Influence of substrate temperature on electrochemical supercapacitive perfor-
mance of spray deposited nickel oxide thin films

Abhijit A. Yadav, U.J. Chavan

PII: S1572-6657(16)30526-4
DOI: doi: 10.1016/j.jelechem.2016.10.006
Reference: JEAC 2873

To appear in: Journal of Electroanalytical Chemistry

Received date: 7 September 2016

Revised date: 1 October 2016
Accepted date: 4 October 2016

Please cite this article as: Abhijit A. Yadav, U.J. Chavan, Inuence of substrate tempera-
ture on electrochemical supercapacitive performance of spray deposited nickel oxide thin
lms, Journal of Electroanalytical Chemistry (2016), doi: 10.1016/j.jelechem.2016.10.006

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 ACCEPTED MANUSCRIPT
Influence of substrate temperature on electrochemical supercapacitive
performance of spray deposited nickel oxide thin films
Abhijit A. Yadav*, U.J. Chavan
Thin Film Physics Laboratory, Department of Physics, Electronics and Photonics,

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Rajarshi Shahu Mahavidyalaya, Latur (Autonomous), 413512, Maharashtra, India

Abstract

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Nickel oxide (NiO) has been considered widely as an electrochemical capacitor or supercapacitor
electrode material. NiO thin films are successfully deposited at various substrate temperatures.

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Influence of substrate temperature on various physical and electrochemical properties has been
studied. X-ray diffraction analysis confirms cubic phase of polycrystalline nickel oxide. SEM

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images show porous surface having inhomogeneous randomly shaped heaps. Optical band gap
energy is found to be in the range of 3.04-3.28 eV. Electrical resistivity confirms the
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semiconducting behavior of NiO with room temperature activation energies 0.30-0.38 eV.
Electrochemical characterization is carried out by testing the NiO electrodes for cyclic
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voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy.

Specific capacitance of 405 Fg-1 at the scan rate of 5 mVs-1 is observed. Galvanostatic charge-
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discharge study confirmed the pseudocapacitive nature. Furthermore, the specific capacitance of the
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NiO can still keep a good retention of 92.10% after 1000 cycles at 1 Ag-1, demonstrating the
outstanding long-term electrochemical stability. This work offers useful reference for
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supercapacitor applications in the future.

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Keywords: Spray pyrolysis; NiO thin film; Electrical resistivity; Supercapacitor; Electrochemical
impedance spectroscopy;

*Corresponding author: aay_physics@yahoo.co.in,

Phone: +919975213852 Fax: +912382253645
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1. Introduction
In recent years, the interest in energy storage devices has been increased due to energy
catastrophe and environmental concerns. Problem of energy crisis can be minimized by developing
efficient energy storage devices such as batteries, fuel cells and supercapacitors. Among these, the
electrochemical supercapacitor is most proficient energy storage device with high power and

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energy density along with good cycle stability. Electrochemical supercapacitors can fill the gap
between the battery and conventional capacitors with high power density than batteries and high

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energy density than conventional capacitors [1-2]. Supercapacitors are broadly divided into two
groups; namely electric double layer capacitor (EDLC) and pseudocapacitor [3-6]. EDLCs store
charges by forming an electric double layer at the electrolyte-electrode interface. EDLCs are

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mainly composed of carbon materials such as activated carbons, carbon aerogel, carbon nanotubes
and recently graphene. Pseudocapacitors are built by conducting polymers and metal oxides. The
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amalgamation of two electrodes one from the electric double layer and other from pseudocapacitors
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gives hybrid capacitors [7-9].
It is observed that the pseudocapacitors show high specific capacitance as compared to
EDLCs because of the charges accumulated by faradaic reactions [10]. The challenge for
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researchers is the cost efficient supercapacitor with superior performance. Many researchers are
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developing environment-friendly, cost-effective and efficient supercapacitors using different

