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First report on synthesis of ZnFe2O4 thin film using successive ionic layer
adsorption and reaction: Approach towards solid-state symmetric
supercapacitor device

Article  in  Electrochimica Acta · March 2016

DOI: 10.1016/j.electacta.2016.03.059

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 Electrochimica Acta 198 (2016) 203–211

Contents lists available at ScienceDirect

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

First report on synthesis of ZnFe2O4 thin film using successive ionic

layer adsorption and reaction: Approach towards solid-state
symmetric supercapacitor device
Shrikant S. Raut, Babasaheb R. Sankapal*
Nano Materials and Device Laboratory, Department of Applied Physics, Visvesvaraya National Institute of Technology, South Ambazari Road, Nagpur 440010,
MS, India

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

Article history: ZnFe2O4 thin film has been synthesized by a simple and low cost successive ionic layer adsorption and
Received 5 February 2016 reaction (SILAR) method without the use of surfactant or template. The nanoplate composed of
Received in revised form 8 March 2016 nanoparticles with porous surface morphology has been revealed which is beneficial towards
Accepted 9 March 2016
supercapacitor application. Formed ZnFe2O4 thin film has been tested as an electrode material for
Available online 10 March 2016
supercapacitor through electrochemical analysis. First attempt for SILAR synthesized ZnFe2O4 thin film
exhibited a specific capacitance of 471 Fg
1 at a scan rate of 5 mVs
1 in 1 M NaOH aqueous solution.
Keywords:
Further, ZnFe2O4 solid-state symmetric (SSS) supercapacitor device demonstrated voltage window of
Mixed transition metal oxides (MTMO)
SILAR
1.0 V with specific capacitance of 32 Fg
1, energy density of 4.47 Whkg
1 and power density of 277 Wkg
1
solid-state symmetric (SSS) supercapacitor at 1 Ag
1 current density. Such high performance capacitive behavior indicates ZnFe2O4 thin film is
promising and low cost electrode material towards energy storage devices for various portable electronic
systems.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Among the various energy storage systems, supercapacitors are
important source of energy storage devices and power outputs.
Typically, supercapacitor shows reasonable energy with high
power density and long cycle life. There are growing demands for
the next generation flexible and lightweight energy storage devices
with high power density and high energy density, as their special
features and potential applications in variety of portable electronic
devices such as smart sensors, mobiles, flexible touch screen and
electronic newspaper etc [1]. Nanostructure electrode materials
have been extensively studied in supercapacitor due to their high
surface area which results in higher electrode-electrolyte contact
area, short path length for cation transport and high power
performance [2]. Currently, variety of electrode materials have
potential candidates for supercapacitor which store/deliver energy
with different working principles [3]. Activated carbon, carbon
* Corresponding author. Tel.: + 91 712 2801170; fax: +91 712 2223230.
E-mail addresses: brsankapal@phy.vnit.ac.in, brsankapal@gmail.com
(B.R. Sankapal).
aerogels and carbon nanotube have been used as electric double
layer capacitors (EDLCs) where charges are stored non-faradically
at the electrode-electrolyte interface; on the other hand, transition
metal oxides and conducting polymers shows pseudocapacitive
behavior through redox mechanism at the electrode surface [4].
Mixed transition metal oxides (MTMO) with two different metal
cations have been studied extensively as an electrode material for
supercapacitor to improve the energy density and overall perfor-
mance [5]. The use of MTMO as an electrode material for
supecapacitor, the storing of charge primarily originates from the
pseudocapacitive mechanism [6]. Furthermore, the presence of
complex chemical composition and the synergic effect of multiple
valences of the metal cations in MTMOs are helpful to obtain the
desirable electrochemical behavior. Recently, Fe-based spinel mixed
transition metal oxides such as CoFe2O4 [7], NiFe2O4 [8]. and
MnFe2O4 [9] have attracted a great attention because it reach redox
reaction and improved electronic conductivity which is beneficial for
electrochemical application in comparison with the FexOy metal
oxide. ZnO is one of the potential material with higher band gap [10]
while Fe2O3 offers low environmental impact and variable oxidation
state. Among the spinel metal ferrites, ZnFe2O4 is promising material
due to its low toxicity, high specific surface area, low resistance and

