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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 Fg1 at a scan rate of 5 mVs1 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 Fg1, energy density of 4.47 Whkg1 and power density of 277 Wkg1
solid-state symmetric (SSS) supercapacitor at 1 Ag1 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 aerogels and carbon nanotube have been used as electric double
layer capacitors (EDLCs) where charges are stored non-faradically
Among the various energy storage systems, supercapacitors are at the electrode-electrolyte interface; on the other hand, transition
important source of energy storage devices and power outputs. metal oxides and conducting polymers shows pseudocapacitive
Typically, supercapacitor shows reasonable energy with high behavior through redox mechanism at the electrode surface [4].
power density and long cycle life. There are growing demands for Mixed transition metal oxides (MTMO) with two different metal
the next generation flexible and lightweight energy storage devices cations have been studied extensively as an electrode material for
with high power density and high energy density, as their special supercapacitor to improve the energy density and overall perfor-
features and potential applications in variety of portable electronic mance [5]. The use of MTMO as an electrode material for
devices such as smart sensors, mobiles, flexible touch screen and supecapacitor, the storing of charge primarily originates from the
electronic newspaper etc [1]. Nanostructure electrode materials pseudocapacitive mechanism [6]. Furthermore, the presence of
have been extensively studied in supercapacitor due to their high complex chemical composition and the synergic effect of multiple
surface area which results in higher electrode-electrolyte contact valences of the metal cations in MTMOs are helpful to obtain the
area, short path length for cation transport and high power desirable electrochemical behavior. Recently, Fe-based spinel mixed
performance [2]. Currently, variety of electrode materials have transition metal oxides such as CoFe2O4 [7], NiFe2O4 [8]. and
potential candidates for supercapacitor which store/deliver energy MnFe2O4 [9] have attracted a great attention because it reach redox
with different working principles [3]. Activated carbon, carbon 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]
* Corresponding author. Tel.: + 91 712 2801170; fax: +91 712 2223230.
while Fe2O3 offers low environmental impact and variable oxidation
E-mail addresses: brsankapal@phy.vnit.ac.in, brsankapal@gmail.com state. Among the spinel metal ferrites, ZnFe2O4 is promising material
(B.R. Sankapal). 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 alcohol (PVA) and lithium perchlorate (LiClO4) were purchased from
important material with applications in lithium-ion batteries [12], Merck India private Ltd. The chemicals and solvents were of
chemical sensors [13] and photocatalytic activity [14]. analytical grade and used as received. Stainless steel (grade 304,
A very few reports are available for the utilization of ZnFe2O4 as 0.021 mm thick) were purchased locally and used as substrate.
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 2.1. Synthesis and reaction kinetics of ZnFe2O4 thin film formation
single electrode had a specific capacitance of 131 Fg1 and stable
cycling performance with 92% capacity retention over 1000 cycles The growth kinetics of thin film formation in the SILAR
[15]. Liu et al. investigated the ZnFe2O4 replica with biological method is based on the principle of ion-by-ion growth, which
hierarchical structure and showed a much higher specific involves the ion-by-ion deposition at nucleation sites on the
capacitance of 294 Fg1 at 10 mVs1 (single electrode) [16]. immersed surfaces [19]. ZnFe2O4 thin film was prepared by
However, the fabrication of ZnFe2O4 as an anode material capable SILAR method on stainless steel (SS) substrate. In this method,
to keep high specific capacitance, active long term cycling life ZnFe2O4 thin film were deposited by alternative immersion of
particularly when operating at high specific currents and good rate the substrate in two cationic precursors (0.05 M ZnSO4 and
capability still remains a great challenge. 0.1 M FeSO4 solution) and two anionic precursors (1% H2O2 and
Although various metal oxide or conducting polymers were 0.02 M NaOH solution). The schematic for the formation of
successfully synthesized by using different methods for super- ZnFe2O4 thin film by SILAR method is depicted in Fig. 1. A
capacitor, so far few studies has been reported for the fabrication of cationic precursor of ZnSO4 solution was complexed by using
symmetric supercapacitor device. Assembling symmetric super- aqueous ammonia (30% NH4OH) solution (pH 12) (I-beaker,
capacitor device using metal oxides as both anode and cathode 300 K). A well cleaned SS substrate was immersed in this
electrode material could simplify the fabrication procedure [17]. solution for 20 s where tetra ammonium zinc (II) complex get
Fe-based mixed transition metal oxides possess high hydrogen adsorbed onto the substrate surface due to the attractive forces
evolution potential in aqueous solution, thus making them a between the ions in the solution and surface of substrate [Fig. 1
promising candidate in symmetric supercapacitor device. (a)] [20] as per the following reaction:
This work focuses on the first report for the synthesis of
ZnFe2O4 thin films via successive ionic layer adsorption and Zn2þ þ 4NH4 OH ! ½ZnðNH3 Þ4 2þ þ 4H2 O ð1Þ
reaction (SILAR) method and its use as an electrode material for
supercapacitor. The SILAR method avoids unnecessary formation The reaction of pre-adsorbed zinc complex with H2O2 was
of precipitation and loss of materials as appeared in chemical bath performed by immersing the substrate in the H2O2 solution (II-
deposition (CBD). This process is advantageous for the synthesis beaker, 343 K) for 20 s to form Zn(OH)2 thin film [Fig. 1 (b)] as per
of nanostructures since the basic building blocks are ions instead the following reaction:
of atoms. It is a low cost, low temperature soft chemical solution 343K
½ZnðNH3 Þ4 2þ þ H2 O2 ! ZnðOHÞ2 þ NH4 OH ð2Þ
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 Then, the substrate with Zn(OH)2 thin film was dipped into
cathode and anode solidified in polyvinyl alcohol-lithium 0.1 M ferrous sulphate solution (III-beaker, 300 K) for 20 s in order
perchlorate (PVA-LiClO4) gel electrolyte and detail results are to absorb Fe2+ ions [Fig. 1 (c)]. Furthermore, the absorbed Fe2+ ions
discussed. were rinsed in double distilled water (DDW) for 10 s in order to
remove the loosely bounded Fe2+ ions. This is followed by dipping
2. Experimental the substrate in NaOH solution (IV-beaker, 343 K), where OH ions
react with Fe2+ ions [Fig. 1 (d)] and form FeOOH [21].
Iron (III) sulphate (FeSO4), zinc sulphate (ZnSO4), sodium 343K OH
hydroxide (NaOH), hydrogen peroxide (H2O2), ammonia, polyvinyl Fe2þ þ 2NaOH ! FeðOHÞ2 ! FeOOH ð3Þ