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materials. Transition metal oxides show a high theoretical capacitance and also they are
inexpensive with high abundance and low toxicity [11-12]. Ruthenium oxide in the aqueous acidic
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electrolyte gives remarkable electrochemical performance. But its toxic nature and high cost limits
the large-scale application [13-14]. Other transition metal oxides used are manganese oxide, cobalt
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oxide, nickel oxide, tin oxide and ferrous oxide. Out of these, nickel oxide has shown good
electrochemical performance [15-17]. NiO is a stable semiconductor having wide band gap in the
range of 3-4 eV with p-type conductivity [18]. The resistivity of stoichiometric NiO is of the order
of 1013 cm at room temperature [19]. Resistivity of NiO can be lowered by doping with
monovalent ions [20]. There are various applications of NiO thin films together with LCD, LED,
memory devices and in energy conversion systems such as solar cells, Li-ion batteries and
supercapacitors [15, 19-20]. There are number of methods to synthesize NiO thin films, generally
physical vapor deposition, magnetron sputtering, electron beam evaporation, electrodeposition,
spray pyrolysis, chemical bath deposition, chemical vapor deposition, SILAR, and dip coating are
used [21]. Spray pyrolysis is generally preferred because of its advantages such as low cost,
possibility for large area deposition; it does not require vacuum and much more [22]. Now a day,
the spray pyrolysis technique is largely applied for deposition of metal oxides with high
transparency [23-25]. Undoped and lithium doped nickel oxide films have been prepared onto
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quartz and alumina substrates at high substrate temperature (600C) by Garduno et al. [26]. It is
observed that pure NiO thin films have electrical resistivity of the order of 106 cm and after the
doping of Li in the NiO thin films there is drop in resistivity to 102 cm. Different Ni sources are
used for the preparation of nickel oxide thin films [25-27].
Patil et al. [28] have reported the specific capacitance of 167 Fg-1 in 2M KOH electrolyte

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for chemically deposited nanocrystalline NiO thin films. Porous nickel oxide thin films were
synthesized by chemical bath deposition technique with a specific capacitance of 127 Fg-1 in NaOH

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electrolyte and 69.8 Fg-1 in KOH electrolyte [29]. Zheng and coworkers [30] have synthesized NiO

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by hydrothermal method with specific capacitance of 137.7 Fg-1 at the current density of 0.2 Ag-1 in
the potential window of 00.46 V in 2M KOH electrolyte. From these and other [15-17] studies, it

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is well understood that NiO is the most advantageous material for the supercapacitor applications.
In the present study, the influence of substrate temperature on various physical and electrochemical
properties of NiO thin films is studied. N
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2. Experimental
For synthesis of NiO thin films nickel (II) chloride hexahydrate is used as a starting
material. The 0.5M nickel chloride hexahydrate is dissolved in double distilled water to prepare
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precursor solution. Then an equal amount of propan-2-ol is added to spray solution just before
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starting the spray. Spray solution is sprayed in fine droplets onto preheated glass substrates using
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computerized spray pyrolysis technique discussed elsewhere [31]. Distance between spray nozzle
and substrate is kept constant at 30 cm. Spray rate employed is 3 mlmin-1. Substrate temperature is
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varied from 425-500C at the interval of 25C, to produce NO425, NO450, NO475 and NO500
samples of NiO thin films, respectively.
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NiO thin films deposited at different substrate temperatures are used for characterization.
Structural properties are studied by X-Ray Diffraction using a Bruker D8 advance X-ray
diffractometer with Cu-K ( = 1.5406) radiations for 2 values in the range of 10-90. Scanning
electron microscopy analysis is carried out through JEOL-JSM-6360A analytical scanning electron
microscope. Optical band gap of NiO thin films is estimated by recording absorption spectra in the
wavelength range 350-1100 nm. Electrical resistivity is measured at room temperature by well-
known DC two point probe method. Further, the supercapacitive performance of NiO thin films
was studied by the electrochemical analyzer supplied by CH instruments. Cyclic voltammetry is
carried out in potential range 0.15 to 0.55 V in 2M aqueous KOH electrolyte.
3. Results and discussion
Thermal decomposition of the fine droplets of aqueous solution of nickel chloride on the
glass substrate results in the formation of NiO. The possible chemical reaction is as follows:
NiCl26H2O NiO + 2HCl + 5H2O (1)
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Similar type of reaction has been reported earlier for NiO thin films by Sharma et al. [32]. Film
thickness is calculated by using gravimetric weight difference method by considering the bulk
density of NiO ( = 6.67 g/cm). Variation of film thickness with substrate temperature for spray
deposited NiO thin films is shown in Fig. 1. Relatively higher thickness is found to be 350nm for
NO450. It is seen that the film thickness increases with increasing substrate temperature from

