam suggest that the specific capacitance
contribution from the annealed Ni foam is negligible.17 The
curves clearly show a pair of redox peaks, indicating the
electrochemical performance of the electrodes resulting from
pseudocapacitive behavior that occurs by the adsorption of
electrolyte ions onto the surface of the electroactive materials
during the reversible reaction. The distinct redox peaks in NCO,
NCSe, and NCS can be attributed to the reversible redox
reactions of the Co3+/Co4+, Co2+/Co3+, and Ni2+/Ni3+ transition
based on the following equation.24
NiCo2S4 + 2OH = NiS4–2xOH + 2CoSxOH + 2e
CoSxOH + OH = CoSxO + H2O + e
In the CV results, the NCS exhibited the maximum, covering the
typical oxidation and reduction peaks. In addition, the CV
curves of the NCS presented a much larger integral area than
those of the NCO and NCSe electrodes, indicating the larger
specific capacitance of the NCS electrode.
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Fig. 2 (a) XRD and X-ray photoelectron spectroscopy (XPS) of (b) NiCo2S4, (c) Ni2p, (d) Co2p, and (e) S2p of the as-fabricated NiCo2S4 on the Ni foam substrate.

Fig. 3 HR-SEM images of the NCO (a), NCSe (b), and NCS (c) films deposited on Ni foam substrates. (a–c) Low-magnification and (a1, a2, b1, b2, c1 and
c2) high-magnification images.

Fig. 4c shows the CV curves for the NCS electrode in the peaks shifted, which could be due to the increase in internal
potential window of 0.1 to 0.7 V at different scan rates. With an resistance in the electroactive material.25 In addition, the NCS
increasing scan rate, the position of the oxidation and reduction electrode exhibited no obvious deviation despite the oxidation

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Fig. 4 Electrochemical characteristics of the prepared thin films on the Ni foam substrate: (a) CV curves of the NCO, NCSe and NCS at a scan rate of
20 mV s1 and (b) their oxidation and reduction current values. (c) CV curves of the NCS electrode at various scan rates of 5 to 40 mV s1, and
(d) interrelationship between anodic and cathodic peak currents and scan rates for the redox peaks of the NCS electrode.

peaks moving positively and the reduction peaks moving
negatively with increasing scan rates, which is mostly interrelated
to the internal resistance of the electrode. On the other hand, the
specific capacitance of the device decreased with an increasing
scan rate ranging from 5 to 40 mV s1. This was attributed to the
limited diffusion rate of the electrolyte and charge transfer, which
is not fast enough to satisfy the electrochemical reactions of the
NCS electrode material.26,27 Fig. 4d shows the relationship
between the anodic and cathodic peak currents as a function of
the sweep rates obtained from the experimental data in Fig. 4c.
These results emphasize that the anodic and cathodic peak
currents show a linear dependence on the square root of the
scan rate. These anodic and cathodic current values with respect
to the scan rate are provided in the ESI† (Table S1). At a low scan
rate, the NCS electrode performed efficiently because the ions
from the KOH electrolyte have sufficient time to utilize both the
outer and inner surface of the electrode. At a high scan rate,
however, the area occupied by ions from KOH decreased due to a
decrease in the diffusive path length.
EIS of the NCS thin film electrodes before and after 1000
cycles were also measured to provide kinetic and mechanistic
information on the electroactive materials. The Nyquist plots in
Fig. 5a were obtained over the frequency range of 0.1 Hz–100 kHz,
in a 1 M KOH electrolyte. Both plots were semi-circular in the
high frequency region and exhibited a deep-rising straight
line in the low frequency region, which were related to the
charge-transfer resistance and diffusion of electrolyte ions
within the structure of the prepared electrodes. HR-SEM
showed several accumulated sulfide particles on the external
surface of the NCS/Ni foam electrode, which may increase the
contact with the electrolyte. Moreover, the interaction between
the NCS electrode and electrolyte is strong and the outer surface
of the electrode enhances the diffusion of the electrolyte, which
facilitates the interaction of NCS with the electrolyte.28 In the
equivalent circuit, the internal resistance (Rs, i.e. the sum of the
intrinsic resistance of the electroactive material, ionic resistance
of the electrolyte, and contact resistance at the electroactive
material/NCS electrode interface) was connected in series with
the charge transfer resistance (Rct), Warburg impedance (Zw), and
constant phase element (CPE), respectively. The size of the semi-
circle, which is equal to Rct, was clearly the same for both curves
(1 O for before and 1.2 O for after 1000 cycles) due to the faster
electrolyte diffusion into the NCS nanowires. These lower Rct
values for the NCS are favorable for efficient electrochemical
properties. The slope of the straight line and Rs values were
obviously lower for the NCS compared to those of previous
studies, which may be caused by the slight fading of the
capacitance. The EIS experimental data were also analyzed using
the Bode plot to show the maximum and similar phase angle of
before and after 1000 cycles for the NCS-based electrodes, which
is close to the phase angle of B901 for ideal capacitive behavior.
Based on these results, the specific capacitance of the NCS