http://dx.doi.org/10.1016/j.electacta.2016.03.059
0013-4686/ ã 2016 Elsevier Ltd. All rights reserved.
204 S.S. Raut, B.R. Sankapal / Electrochimica Acta 198 (2016) 203–211
fascinating electrochemical behavior [11]. ZnFe2O4 is technologically
important material with applications in lithium-ion batteries [12],
chemical sensors [13] and photocatalytic activity [14].
A very few reports are available for the utilization of ZnFe2O4 as
an anode electrode material for lithium ion battery and super-
capacitor application. Zhu et al. investigated ZnFe2O4 microsperes
for supercapacitor applications and result showed that the ZnFe2O4
single electrode had a specific capacitance of 131 Fg
1 and stable
cycling performance with 92% capacity retention over 1000 cycles
[15]. Liu et al. investigated the ZnFe2O4 replica with biological
hierarchical structure and showed a much higher specific
capacitance of 294 Fg
1 at 10 mVs
1 (single electrode) [16].
However, the fabrication of ZnFe2O4 as an anode material capable
to keep high specific capacitance, active long term cycling life
particularly when operating at high specific currents and good rate
capability still remains a great challenge.
Although various metal oxide or conducting polymers were
successfully synthesized by using different methods for super-
capacitor, so far few studies has been reported for the fabrication of
symmetric supercapacitor device. Assembling symmetric super-
capacitor device using metal oxides as both anode and cathode
electrode material could simplify the fabrication procedure [17].
Fe-based mixed transition metal oxides possess high hydrogen
evolution potential in aqueous solution, thus making them a
promising candidate in symmetric supercapacitor device.
This work focuses on the first report for the synthesis of
ZnFe2O4 thin films via successive ionic layer adsorption and
reaction (SILAR) method and its use as an electrode material for
supercapacitor. The SILAR method avoids unnecessary formation
of precipitation and loss of materials as appeared in chemical bath
deposition (CBD). This process is advantageous for the synthesis
of nanostructures since the basic building blocks are ions instead
of atoms. It is a low cost, low temperature soft chemical solution
method and convenient for large area deposition [18]. Further-
more, a solid-state symmetric (SSS) supercapacitor device has
been fabricated by using two similar ZnFe2O4 electrodes as a
cathode and anode solidified in polyvinyl alcohol-lithium
perchlorate (PVA-LiClO4) gel electrolyte and detail results are
discussed.
2. Experimental
Iron (III) sulphate (FeSO4), zinc sulphate (ZnSO4), sodium
hydroxide (NaOH), hydrogen peroxide (H2O2), ammonia, polyvinyl
Fig. 1. Schematic presentation for the synthesis of ZnFe2O4 thin film by using SILAR method. FE-SEM image shows formed ZnFe2O4 thin film on SS substrate.
alcohol (PVA) and lithium perchlorate (LiClO4) were purchased from
Merck India private Ltd. The chemicals and solvents were of
analytical grade and used as received. Stainless steel (grade 304,
0.021 mm thick) were purchased locally and used as substrate.
2.1. Synthesis and reaction kinetics of ZnFe2O4 thin film formation
The growth kinetics of thin film formation in the SILAR
method is based on the principle of ion-by-ion growth, which
involves the ion-by-ion deposition at nucleation sites on the
immersed surfaces [19]. ZnFe2O4 thin film was prepared by
SILAR method on stainless steel (SS) substrate. In this method,
ZnFe2O4 thin film were deposited by alternative immersion of
the substrate in two cationic precursors (0.05 M ZnSO4 and
0.1 M FeSO4 solution) and two anionic precursors (1% H2O2 and
0.02 M NaOH solution). The schematic for the formation of
ZnFe2O4 thin film by SILAR method is depicted in Fig. 1. A
cationic precursor of ZnSO4 solution was complexed by using
aqueous ammonia (30% NH4OH) solution (pH 12) (I-beaker,
300 K). A well cleaned SS substrate was immersed in this
solution for 20 s where tetra ammonium zinc (II) complex get
adsorbed onto the substrate surface due to the attractive forces
between the ions in the solution and surface of substrate [Fig. 1
(a)] [20] as per the following reaction:
Zn2þ þ 4NH4 OH ! ½ZnðNH3 Þ4 2þ þ 4H2 O ð1Þ
The reaction of pre-adsorbed zinc complex with H2O2 was
performed by immersing the substrate in the H2O2 solution (II-
beaker, 343 K) for 20 s to form Zn(OH)2 thin film [Fig. 1 (b)] as per
the following reaction:
343K
½ZnðNH3 Þ4 2þ þ H2 O2 ! ZnðOHÞ2 þ NH4 OH ð2Þ
Then, the substrate with Zn(OH)2 thin film was dipped into
0.1 M ferrous sulphate solution (III-beaker, 300 K) for 20 s in order
to absorb Fe2+ ions [Fig. 1 (c)]. Furthermore, the absorbed Fe2+ ions
were rinsed in double distilled water (DDW) for 10 s in order to
remove the loosely bounded Fe2+ ions. This is followed by dipping
the substrate in NaOH solution (IV-beaker, 343 K), where OH
ions
react with Fe2+ ions [Fig. 1 (d)] and form FeOOH [21].
343K OH

Fe2þ þ 2NaOH ! FeðOHÞ2 ! FeOOH ð3Þ
 S.S. Raut, B.R. Sankapal / Electrochimica Acta 198 (2016) 203–211 205