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425C to 450C, attains terminal value for NO450 (350 nm), beyond which it decreases. This can
be explained as follows: initially, at lower substrate temperatures, e.g. 425C, the temperature may

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not be sufficient to decompose the sprayed droplets of Ni2+ ions from the solution and this

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therefore, results in a low thickness. At a particular substrate temperature 450C, decomposition
occurs at the optimum rate resulting in the terminal thickness being attained. A clear decrease of the

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film thickness with increasing the substrate temperature is observed after substrate temperature
450C. This decrease may be attributed to re-evaporation of film material after deposition or to
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thermal convection of the sprayed droplet during the deposition process or both. The decrease in
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film thickness at higher substrate temperatures may be due to a higher evaporation rate of the initial
ingredients of the solution. Similar type of behavior was earlier reported for spray deposited F:SnO2
thin films [33].
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3.1 Structural properties

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Structural analysis of spray deposited NiO thin films on amorphous glass substrates is
carried out by X-ray diffraction. Fig. 2 shows the XRD pattern of nickel oxide thin films prepared
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at various substrate temperatures. Substrate temperature affects the structural properties nickel
oxide thin films deposited with 0.5M nickel chloride. Peaks observed at angle 2=37.51, 43.41,
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62.93 and 79.70 corresponds to (111), (200), (220) and (222) planes of NiO. From JCPDS data
card No. 47-1049 the matching of observed and standard d values confirm that the NiO has cubic
phase. Results show that the films having preferential orientation along (111) direction, which is
most suitable direction for ion exchange and weak reflections along other peaks (200), (220), and
(222). From XRD, it is observed that the intensity of peaks for plane (111) goes on increasing with
rise in substrate temperature. This reveals that growth of NiO takes place along (111) orientation as
substrate temperature increases. Substrate temperature affects the film crystallinity. The lattice
parameter for cubic NiO thin film is calculated by using standard relation

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2 = 2 +2 +2 (2)

Where d is the inter planner spacing, a is the lattice parameter and (hkl) are values Miller indices
of the plane. Average lattice parameter is found to be 4.16 which is in great agreement with value
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reported by Kamal et al. [34] for nickel oxide films deposited from nickel chloride by spray
pyrolysis. Calculated values of interplanar spacing d and lattice parameters are listed in Table 1.

3.2 Surface morphology

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Surface morphology of NiO thin films deposited on amorphous glass substrates by spray
pyrolysis technique is studied by using SEM. The resultant morphology observed under

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microscopy is shown in Fig. 3 (a-d) for NO425, NO450, NO475 and NO500 specimens

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respectively. Films are inhomogeneous in nature. There are randomly shaped heaps seen on the
smooth surface. There are no cracks on the surface of films. Also, it is observed that as the substrate

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temperature increases the heaps comes closer and closer. Similar heaps type morphology is also
observed by Cattin et al. by using NiCl2 as a precursor solution [35]. The average diameter of these
heaps decreases from 2.5 m to 1 m as substrate temperature changes from 425C to 500C.
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3.3 Optical study
Optical study of NiO thin films on amorphous glass substrates spray deposited at various
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substrate temperatures is performed using UV-VIS spectrophotometer. Transmission spectra of

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spray deposited NiO thin films at various substrate temperatures are measured in the wavelength
range 310-1100 nm. It is observed that the transmission of NiO thin films initially decreases as
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substrate temperature increases from 425C to 450C and again increases as substrate temperature
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increases above 450C. Average transmission observed is about 70% at higher wavelength for
NO500 film. Initially, there was fall in transmission because of increase in the film thickness. Film
thickness largely affects the optical properties of the material. Optical band gap energy is calculated
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by using the absorption coefficient () given by Taucs relation [36]