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Fig. 5 (a and b) Electrochemical impedance spectroscopy and Bode plot stability of the NCS electrode before and after 1000 cycles. (c) Schematic
diagram of the NCS electrode and their electron and ion transport pathways, the electrolyte ions in KOH solution can diffuse into/out of the inner side of
the hierarchical nanostructure.
electrodes can also be calculated from the EIS data using the
well-known formula (5), as follows:
Csp = [1/(2pf Z00 m)] F g1
where Z00 is the imaginary value of the impedance, 2pf is the
angular frequency, and m is the mass of the active material.
Fig. 5c shows a schematic diagram of the as-prepared NCS on
the Ni foam via an anion-exchange reaction for electrochemical
energy storage. As shown in Fig. 5c, it can facilitate the rapid
penetration, high surface roughness, and diffusion of OH ions
(electrolyte ions) and e (electrons). The accumulated NCS
nanowires on the Ni foam substrate increase the contact area
between the active material and electrolyte ions and the good
adhesion, which leads to the higher diffusion of electrolyte ions
from the surface of the NCS. As a result, in the NCS electrode
with a large surface area, intrinsic electrical conductivity builds
up rapid pathways for electron transport, the high porosity
eliminates the use of conductive additives, and the polymer
binders can be favorable for binder-free high performance
energy storage devices.
Fig. 6a–c show GCD curves of the NCO, NCSe and NCS thin
film electrodes at a current density of 6.66 A g1. The specific
capacitance (Csp), which indicates the electrosorption rate and
capacity of the sample, was calculated from the galvanostatic
discharge curves using eqn (2). A significantly higher charge
storage capacity with NCS (1560.81 F g1 at 6.66 A g1) was
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observed compared to that of the NCO (693.6 F g1) and NCSe
(1401.4 F g1). In addition, the internal resistance of the NCS/Ni
foam was reduced considerably compared to that of the NCO
(5)
and NCSe-based film. The intended Csp decreased gradually
with increasing applied current density. At a high current
density, the ions that access only the outer surface are used
for the charge storage due to the limited accessible time from
the electrolyte while at a low current density, the ions from the
electrolyte have adequate time to adsorb/desorb completely at
the outer and inner surfaces of the active material.29,30 From
these results, the observed Csp values were greater at a low
current density (as shown in Fig. 5d) and vice versa, which
shows that the electrolyte ions cannot penetrate the micropores
at high current densities or high frequencies. The better super-
capacitive performance of the NCS was attributed to the unique
nanotube morphology and outstanding capability of the NCS
electroactive material. The merits of the as-prepared NCS arrays
on Ni foam are as follows: (1) The hierarchical nanostructured
morphology can effectively alleviate the volume change compared
to nanowires during the ion insertion/desertion process. (2) These
hierarchical nanostructured materials have a much high specific
surface area, resulting in improved cycling stability that can
provide more electroactive sites for electrochemical storage. (3)
The NCS electroactive material possesses higher conductivity
than NCO and NCSe, which can facilitate a pathway for electron
transport along the nanotube wall, as shown schematically
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Fig. 6 Galvanostatic charge–discharge curves of the (a) NCO, (b) NCSe, and (c) NCS at a current density of 6.66 A g1. (d) GCD curves of NCS nanotube
arrays on the Ni foam with different current densities. (e) Specific capacitance (F g1) as a function of the different current densities of 5, 8, 11.6, 15, 20,
23.3, 26.5, and 30 A g1. (f) Cycling performance of the NCS electrode at a current density of 23.33 A g1.