Finally, the substrate again rinsed in DDW for 10 s to remove Further, galvanostatic charge-discharge curves were used to
loosely bounded and unreacted species. This completes one SILAR calculate the specific capacitance, energy density and power
cycle; such cycle was repeated for 25 times in order to get density by using following equations [23]:
appropriate thickness. The reaction of zinc hydroxide and iron
Id  T d
oxyhydroxide take place by annealing the film at 573 K for one hour Cs ¼ ð6Þ
to remove hydroxide phase in order to form crystalline zinc ferrite
DV  m
on the substrate [Fig. 1 (e)].
573K
ZnðOHÞ2 þ 2FeOOH ! ZnFe2 O4 þ 2H2 O " ð4Þ

2.2. Material Characterizations

Structure of the ZnFe2O4 thin film was examined by X-ray

diffractometer (XRD) (Bruker D8 Advance diffractometer) with
copper radiations (Ka, l = 1.5406 A ). Fourier transform infrared
(FTIR) spectra of powder sample were recorded by a JASCO
410 spectrometer in transmission mode in the wave number
4000–400 cm
1. The surface morphology of thin films were
investigated by using scanning electron microscope (FE-SEM:
Hitachi S 4800) unit coupled with EDAX. Transmission electron
microscope (TEM) and high resolution TEM (HR-TEM) were
carried out by using PHILIPS CM200, HRTEM: JEOL JEM 2100.