(hEg)1/2
=A (3)
h

Where A is constant and h is the photon energy. Optical band gap energies for NiO thin films are
estimated by extrapolating straight line portion of (h)2 versus h curve to zero absorption. Fig. 4
shows Tauc plots (h)2 vs h for NiO thin films spray deposited at various substrate temperatures.
The nature of plot is linear showing that NiO films have direct allowed transition. It is found that
the NO450 show lowest value of band gap 3.04 eV. Other films have band gap in between 3.04 eV
to 3.28 eV. These values are in agreement with band gap of 3.11 eV reported by Hakim et al. [37]
for electron beam evaporated NiO thin films. The variation in band gap with substrate temperature
is due to the change in film thickness and crystallinity with respect to temperature.

3.4 Electrical resistivity

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Electrical resistivity of spray deposited NiO thin films on amorphous glass substrates is
measured by simple DC two point probe method and results are plotted in Fig. 5. It is observed that
the electrical resistivity decreases with rise in temperature signifying typical semiconducting
behavior of the NiO thin films. Also, the resistivity decreases as substrate temperature increases.
The relation between the temperature and resistivity of thin films is linear in nature. Electrical

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resistivity of NiO thin films at room temperature is observed to be of the order of 104-105 cm. The
change in electrical resistivity with substrate temperature is due to the essentially uncontrolled

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nucleation and growth of crystallites comprising the film. This can be explained using Petritz's
barrier model [38], since the films are polycrystalline. The model visualizes the polycrystalline
semiconductor films to be composed of a system of high conductive crystallites separated by high

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resistivity intercrystalline barriers. Crystallites are made up of the semiconductor compound
whereas the intercrystalline barriers are oxides of the constituents or compound itself. Since the
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crystallites do not grow sufficiently at low deposition temperature, the intercrystalline regions are
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wide which offer a high resistance to the motion of charge carriers. Higher substrate temperature
favours the formation of fewer nucleation centers resulting in larger crystallite size and hence the
intercrystalline barrier decreases. Now the charge carriers have to cross comparatively small
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intercrystalline region and hence decrease the resistivity. However, the resistivity of the NiO thin
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films deposited at higher substrate temperatures (above 450C) is increased and it can be attributed
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due to the deviation from stoichiometric composition of the films. Values of room temperature
electrical resistivity are in agreement with reported value of 10 4 -cm by Patil et al. [39] for nickel
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oxide thin films. Activation energy is calculated from the Arrhenius relation [40]
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= 0 exp (kTa ) (4)
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Where, represents the resistivity at temperature T, 0 is a constant, k is the Boltzmann constant, T

is the absolute temperature and Ea represents the activation energy. Activation energies calculated
from above relation for NiO thin films are found to decrease from 0.36 to 0.30 eV with the increase
the substrate temperature from 425C to 450C. The activation energies are found to decrease with
the increase of the substrate temperature. The substrate temperature has a significant effect on
structure, orientation, and stoichiometry of NiO thin films. The crystallinity of the films is
increased with increasing the substrate temperature and the films grown at lower substrate
temperatures have a random orientation. At higher substrate temperature (500C), the higher value
of activation energy may be due to the presence of additional phase in the film [38]. Akaltun et al.
[41] have reported the activation energies 0.25 to 0.29 eV, which is in agreement with present
study. Activation energy values corresponding to the higher temperature range and room
temperature range are listed in table 2.
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3.5 Electrochemical characterization

Electrochemical performance of spray deposited NiO thin films at various substrate
temperatures is studied. Specific capacitance is calculated using cyclic voltammetry. Charge-
discharge study confirmed the charge storage behavior of NiO films. EIS study gives electrolytic

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solution resistance and charge transfer resistance.
3.5.1 Cyclic voltammetry

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Supercapacitive behavior of NiO thin films is investigated by recording CV with the help of
electrochemical analyzer supplied by CH instrument. This is a three-electrode system with
Ag/AgCl as a reference electrode, platinum wire as a counter electrode and NiO thin film as a