in Fig. 5c. Furthermore, the NCS electrode which obtains the
highest specific capacitance values even at an extremely high
current density as shown in Fig. S3 in the ESI† (1066.66 F g1 at
26.66 A g1, 1020 F g1 at 30 A g1 and 1005.55 F g1 at 33.33 A g1)
possesses the biggest specific surface area compared to the other
two electrodes.
The cycling stability is another key performance that determines
the practical applications of electroactive materials for super-
capacitors. Fig. 6f shows the first 20 cycles for the NCS decorated
on the Ni foam substrates in a 1 M KOH solution within the
potential range of 0 to 0.5 V at a current density of 23.33 A g1. As
shown in Fig. 6f, the first 20 cycles exhibited a symmetrical shape
and a similar time response and potential without any disparity
in the cycles, which indicates a highly reversible and fast current–
voltage response during the charge–discharge process. The
specific capacitance of the NCS electrode increased slightly after
the first cycle due to activation of the NCS electrode caused by
the increased contact area between the NCS and the KOH
during cycling. When a current density of 23.33 A g1 was
applied, a specific capacitance of 1165.74, 1140.87, 1101 and
1004.15 F g1 was observed for the first, 600, 1200 and 2000 cycle,
indicating a capacitance retention of 87.1% after 2000 charge
discharge cycles, confirming that the NCS has an excellent cycling
stability. After the cycling process, the surface morphology and the
observation of Ni, Co, and S from HR-SEM were well retained.
Such efficient electrodes, structural stability, and morphology

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Fig. 7 Photographic images of the NCS electrodes on the Ni foam substrate under a normal and bending position in a three-electrode cell system in 1 M
KOH aqueous solution.

can be attributed to the large surface area, strong adhesion on
the substrate, and the hierarchical nature of the NCS/Ni foam.
To examine its potential as a flexible pseudocapacitive
electrode, the electrochemical characteristics of the as-prepared
NCS/Ni foam were investigated by CV under normal and bending
conditions in a three electrode cell using a freshly-prepared 1 M
KOH solution. To prepare the NCS electrode for the bending test,
the NCS electrode was bent carefully up to a 1801 angle. Fig. 7a
and b present photographic images of the normal and bending
position in the three electrode cell system. As shown in the CV
curves, there was no clear change in the redox current and a
negligible change was observed in the oxidation current under
normal and bending conditions. This indicates that the bending
of the NCS/Ni foam electrode does not influence the Faradaic
redox reactions in the active material. Moreover, the specific
capacitance under the normal and bending position for the NCS
electrode was calculated and showed identical charge–discharge
time behavior at a current density of 16.66 A g1. As a result, the
NCS on the Ni foam showed excellent mechanical stability as a
flexible pseudocapacitive electrode for efficient energy storage
device applications.
The corresponding supercapacitor electrode (NCS) was also
analyzed in QDSSCs using a polysulfide redox electrolyte. The
NICo2S4 nanotube arrays were coated on fluorine-doped tin

Fig. 8 (a) Comparison of the current density–voltage curves of NCO, NCSe and NCS counter electrodes using the TiO2/CdS/CdSe/ZnS photoanodes.
(b) Tafel polarization curves measured using a symmetrical cell with two identical electrodes and (c) schematic view of quantum dot sensitized solar cells
based on different counter electrodes and the polysulfide redox electrolyte.