2.3. Electrochemical measurements

The electrochemical measurements were conducted by using

Potentiostat/Galvanostat (Princeton Applied Research USA, PAR-
STAT-4000) with an electrochemical cell. Three electrodes system
has been used to study the electrochemical properties of single
electrode consisting of prepared thin film as a working electrode,
Ag/AgCl and platinum as the reference and counter electrodes,
respectively in an aqueous electrolyte. However, two electrodes
system has been used for solid-state symmetric (SSS) super-
capacitor device.
For the fabrication of SSS supercapacitor device, first polyvinyl
alcohol-lithium perchlorate (PVA-LiClO4) gel electrolyte was
prepared by using 6 g of PVA with 1 M lithium perchlorate in
30 ml double distilled water. The prepared solution was stirred at
338 K temperature in order to get clear solution. After complete
dissolution, the solution was continuously stirred at room
temperature until it got homogeneous viscous appearance.
Further, symmetric supercapacitor device was fabricated as
follows: two identical ZnFe2O4 thin film electrode were painted
with PVA-LiClO4 gel electrolyte by Doctor Blade in order to form a
thin layer of gel electrolyte and then the two electrodes were
sandwiched in order to assemble the device. In addition, a definite
pressure was applied for 10 minute on the assembled device, with
intention of good contact and to improve its mechanical strength.
The cyclic voltammetry, galvanostatic charge-discharge and
electrochemical impedance analysis were performed by using the
Versa Studio 2.42.3 software. The impedance matching with
equivalent circuit was performed by using the ZSimpWin
3.21 electrochemical workstation. The mass loading of sample
on substrate was measured by gravimetric weight difference
method with the help of sensitive microbalance.
From cyclic voltammetry (CV) curve, the specific capacitance of
ZnFe2O4 thin film was estimated by the following equation [22].
Z Vc
1
Cs ¼ IdV ð5Þ
mvðV c
V a Þ V a
R
where, ‘Cs’ is the specific capacitance (Fg
1), ‘ IdV’ is the total
integral area of the CV curve, ‘(Vc-Va)’ is an operational potential
window, ‘v’ represents the scan rate (mVs
1) and ‘m’ is the Fig. 2. (a) XRD patterns of as-deposited and annealed (573 K and 773 K) ZnFe2O4
thin films on SS substrate, (b) FT-IR spectra of as-deposited and annealed (573 K)
deposited mass of the sample electrode on 1 cm2 area of stainless
ZnFe2O4 scratch powder sample. (c) Raman spectra of annealed (573 K) ZnFe2O4
steel substrate. scratched powder sample.
206 S.S. Raut, B.R. Sankapal / Electrochimica Acta 198 (2016) 203–211
R at 599 cm
1 corresponds to the Zn-O tetrahedral stretching
I V ðtÞdt
E¼
3:6m
E  3600
P¼
Td
where, ‘Cs’ is the specific capacitance, ‘Id’ is discharge current, ‘Td’ is
the discharge time, ‘DV’ is the potential window, ‘m’ is the mass of
R
active material, ‘E’ is the energy density, ‘ V(t)dt’ is integral area of
the discharging curve and ‘P’ is the power density.
3. Results and discussion
3.1. Structural and chemical bond analysis
Fig. 2(a) shows the X-ray diffraction pattern (XRD) of as-
deposited (ZnFe hydroxide) and annealed ZnFe2O4 thin films on SS
substrate. XRD pattern of as-deposited thin film without heat
treatment represents an amorphous structure that there was no
noticeable diffraction peaks other than SS substrate. After
annealing at 573 K for 1 hour, broad tiny peaks appeared
corresponding to (311), (222) and (440) planes of zinc ferrite
with cubic spinel structure (JCPDS, no. 89-4926) confirming the
formation of ZnFe2O4. These tiny peaks are attributed to the
existence of fine grains. Annealing at 773 K, peak intensity becomes
stronger alongwith the presence of trace amount of a-Fe2O3 was
observed.
Fig. 2(b) shows the FTIR spectra of as-deposited ZnFe hydroxide
and annealed ZnFe2O4 powder samples in the range of 4000–
400 cm
1 where two lattice vibrations of metal-oxygen bond in the
Fig. 3. FE-SEM images of (a) SS substrate and (b) ZnFe2O4 thin film. (c) Cross-sectional SEM image of ZnFe2O4 thin film. (d) EDAX pattern of ZnFe2O4 scratched powder.
region of 400–600 cm
1 have been observed. High frequency band
ð7Þ vibration and the low frequency band at 433 cm
1 corresponds
to the octahedral stretching vibration of Fe-O [24]. In addition, the
vibration band at 1647 cm
1 and 3443 cm
1 are assigned to the O-
H bending and O-H stretching, respectively [25]. In as-deposited
ð8Þ ZnFe hydroxide, band observed at 1095 cm
1 shows the residual of
lepidocrocite (F-FeOOH) [26]. The extra band at 1495 cm
1 and
1371 cm
1 are due to C-H bending mode and symmetric stretching
of C-N [27], which is possibly from the surface contaminated
carbon, as usually observed in chemical deposited films [28]. In
annealed sample (573 K), the O-H stretching bond was likely to be
shifted towards higher frequency with decreasing in intensity due
to the release of hydroxide to form oxide. The band at 1124 cm
1 is
due to the formation of Zn-O-Fe bond, similar appearance was
reported by Changlin et al. [29].
Further, ZnFe2O4 scratched powder sample were characterized
by Raman spectrophotometer and the resulting spectra is depicted
in Fig. 2(c). ZnFe2O4 Raman spectra exhibits much stronger five
active Raman modes (A1g + Eg + 3F2g) at 210, 271, 335, 476 and
648 cm
1 which revealed cubic spinel structure of ZnFe2O4 sample.
It has been reported that, Raman signal of cubic spinel ferrite at
648 cm
1(above 600 cm
1) is reasonably considered to have A1g
symmetry of oxygen in tetrahedral AO4 group while the other low
frequency modes at 271 cm
1(E2g) and at 210, 335, 476 cm
1 (F2g)
i.e. (Eg + 3F2g) representing the characteristics of the octahedral
sites (BO6) [30].