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working electrode. All the measurements are taken in 2M aqueous KOH electrolyte within
potential window 0.15 to 0.55 V. Fig. 6 (a-d) shows CV curves at different scan rates of NiO thin
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films prepared at various substrate temperatures. The shape of CV curve indicates that the
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capacitance is mainly associated with the faradaic pseudocapacitance [42]. From Fig. 6, it is
observed that the shape of all CV curves nearly same with two strong redox peaks. Oxidation peak
related to charging process, whereas the reduction peak shows the discharge process [43]. Specific
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capacitance Csp is calculated from the relation [7, 15];

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1
= ( ) () (5)
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Where, v is the potential scan rate (mVs-1), (Vc-Va) is a working potential window, I is the current
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response (mA) of the NiO electrode for unit area (1cm2) dipped in the 2M aqueous KOH electrolyte
and m is deposited mass of NiO on 1cm2 surface of FTO coated glass substrate.
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It is observed that the area under the curve increases as scan rate increases. The peak current
increases as scan rate increases showing good reversibility for fast charge-discharge response. Even
at low scan rate of 5 mVs-1, a pair of well redox peaks is seen. With increase the scan rate, a little
shift in both cathodic and anodic peak potentials is witnessed due to the polarization. Also, the
small peak-to-peak separations suggest a fast electron transfer behavior, which is very helpful to
high-current charge/discharge [44-45]. From Fig. 7 (a) it is observed that the value of specific
capacitance decreases with increase in scan rate. This may be due to the fact that at low scan rate
there is sufficient time for transfer of protons between electrolyte and electrode interface. At higher
scan rates there may be partial transfer of protons which leads to either depletion or saturation of
the protons. The drop in specific capacitance is observed due to the increase of ionic resistivity also
[29]. Maximum specific capacitance is found to be 405 Fg-1 at scan rate of 5 mVs-1 for NO450
specimen. Fig. 7 (b) shows the variation of specific capacitance with substrate temperature.
Initially, the specific capacitance increases with increase in substrate temperature up to 450C and
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then falls with further rise in substrate temperature. Specific capacitance observed in the present
study is higher than the 157 Fg-1 in 2M KOH electrolyte reported by Patil et al. [28] for NiO thin
film. Jagdale and coworkers [29] have reported potentiodynamically deposited NiO nanoflakes
with specific capacitance 222 Fg-1. Recently there are efforts to increase the specific capacitance
the NiO composite with graphene by increasing the surface area as well as conductivity. Nickel

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oxide with graphene has shown high specific capacitance values [46-48].

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3.5.2 Galvanostatic charge/discharge
In order to evaluate the further electrochemical performance of NiO electrode deposited by
spray pyrolysis, we have measured the galvanostatic charging/discharging curves in 2M aqueous

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KOH solution with different current densities. Galvanostatic charge/discharge curves in the
potential range from 0.15-0.45V for NO450 electrode supercapacitors at different current densities
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are shown in Fig. 8 (a). Charge/discharge curves are nearly symmetric and repetitive, indicating
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that the electrochemical reactions are reversible for NiO electrode. The shape of the discharge
curves predicts the charge storage mechanism is faradaic and does not show the characteristics of a
pure EDLC but mainly pseudocapacitance, which is concord with the investigation of CV
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measurements. Specific capacitance (Csp, Fg1), is calculated by using formula given elsewhere [49-
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50]. Specific capacitance was 380 Fg1 at a current density of 1 Ag1, which is decreased to 334 Fg
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1
, even at the high current density of 4 Ag1. This value of specific capacitance is higher than
specific capacitance of 81.67 Fg1 at the current density of 0.5 Ag1 observed for NiO nanosheets
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fabricated through a facile hydrothermal route [51] and a specific capacitance of 266.7 Fg1 at 0.5
Ag1 for NiO@MnO2 core/shell nanocomposites fabricated by a two-step method [52].
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Fig. 8 (b) shows the long-term charge/discharge cycle stability of the NO450 electrode at a
current density of 1 Ag1 for 1000 cycles. Specific capacitance maintains 92.10 % of its initial
value, showing noteworthy cycle stability. Charge-discharge curves for first 10 cycles are given in
the inset of Fig. 8 (b), which shows almost the same symmetric curves. After an activation process
for 1000 cycles, the retention of capacitance value is higher than 92%, revealing that the NiO
electrode possesses good cycling stability, which is better than cycle-life stability with 78.5% of its
discharge specific capacitance retention for as-synthesized NiO nanosheets [51] and cycling
stability of 81.7% after 2000 cycles at 1 Ag1 for NiO@MnO2 core/shell nanocomposites [52].