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Paper
Table 1 Galvanostatic charge discharge and photovoltaic parameters
extracted from J–V curves of NCO, NCSe and NCS CEs and TiO2/CdS/
CdSe/ZnS photoanodes
Sample’s name NCO NCSe NCS
1
Cs (F g ) 693.6 1401.4 1612.95
E.D (W h kg1) 24.08 48.65 56
PCE (%) 1.81 3.86 3.94
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FF 0.53 0.56 0.54
Voc (V) 0.64 0.58 0.58
Jsc (mA cm2) 5.20 11.56 12.27
oxide (FTO) substrates and used as a counter electrode in QDSSCs.
The QDSSCs were fabricated by sandwiching a quantum-dot-
sensitized TiO2 photoanode (TiO2 prepared by using the doctor-
blade method, and CdS, CdSe, and ZnS sensitized on TiO2 by
using the successive ionic layer absorption and reaction
method) and NCS CE using a 50 mm hot melt sealing sheet
(double sheet of SX 1170-25, Solaronix).31–35 Fig. 8a and Table 1
present the resulting photocurrent–voltage (J–V) curves and the
corresponding FF, Jsc, PCE, and Voc. In previous reports, the
QDSSCs with Pt, CuS, and NiS CEs showed a poor PCE of 1.64%,
2.73%, and 1.82%, respectively.9,34 The poor PCE of these CEs
was attributed to (1) negative corrosion potential (0.024 V in
Tafel polarization), (2) higher anodic slope in the Tafel plot than
the cathodic slope, and (3) lower exchange current density. In
this study, the NCS CE in the QDSSCs showed higher Jsc values
of 12.18 mA cm2 and exhibited a better PCE of 4.56%, respectively,
due to the greater catalytic activity, higher electron transport
resistance through the photoanode, and lower series resistance
of the cell.
Tafel polarization measurements were performed in an
aqueous S2/Sn2 redox couple solution in symmetrical dummy
cells prepared with two identical CEs to examine the interfacial
charge-transfer properties of the NCO, NCSe, and NCS. Fig. 8b
shows the Tafel measurements of the logarithmic current density
across the range of applied overpotentials: NCS 4 NCSe 4 NCO.
The electrocatalytic ability of an electrode is related directly to the
exchange current density (Jo) and can be calculated using eqn (4),
which indicates the high electrocatalytic activity of NCS/FTO
compared to the NCO and NCSe CEs toward the polysulfide
reduction. The substantial progress in PCE can be elucidated
from the following factors: (1) the formation of NiCo2S4 improved
the catalytic activity significantly; (2) the incorporation of S2 ions
via an anion-exchange reaction greatly enhanced the interface
adhesion between the active material and FTO, leading to excel-
lent mechanical and chemical stability in the S2/Sn2 redox
couple; and (3) the fabrication of NiCo2S4 with a large surface
area, conductivity, and sufficient infiltration of the electrolyte into
the counter electrode was found to be significant.
4. Conclusions
In summary, an NCS hierarchical nanostructure was prepared
via a facile hydrothermal reaction combined with a post anion-
exchange reaction for a cost-effective pseudocapacitor and as a
counter electrode in quantum-dot sensitized solar cells (QDSSCs).
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The hybrid electrode showed rapid electron transport, diffusion
of electrolyte ions and good structural stability, which leads to
excellent electrochemical characteristics due to the superior
capability of the NCS electroactive material and the specific
hierarchical nanostructure. The conductivity was amplified by
an anion-exchange reaction with NiCo2(Co3)1.5(OH)3, which
produced a very low Rs (0.93 O) and Rce (1.23 O). The QDSSCs
with the NCS CE showed a higher PCE of 3.94% with a Jsc of
12.27 mA cm2, Voc of 0.58, and FF of 0.54. This PCE is greater
than the values obtained for NCO and NCSe (1.81% and 3.86%)
due to its low electron transfer resistance toward the aqueous
polysulfide electrolyte and large surface area. Moreover, the NCS
electrode exhibited a higher specific capacitance of 1612.95 F g1 at
5 A g1, energy density of 56 W h kg1, good cycling stability with
only 3% loss after 1000 cycles at 6 A g1 in a 1 M KOH electrolyte
solution, and even a high capacitance of 1005.55 F g1 at 33.33A g1.
This low-cost and facile strategy of NCS on Ni foam is desirable in
applications of advanced electrochemical electrode materials
for flexible electronics and energy storage applications.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This research was supported by the Basic Research Laboratory
through the National Research Foundation of Korea funded
by the Ministry of Science, ICT and Future Planning (NRF-
2015R1A4A1041584). We also thank KBSI for HR-SEM, EDX,
XRD and XPS measurements.
References
1 D. Choi, G. E. Blomgren and P. N. Kumta, Adv. Mater., 2006,
18, 1178–1182.
2 C. Liu, F. Li, L. P. Ma and H. M. Cheng, Adv. Mater., 2010,
22, E28–E62.
3 B. Xu, D. Qian, Z. Y. Wang and Y. S. Meng, Mater. Sci. Eng.,
R, 2012, 73, 51–66.
4 Q. Q. Xiong, J. P. Tu, X. H. Xia, X. Y. Zhao, C. D. Gu and
X. L. Wang, Nanoscale, 2013, 5, 7906–7912.
5 P. Simon and Y. Gogotsi, Nat. Mater., 2008, 7, 845–854.
6 G. Nagaraju, G. S. R. Raju, Y. Hwan and J. S. Yu, Nanoscale,
2016, 8, 812–825.
7 G. Wang, L. Zhang and J. Zhang, Chem. Soc. Rev., 2011, 41,
797–828.
8 K. Naio, S. Ishimoto, J. Miyamoto and W. Naoi, Energy
Environ. Sci., 2012, 5, 9363–9373.
9 H. J. Kim, S. M. Suh, S. S. Rao, D. Punnoose, C. V. Tulasivarma,
C. V. V. M. Gopi, N. Kundakarla, S. Ravi and I. K. Durga,
J. Electroanal. Chem., 2016, 777, 123–132.
10 H. J. Kim, J. H. Kim, I. K. Durga, D. Punnoose, N. Kundakarla,
A. E. Reddy and S. S. Rao, New J. Chem., 2016, 40, 9176–9186.