3.2. Surface morphological studies
Fig. 3 (a) shows the FE-SEM image of SS substrate as reference.
Fig. 3 (b) shows FE-SEM image of ZnFe2O4 thin film on SS substrate
 S.S. Raut, B.R. Sankapal / Electrochimica Acta 198 (2016) 203–211
where the formation of nanoparticles of ZnFe2O4 attached on the
surface of nanoplate is observed. The cross-sectional SEM image
indicates the porous structured film onto SS substrate with the
average film thickness about 41 mm as shown in Fig. 3 (c). The
chemical composition of the particles scratched from the film was
analysed by EDS. The strong peak of Zn, Fe and O elements were
observed in the spectrum which shows the inclusion of elements in
formed compound [Fig. 3 (d)].
In order to get insight view about shape, size and distribution of
ZnFe2O4 nanostructures, TEM and high resolution TEM (HR-TEM)
images have been recorded. A TEM image clearly shows the
ZnFe2O4 nanoparticles of size 10–20 nm [Fig. 4(a)]. The electron
diffraction pattern of the ZnFe2O4 displays several concentric
diffraction rings, indicating the nanocrystalline nature of the
formed ZnFe2O4 [Inset, Fig. 4(a)]. Fig. 4(b) shows HR-TEM image of
ZnFe2O4 where clear evidence of the lattice fringes with
interplanar spacing of 0.242 nm is observed which corresponds
to (222) plane of ZnFe2O4 exhibiting cubic spinel structure which
well supports with the results obtained by XRD studies.
Fig. 4. (a) TEM image of ZnFe2O4 (inset is electron diffraction pattern of ZnFe2O4)
and (b) HR-TEM image of ZnFe2O4.
207
3.3. Electrochemical supercapacitor studies of ZnFe2O4 thin film
The electrochemical performance of ZnFe2O4 thin film as a
working electrode was studied in a three electrode system. The
effect of mass loading on cyclic voltammetry was studied by
controlling the number of SILAR cycles [Fig. 5(a)]. For 20 SILAR
cycles, the response of ZnFe2O4 was very close to pseudocapacitive
behavior with good reversibility represented by two noticeable
peaks, whereas electrode for 25 SILAR cycles exhibits only
oxidation peak and not showing reversibility. Above 25 cycles,
the film peel off due to the development of tensile stress that tends
to cause delamination as the film becomes thicker [31]. Hence
supercapacitor properties were studied for 20 SILAR cycle
deposited film in order to get good reversibility. For finding the
suitable electrolyte concentration, the cyclic voltammetry (CV) of
ZnFe2O4 thin film electrode was examined in three concentrations
of NaOH electrolyte in the voltage range of 0 to
1.0 V at 5 mVs
1
scan rate [Fig. 5(b)]. With variation in concentration from 0.1 to
1.5 M, distortion in CV curve was observed at lower electrolyte
concentration however the increase in current under the curve
with well resolved redox peak is observed at higher concentration.
The effect of scan rate (5 to 100 mVs
1) on the ZnFe2O4 thin film
electrode was studied in 1 M NaOH electrolyte with 0 to
1.0 V
operational voltage window [Fig. 5(c)]. The response of the
ZnFe2O4 thin film electrode characteristic is different from the
electric double layer capacitance, in which the shape of CV is
normally close to an ideal rectangular shape indicating pseudo-
capacitive behavior [32]. A pair of redox peak which suggest that
the capacitance mainly results from a pseudocapacitive behavior
caused by reversible electrochemical reactions related to Zn (or
Fe)-O/Zn(or Fe)-O-OH. In addition, CV curve exhibiting a linear
dependence of charge stored with the potential windows
designate the ZnFe2O4 thin film electrode have electrochemical
signature of capacitive electrode [33]. From equation (5), the
maximum value of specific capacitance was achieved as 471 Fg
1 at
a 5 mVs
1 scan rate. In addition, the specific capacitance still
remains to 230 Fg
1 at 100 mVs
1 scan rate. The variation in the
specific capacitance of the ZnFe2O4 thin film electrode as a function
of scan rate is depicted in Fig. 5(d) which shows the decrease in
specific capacitance with increase in scan rate. The decrease in
specific capacitance is due to the fact that at lower scan rate, both
outer and inner pore surface of the porous electrode are effectively
utilized for intercalation whereas at high scan rate, mainly outer
regions of the pores are accessed by the ions [34].
The galvanostatic charge-discharge of ZnFe2O4 thin film
electrode were studied at different current densities, which offer
to judge the rate of change of voltage with time during both
charging and discharging [Fig. 6(a)]. The charge-discharge study
shows a sudden drop in current at the starting of discharging
which is mainly due to the internal resistance [35]. The linear
dependence of charge stored with changing potential within the
potential windows of 0 to
1.0 V, suggesting an excellent
reversibility of the electrode material [36]. Furthermore, the
charge-discharge curves is utilized to calculate the energy density
and power density of ZnFe2O4 thin film electrode by using equation
(7) and (8), respectively. The energy and power density was found
to be 53.22 Whkg
1 and 1.87 kWkg
1, respectively at current
density of 2.72 Ag
1. The Ragone plot (energy density Vs power
density) of the ZnFe2O4 thin film electrode is illustrated in Fig. 6(b).
Ragone plot shows decrease in energy density with the increasing
power density. SILAR deposited ZnFe2O4 exhibits comparative
lower specific capacitance than reported by rotational chemical
bath deposition method [37]; however the SILAR method avoids
unnecessary formation of the precipitate and loss of materials as
appeared in chemical bath deposition which can further reduce the
entire cost of the deposited film.
208 S.S. Raut, B.R. Sankapal / Electrochimica Acta 198 (2016) 203–211