3.5.3 Electrochemical impedance spectroscopy (EIS)

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To investigate the electrolytic conductivity of NiO electrode, the electrochemical impedance
spectroscopy (EIS) analysis is performed in the frequency range of 0.01 Hz to 1 MHz. Fig. 9 shows
the Nyquist plot for NiO electrodes in 2M aqueous KOH electrolyte. In the low frequency region,
the approximate straight line was observed while in high frequency region the small semicircle was
observed. There are different types of resistances. Solution resistance (Rs) which is non-zero

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intercept of high frequency region curve, charge transfer resistance (Rct) which is at
electrode/electrolyte interface parallel with chemical capacitance and Warburg impedance (Zw) in

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the electrolyte [52]. As we know the small semicircle represents the charge transfer resistance and
the straight line indicates the diffusion of ions. Charge transfer resistance (Rct) and the solution
resistance (Rs) are found to be 10.05 cm2 and 0.35 respectively for NO450 specimen. These

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values indicate that charges are easily transferred to electrolyte but diffusion of ions is much slower
in the electrolyte. Values of various parameters obtained from Nyquist plots are given in Table 2.
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4. Conclusions
Nickel oxide (NiO) thin films are successfully deposited on amorphous and FTO coated glass
substrates at various substrate temperatures by chemical spray pyrolysis. Spray deposited NiO thin
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films show cubic nature with a porous morphology. The lowest optical band gap energy is found to
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be 3.04 eV for NO450 specimen. Electrical resistivity is of the order of 104 cm at room
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temperature. Influence of substrate temperature on specific capacitance observed by cyclic

voltammetry reveals that the highest specific capacitance is 405 Fg-1 for NO450 thin film. This
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study gives good result indicating that with increase in conductivity of film there will be
enhancement in the specific capacitance. Galvanostatic charge/discharge study shows noteworthy
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cycle stability. EIS study also suggests that NiO is good candidate for supercapacitor applications.

Acknowledgement
Dr. A. A. Yadav is grateful to the Science and Engineering Research Board, Department of
Science and Technology, New Delhi, India for the financial assistance through the Project under
the SERC Fast Track Scheme for Young Scientist (File No. SB/FTP/PS- 068/2013).
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[32] Ratnesh Sharma, A.D. Acharya, S.B. Shrivastava, Manju Mishra Patidar, Mohan Gangrade, T.
Shripathi, V. Ganesan, Optik Inter. J. Light Electron Optics 127 (2016) 4661-4668.
AC

[33] A.A. Yadav, E.U. Masumdar, A.V. Moholkar, M. Neumann-Spallart, K.Y. Rajpure, C.H.
Bhosale, J. Alloys Comp. 488 (2010) 350355.
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(2008) 5814-5821.
[36] A.A. Yadav, S.C. Pawar, D.H. Patil, M.D. Ghogare, J. Alloys Comp. 652 (2015) 145-152.
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[38] K.L. Chopra, S.R. Das, Thin Film Solar Cells, Spring. Sci. & Business Media, (2013) pp 35.
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[40] A.A. Yadav, J. Mater. Sci.: Mater. Electron. 25 (2014) 1251-1257.
[41] Y. Akaltun, T. Cayr, J. Alloys Comp. 625 (2015) 144-148.
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[44] M. Yu, J. Chen, J. Liu, S. Li, Y. Ma, J. Zhang, J. An, Electrochim. Acta 151 (2015) 99-108.
[45] M. Jing, C. Wang, H. Hou, Z. Wu, Y. Zhu, Y. Yang, X. Jia, Y. Zhang, X. Ji, J. Power Sources
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PT
Ener. 39 (2014) 16171-16178.
[48] B.E. Conway, Electrochemical Supercapacitors: Scientific Fundamentals and Technological

I
CR
Applications, Kluwer Academic/Plenum Publishers, New York, NY, (1999).
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Nano Ener. 11 (2015) 211218.