NJC
11 S. S. Rao, I. K. Durga, T. S. Kang, S. K. Kim, D. Punnoose,
C. V. V. M. Gopi, A. E. Reddy, T. N. V. Krishna and H. J. Kim,
Dalton Trans., 2016, 45, 3450–3463.
12 K. V. Sankar and R. K. Selvan, RSC Adv., 2014, 4, 17555–17566.
13 Y. Cheng, H. Zhang, S. Lu, V. V. Chakrapani and J. Liu,
Nanoscale, 2013, 5, 1067–1073.
14 J. Joseph, R. Rajagopalan, S. S. Anoop, V. Amruthalakshmi,
Published on 08 August 2017. Downloaded by PUSAN NATIONAL UNIVERSITY on 04/10/2017 08:20:38.
A. Ajay, S. V. Nair and A. Balakrishnan, RSC Adv., 2014, 4,
39378–39385.
15 J. Huang, P. Xu, D. Cao, X. Zhou, S. Yang, Y. Li and G. Wang,
J. Power Sources, 2014, 246, 371–376.
16 S. Zhang and N. Pan, Adv. Energy Mater., 2015, 5, 1401–1407.
17 T. Wang, Q. Le, G. Zhang, S. Zhu, B. Guan, J. Zhang, S. Xing
and Y. Zhang, Electrochim. Acta, 2016, 211, 627–635.
18 H. Chen, X. L. Liu, J. M. Zhang, F. Dong and Y. X. Zhang,
Ceram. Int., 2016, 42, 8909–8914.
19 X. Liu, S. Shi, Q. Xiong, L. Li, Y. Zhang, H. Tang, C. Gu, X. Wang
and J. Tu, ACS Appl. Mater. Interfaces, 2013, 5, 8790–8795.
20 X. Cai, X. Shen, L. Ma, Z. Ji, C. Xu and A. Yuan, Chem. Eng. J.,
2015, 268, 251–260.
21 D. Li, Y. Gang and C. Pan, Sci. Rep., 2016, 6(29788), 1–7.
22 H. Chen, J. Jiang, L. Zhang, H. Wan, T. Qi and D. Xia,
Nanoscale, 2013, 5, 8879–8883.
23 J. Pu, F. Cui, S. Chu, T. Wang, E. Sheng and Z. Wang, ACS
Sustainable Chem. Eng., 2014, 2, 809–815.
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
View publication stats
View Article Online
Paper
24 L. Mei, T. Yang, C. Xu, M. Zhang, L. Chen, Q. Li and
T. Wang, Nano Energy, 2014, 3, 36–45.
25 H. Xia, D. Zhu, Z. Luo, Y. Yu, X. Shi, G. Yuan and J. Xie, Sci.
Rep., 2013, 3(2978), 1–7.
26 W. F. Wei, X. W. Cui, W. X. Chen and D. G. Ivey, J. Phys.
Chem. C, 2008, 112, 15075–15083.
27 C. H. Tang, Z. Tang and H. Gong, J. Electrochem. Soc., 2012,
159, A651–A656.
28 H. Q. Wang, Z. S. Li, Y. G. Huang, Q. Y. Li and X. Y. Wang,
J. Mater. Chem., 2010, 20, 3883–3889.
29 M. D. Stoller and R. S. Ruoff, Energy Environ. Sci., 2010, 3,
1294–1301.
30 M. H. Naveen, K. Shim, Md. S. A. Hossain, J. H. Kim and
Y. B. Shim, Adv. Energy Mater., 2016, 1602002, 1–9.
31 S. S. Rao, I. K. Durga, C. V. Tulasivarma, D. Punnoose,
S. K. Kim and H. J. Kim, Org. Electron., 2015, 26, 200–207.
32 H. J. Kim, J. H. Kim, CH. S. S. Pavan Kumar, D. Punnoose,
S. K. Kim, C. V. V. M. Gopi and S. S. Rao, J. Electroanal.
Chem., 2015, 739, 20–27.
33 N. Kundakarla, S. Lindeman, M. H. Rahman and
M. D. Ryan, Inorg. Chem., 2016, 55(5), 2070–2075.
34 S. S. Rao, D. Punnoose, S. K. Kim and H. J. Kim, Electron.
Mater. Lett., 2015, 11, 485–493.
35 S. Ruhle, M. Shalom and A. Zaban, ChemPhysChem, 2010,
11, 2290–2304.
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