Fig. 5. Cyclic voltammetry (CV) curves of ZnFe2O4 thin film electrode in (a) different SILAR cycle deposited films (b) different electrolyte concentration at 5 mVs
1 scan rate.
(c) CV curves of ZnFe2O4 thin film electrode at different scan rate in 1 M NaOH electrolyte, and (d) Variation of the specific capacitance for ZnFe2O4 thin film electrode as a
function of scan rate.

Fig. 6. (a) Constant current charge-discharge curve of ZnFe2O4 thin film at different current density in 1 M NaOH electrolyte. (b) The energy density vs. power density of
ZnFe2O4 thin film in Ragone plot. (c) Variation of capacity retention of ZnFe2O4 thin film electrode with the number of cycles (inset is CV curves of ZnFe2O4 thin film for
different number of cycles at a 50 mVs
1 scan rate). (d) Nyquist plots of ZnFe2O4 thin film with AC voltage amplitude of 10 mV.
 S.S. Raut, B.R. Sankapal / Electrochimica Acta 198 (2016) 203–211 209

Fig. 7. (a) CV curves of ZnFe2O4-SSS supercapacitor device at different scan rate. (b) Variation of the specific capacitance for ZnFe2O4-SSS supercapacitor device as a function of
scan rate.

The long term electrochemical stability is an important
requirement for supercapacitor electrode; cycling stability of
ZnFe2O4 thin film electrode was tested using CV measurements in
1 M NaOH electrolyte at 50 mVs
1 scan rate [Fig. 6 (c)]. It was
observed that the ZnFe2O4 thin film electrode showed 72%
capacitance retention over 1000 cycles of their initial capacitance.
Decrease in specific capacitance might be due to the loss of
electrical contact between the active materials and wetability issue
[38].
Electrochemical impedance spectroscopy (EIS) measurement of
ZnFe2O4 thin film electrodes were performed at open circuit
potential in the frequency range from 0.1 Hz to 15 kHz in order to
obtain the information of charge transfer resistance (Rct), solution
resistance (Rs) and capacitive behavior. Fig. 6(d) shows the Nyquist
plot consist of experimental and fitted spectra, based on the
equivalent circuit proposed for ZnFe2O4 thin film electrode. Inset of
Fig. 6(d) shows the small semicircle arc in high frequency region
and inclined line in the low frequency region. High frequency
intercept on real axis represents the Rs in combined resistance
including ionic resistance of electrolyte, intrinsic resistance of
substrate and contact resistance of the interface of active material/
current collector whereas semicircle arc corresponds to the Rct and
electrode/electrolyte interface [39]. The appearance of a CPE i.e.
constant phase elements may arise due to the porosity of the
electrode materials and W is the Warburg impedance which
correlated with the frequency dependence of ion diffusion/
transport into the pores on the surface of the electrode during
the transition from the high frequency semicircle to the mid-

Fig. 8. (a) Constant current charge-discharge curve of ZnFe2O4-SSS supercapacitor device at different current density. (b) The energy density vs. power density of ZnFe2O4-SSS
supercapacitor device in Ragone plot. (Inset is the photoimage of glow up of light emitting diode (LED)) (c) Variation of capacity retention of ZnFe2O4-SSS supercapacitor
device with the number of cycles (inset is CV curves of ZnFe2O4-SSS supercapacitor device for different number of cycles at a 50 mVs
1 scan rate). (d) Nyquist plots of ZnFe2O4–
SSS supercapacitor device with AC voltage amplitude of 10 mV.
210 S.S. Raut, B.R. Sankapal / Electrochimica Acta 198 (2016) 203–211

Table 1
The calculated values of specific capacitance, energy density and power density at different current density of ZnFe2O4–SSS supercapacitor device.

Sr. no Current Density (Ag
1) Specific Capacitance (Fg
1) Energy Density (Whkg
1) Power Density (Wkg
1)
1 1 32.22 4.47 277.78
2 1.5 24.16 3.36 416.67
3 2 12.22 1.7 555.56
4 2.5 8.33 1.15 694.44

Table 2
Comparison of electrochemical properties of symmetric supercapacitor device (liquid (L)/solid).

Compounds Electrolyte Potential range (V) Specific capacitance (F g
1) Energy density (Wh kg
1) Power density (W kg
1) Ref.
NiO/MWNT PVA/LiClO4
0.6 to 0.6 24 at 5 mV s
1 – – [41]
Co(OH)2 L-1 M KOH 0 to 1.2 44 at 5 mV s
1 3.96 42(kW kg
1) [42]
Fe3O4 L-1 M H2SO4 0 to 1 15 at 0.25 A g
1 12.4 – [43]
MnO2 L-LiPF6 0 to 1 – 3.4 370 [44]
Carbon L-KOH 0 to
1 – 7.4 200 [45]
ZnFe2O4 PVA-LiClO4 0 to +1 32.22 at 1 A g
1 4.5 277 Present work