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[50] Huanhao Xiao, Shunyu Yao, Hongda Liu, Fengyu Qu, Xu Zhang, Xiang Wu, Prog. Nat. Sci.:
Mater. Inter. 26 (2016) 271-275
N
[51] Junjiao Chen, Ying Huang, Chao Li, Xuefang Chen, Xiang Zhang, Appl. Surf. Sci. 360 (2016)
MA
534-539.
[52] H.J. Kim, S.W. Kim, C. V.V.M. Gopi, S.-K. Kim, S. S. Rao, M. S. Jeong, J. Power Sources
268 (2014) 163-170.
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375

350

325

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Thickness (nm)

300

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275

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250

225 N
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425 450 475 500
o
Substrate temperature ( C)
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Fig.1. Variation of film thickness with substrate temperature for spray deposited NiO thin films.
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(111)
JCPDS data card No. 47-1049

NO500

(200)

PT
(220)

(222)
Intensity (a.u.)

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NO475

CR
NO450

US
NO425

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10 20 30 40 50 60 70 80 90
2 (degree)
E D

Fig. 2. XRD plots for NiO thin films spray deposited at various substrate temperatures.
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(a) NO425

N US
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ED
PT

(b) NO450
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(c) NO475

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I PT
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(d) NO500

N US
Fig. 3. SEM images of spray deposited NiO thin films a) NO425, b) NO450, c) NO475 and d)
MA
NO500, respectively.
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20 NO425
(eVcm ) NO450
NO475
-1

PT
15
NO500

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10
13
h X 10

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5

0
1.5 2.0
N
2.5 3.0 3.5 4.0
MA
heV
Fig. 4 Tauc plots (h)2 vs h for spray deposited NiO thin films.
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5.5
NO425

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NO450
5.0 NO475
NO500

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4.5
log

4.0

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3.5
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3.0
2.4 2.6 2.8 3.0 3.2
-1
1000/T (K )
E D

Fig. 5 Plot of log versus inverse of absolute temperature for spray deposited NiO thin films.
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0.6

Current density (mAcm ) 0.4

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-2

0.2

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0.0

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-0.2
-1
5 mVs

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-1
-0.4 10 mVs
-1
20 mVs
-0.6
50 mVs
-1
N
MA
-0.8
0.1 0.2 0.3 0.4 0.5 0.6
Voltage (V vs Ag/AgCl)
D

(a)
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2
CE

1
AC ) -2
Current density (mAcm

-1
-1 5 mVs
-1
10 mVs
-1
-2 20 mVs
-1
50 mVs

-3
0.1 0.2 0.3 0.4 0.5 0.6
Voltage (V vs Ag/AgCl)

(b)

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1.2
Current density (mAcm ) 0.8
-2

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0.4

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0.0

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-0.4 -1
5 mVs

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-1
-0.8 10 mVs
-1
20 mVs
-1.2

-1.6
50 mVs
-1
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0.1 0.2 0.3 0.4 0.5 0.6

Voltage (V vs Ag/AgCl)
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(c)
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0.8
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)
-2

0.4
Current density (mAcm
AC

0.0

-1
-0.4 5 mVs
-1
10 mVs
-0.8 -1
20 mVs
-1
50 mVs
-1.2
0.1 0.2 0.3 0.4 0.5 0.6
Voltage (V vs Ag/AgCl)

(d)
Fig. 6. (a-d) Cyclic voltammetry plots at different scan rates in 2M aqueous KOH for spray
deposited NiO electrodes (a) NO425, (b) NO450, (c) NO475 and (d) NO500, respectively.