frequency spike. The Rs and Rct values of the fitted EIS spectra of
ZnFe2O4 thin film electrode are 0.8 V cm
2 and 1.05 V cm
2,
respectively.
3.4. Electrochemical properties of solid-state symmetric (SSS)
supercapacitor device
Solid-state symmetric (SSS) supercapacitor device was fabri-
cated by using ZnFe2O4 thin films as a flexible electrode
(2.3  2 cm2) sandwiched by polyvinyl alcohol (PVA)
LiClO4 gel
electrolyte. The cyclic voltammograms (CV) of the flexible
ZnFe2O4-SSS device within the potential windows of 0 to +1.0 V
at different scan rates (2 to 100 mVs
1) are demonstrated in
Fig. 7(a). The CV curves maintain their shape and current under the
CV curves increases with the scan rate which reveals the capacitive
performance of ZnFe2O4-SSS device.
The variation of specific capacitance with scan rate is shown in
Fig. 7(b). The maximum specific capacitance of the ZnFe2O4-SSS
supercapacitor device is found to be 26 Fg
1 at 2 mVs
1 scan rate
based on the total mass (1.80 mg) of active material in two
electrodes. The estimated values of specific capacitance are found
to be decreases from 26 to 10 Fg
1 with increase in scan rate (2–
100 mVs
1).
The galvanostatic charge-discharge of ZnFe2O4-SSS super-
capacitor device at different current density was studied in order
to find out the energy density, power density and device
performance [Fig. 8 (a)]. The Ragone plot relating to energy
density and power density is shown in Fig. 8 (b). ZnFe2O4-SSS
supercapacitor device exhibited a maximum specific capacitance
of 32 Fg
1, high energy density of 4.47 Whkg
1 with power density
of 277 Wkg
1 at 1 Ag
1 current density. Table 1 provides the values
of specific capacitance, energy density, power density at different
current density of ZnFe2O4-SSS supercapacitor device. The
obtained energy density 4.47 Whkg
1 is higher than previously
reported symmetric supercapacitor based on graphene @ carbon
cloth (1.64 Whkg
1) [40]. Inset Fig. 8(b) shows the photoimage of
glow up of light emitting diode (LED) by using series combination
of two ZnFe2O4-SSS supercapacitor device. Table 2 summarizes
some of the results that have been reported with symmetric
supercapacitor device [41–45]. In order to check the stability of
ZnFe2O4-SSS supercapacitor device, CV cycling is repeated for
1000 times at a scan rate of 100 mVs
1 within potential windows of
0 to 1.0 V and as shown in inset of Fig. 8 (c). The plot of capacitance
retention with cycle number shows 66% capacitance retention over
1000CV cycles [Fig. 8 (c)]. The loss of capacitance during cycling
process is due to the slight degradation of the gel electrolyte and
ZnFe2O4. In addition to this, electrochemical impedance analyses
of ZnFe2O4-SSS supercapacitor device were performed at open
circuit potential in the frequency range from 0.1 Hz to 100 kHz.
Nyquist plot consist of experimental and fitted spectra based on
the equivalent circuit proposed for ZnFe2O4-SSS supercapacitor
device shows the half semicircle at high frequency because of the
faradaic charge transfer resistance and 45 phase angle in the low
frequency region, corresponding to the Warburg region and related
to the diffusion of electrolyte ions within the pores of the electrode
[Fig. 8 (d)]. The plot demonstrates a very small equivalent series
resistance of 0.58 V cm
2 and the charge transfer resistance of
4.43 V cm
2 [inset Fig. 8 (d)]. A relatively high charge transfer
resistance is due to the resistive nature of the device and low ionic
conductivity of the solid electrolyte [46].
4. Conclusions
Successive ionic layer adsorption and reaction (SILAR) method
was employed successfully for the synthesis of ZnFe2O4 thin films.
The film exhibited a maximum specific capacitance of 471 Fg
1 at
5 mVs
1 scan rate, with 53.22 Whkg
1 energy density and
1.87 kWkg
1 power density at current density of 2.72 Ag
1 in
1 M NaOH electrolyte. Furthermore, ZnFe2O4-SSS supercapacitor
device was fabricated using PVA–LiClO4 gel electrolyte. The device
exhibits an excellent electrochemical performance with potential
windows of 1.0 V having good energy and power density as well as
long cycle life. Used SILAR method is simple, low cost and
applicable for large scale production of electrode materials
towards supercapacitor application.
Acknowledgements
BRS would like to thank the DST-SERB project, Govt. of India
(Do. No: SB/S2/CMP/032/2013; 4/06/2013) and SSR thanks to VNIT,
Nagpur for Fellowship.
References
[1] X. Lu, M. Yu, G. Wang, Y. Tong, Y. Li, Energy Environ. Sci. 7 (2014) 2160.
[2] S.B. Kulkarni, A.D. Jagadale, V.S. Kumbhar, R.N. Bulakhe, S.S. Joshi, C.D.
Lokhande, Hydrogen Energy 38 (2013) 4046.
[3] S. Santhanagopalan, A. Balram, D.D. Meng, ACS Nano 7 (2013) 2114.
[4] D.P. Dubal, P.G. Romero, B.R. Sankapal, R. Holze, Nano Energy 11 (2015) 377.
[5] D.P. Dubal, R. Holze, P. Gomez-Romero, Scientific Reports 4 (2014) 7349.
[6] S.G. Mohamed, C.J. Chen, C.K. Chen, S.F. Hu, R.S. Liu, ACS Appl. Mater. Interfaces
6 (2014) 22701.
 S.S. Raut, B.R. Sankapal / Electrochimica Acta 198 (2016) 203–211
[7] D.H. Deng, H. Pang, J.M. Du, J.W. Deng, S.J. Li, J. Chen, J.S. Zhang, Cryst. Res.
Technol. 47 (2012) 1032.
[8] Z.Y. Yu, L.F. Chen, S.H. Yu, J. Mater. Chem. A 2 (2014) 10889.
[9] S.L. Kuo, J.F. Lee, N.L. Wu, J. Electrochem. Soc. 154 (2007) A34.
[10] P.K. Baviskar, J.B. Zhang, V. Gupta, S. Chand, B.R. Sankapal, J. Alloys Compd. 510
(2012) 33.
[11] Y. Sharma, N. Sharma, G.V. Subba Rao, B.V.R. Chowdari, Electrochim. Acta 53
(2008) 2380.
[12] J.M. Won, S.H. Choi, Y.J. Hong, Y.N. Ko, Y.C. Kang, Scientific Reports 4 (2014)
5857.
[13] L. Su, J. Feng, X. Zhou, C. Ren, H. Li, X. Chen, Anal. Chem 13 (2012) 5753.
[14] B.Y. Hou, X.Y. Li, Q.D. Zhao, X. Quan, G.H. Chen, Adv. Funct. Mater. 20 (2010)
2165.
[15] M. Zhu, X. Zhang, Y. Zhou, C. Zhuo, J. Huang, S. Li, RSC Adv. 5 (2015)
39270.
[16] H. Liu, Y. Guo, Y. Zhang, F. Wu, Y. Liu, D. Zhang, Mater. Sci. Eng. B 178 (2013)
1057.
[17] H. Xia, B. Li, L. Lu, RSC Adv. 4 (2014) 11111.
[18] B.R. Sankapal, R.S. Mane, C.D. Lokhande, Mater. Res. Bull. 35 (2000) 2027.
[19] H.M. Pathan, C.D. Lokhande, Bull. Mater. Sci. 27 (2004) 85.
[20] P.K. Baviskar, P.R. Nikam, S.S. Gargote, A. Ennaoui, B.R. Sankapal, J. Alloys
Compd. 551 (2013) 233.
[21] S.S. Raut, B.R. Sankapal, New J. Chem. 40 (2016) 2619.
[22] R.R. Salunkhe, K. Jang, S.W. Lee, H. Ahn, RSC Adv. 2 (2012) 3190.
[23] L. Sui, S. Tang, Z. Dai, Z. Zhu, H. Huangfu, X. Qin, Y. Deng, G.M. Haarberg, New J.
Chem. 39 (2015) 9363.
[24] S. Ameer, I.H. Gul, N. Mahmood, M. Mujahid, Mater. Charact. 99 (2015) 254.
[25] M.M. Rahman, S.B. Khan, M. Faisal, A.M. Asiri, K.A. Alamry, Sens. Actuators B
171 (2012) 932.
[26] V.S. Kumbhar, A.D. Jagadale, N.M. Shinde, C.D. Lokhande, Appl. Surf. Sci. 259
(2012) 39.
View publication stats
211
[27] (a) A.H. Elsayed, M.S. Mohy Eldin, A.M. Elsyed, A.H. Abo Elazm, E.M. Younes, H.
A. Motaweh, Int. J. Electrochem. Sci. 6 (2011) 206;
(b) S. Gunasekaran, S. Ponnusamy, Indian J. Pure Appl. Phys. 43 (2005) 838.
[28] B.R. Sankapal, M. Ch. Lux-Steiner, A. Ennaoui, Appl. Surf. Sci. 239 (2005) 165.
[29] Y. Changlin, Y. Kai, S. Qing, Y. Jimmy, C. Fangfang, L. Xin, Z. Xiaochun, Sci China
Chem. 55 (2012) 1802.
[30] O. Akhavan, A. Meidanchi, E. Ghaderi, S. Khoei, J. Mater. Chem. B 2 (2014)
3306.
[31] A.D. Jagadale, V.S. Kumbhar, C.D. Lokhande, J. Colloid Interface Sci. 406 (2013) 225.
[32] B.R. Sankapal, H.B. Gajare, D.P. Dubal, R.B. Gore, R.R. Salunkhe, H. Ahn, Chem.
Eng. J. 247 (2014) 103.
[33] T. Brousse, D. Bélanger, J.W. Long, J. Electrochem. Soc. 162 (2015) A5185.
[34] D.P. Dubal, G.S. Gund, R. Holze, C.D. Lokhande, J. Power Sources 242 (2013) 687.
[35] G.S. Gund, D.P. dubal, B.H. Patil, S.S. Shinde, C.D. Lokhande, Electrochim. Acta
92 (2013) 205.
[36] L.J. Xie, J.F. Wu, C.M. Chen, C.M. Zhang, L. Wan, J.L. Wang, Q.Q. Kong, C.X. Lu, K.X.
Li, G.H. Sun, J. Power Sources 242 (2013) 148.
[37] M.M. Vadiyar, S.C. Bhise, S.K. Patil, S.A. Patil, D.K. Pawar, A.V. Ghule, P.S. Patil, S.
S. Kolekar, RSC Adv. 5 (2015) 45935.
[38] D.P. Dubal, D.S. Dhawale, R.R. Salunkhe, C.D. Lokhande, J. Alloys Compd. 496
(2010) 370.
[39] T.W. Lin, C.S. Dai, K.C. Hung, Scientific Reports 4 (2014) 7274.
[40] S.Y. Wang, B. Pei, X.S. Zhao, R.A.W. Dryfe, Nano Energy 2 (2013) 530.
[41] G.S. Gund, D.P. Dubal, S.S. Shinde, C.D. Lokhande, ACS Appl. Mater. Interfaces 6
(2014) 3176.
[42] A.D. Jagadale, V.S. Kumbhar, D.S. Dhawale, C.D. Lokhande, Electrochim. Acta 98
(2013) 2.
[43] K. Karthikeyan, D. Kalpana, S. Amaresh, Y. Sung Lee, RSC Adv. 2 (2012) 12322.
[44] R.S. Kalubarme, H.S. Jadhav, C.J. Park, Electrochim. Acta 87 (2013) 457.
[45] E. Raymundo-Piñero, F. Leroux, F. Béguin, Adv. Mater. 18 (2006) 1877.
[46] D.P. Dubal, R. Holze, Energy 51 (2013) 407.