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450

Specific capacitance (Fg )

-1
400 NO425
NO450
350 NO475

PT
300 NO500

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250

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200

150

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100

50
0 10 20
N 30 40 50
MA
-1
Scan rate (mVs )

(a)
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Specific capacitance (Fg )

400
-1

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AC

300

200

100
425 450 475 500
o
Substrate temperature ( C)

(b)

Fig.7 Variation of (a) specific capacitance with scan rate and (b) specific capacitance at scan rate of
5mVs-1 with substrate temperature for spray deposited NiO thin film electrodes.
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0.45 -1
1Ag
-1
2Ag
0.40 -1
3Ag

PT
Potential (V)

-1
0.35 4Ag

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0.30

0.25

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0.20

0.15
0 50 100
N 150 200 250
MA
Time (s)
Fig. 8 (a) Galvanostatic charge/discharge curves for NO450 thin film electrode supercapacitor at
D

different current densities.

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Specific capacitance (Fg ) 400 92.10% retention

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-1

0.50

300 0.45

0.40

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Potential (V)

0.35

200 0.30

0.25

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0.20
100 0.15

0.10
0 500
N 1000 1500 2000 2500
MA
Time (s)
0
0 200 400 600 800 1000
Cycle number
E D

Fig. 8 (b) Long term cycling performance of the NO450 thin film electrode at the current density of
PT

1 Ag 1. Inset shows the charge-discharge curves of the first 10 cycles of the NO450 thin film
electrode.
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200

0
45

5
47

42
NO

PT
NO
150

I NO
0
50
- Z" ()

CR
O
100

N
US
50

N
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0
0 25 50 75 100 125 150 175 200

Z' ()
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Fig. 9 Nyquist plot for spray deposited NiO electrode in 2M aqueous KOH electrolyte.
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Table 1 Structural data for NiO thin films spray deposited at various substrate temperatures.
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Sample 2 Sin d cal. d std. (hkl) a cal. a std.
() () () () ()
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PT
NO425 37.45 0.32 2.40 2.41 111 4.16 4.18
43.45 0.37 2.08 2.09 200

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62.82 0.52 1.48 1.48 220
79.54 0.64 1.21 1.21 222
NO450 37.53 0.32 2.40 2.41 111 4.15 4.18

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43.46 0.37 2.10 2.09 200
62.93 0.52 1.48 1.48 220
79.70 0.64 1.20 N 1.21 222
MA
NO475 37.45 0.32 2.40 2.41 111 4.16 4.18
43.50 0.37 2.08 2.09 200
62.75 0.52 1.48 1.48 220
D

79.44 0.64 1.21 1.21 222

E

NO500 37.47 0.32 2.40 2.41 111 4.16 4.18

PT

43.54 0.37 2.08 2.09 200

63.06 0.52 1.48 1.48 220
CE

79.34 0.64 1.21 1.21 222

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Table 2 Film thickness, activation energy, specific capacitance, and electrochemical data for NiO
thin films.
______________________________________________________________________________
Sample Thickness Eg Ea (eV) Csp Rs Rct
(nm) (eV) HT RT (Fg-1) () (cm2)

PT
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NO425 280 3.25 0.16 0.37 262 0.50 11.00

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NO450 350 3.04 0.11 0.30 405 0.35 10.05
NO475 310 3.16 0.12 0.35 310 0.41 10.84
NO500 275 3.28 0.19 0.38 155 0.56 11.59

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Eg; Bandgap energy, Ea; Activation energy, Csp; Specific capacitance from CV, Rs; Solution
resistance, Rct; Charge transfer resistance, N
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Graphical Abstract

0.50

0.45

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0.40

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Potential (V)

0.35

0.30

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0.25

0.20
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0.15

0.10
0 500 1000 1500 2000 2500
D

Time (s)
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Highlights

Electrochemical properties of NiO thin films,

Optical band gap in the range of 3.04-3.28 eV.
Highest specific capacitance of 405Fg1with a wide potential window 0.15 to 0.55V

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