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.
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 cm1. 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 (Fg1), ‘ IdV’ is the total
integral area of the CV curve, ‘(Vc-Va)’ is an operational potential
window, ‘v’ represents the scan rate (mVs1) 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

region of 400–600 cm1 have been observed. High frequency band


R at 599 cm1 corresponds to the Zn-O tetrahedral stretching
I V ðtÞdt
E¼ ð7Þ vibration and the low frequency band at 433 cm1 corresponds
3:6m
to the octahedral stretching vibration of Fe-O [24]. In addition, the
vibration band at 1647 cm1 and 3443 cm1 are assigned to the O-
H bending and O-H stretching, respectively [25]. In as-deposited
E  3600
P¼ ð8Þ ZnFe hydroxide, band observed at 1095 cm1 shows the residual of
Td
lepidocrocite (F-FeOOH) [26]. The extra band at 1495 cm1 and
where, ‘Cs’ is the specific capacitance, ‘Id’ is discharge current, ‘Td’ is 1371 cm1 are due to C-H bending mode and symmetric stretching
the discharge time, ‘DV’ is the potential window, ‘m’ is the mass of of C-N [27], which is possibly from the surface contaminated
R
active material, ‘E’ is the energy density, ‘ V(t)dt’ is integral area of carbon, as usually observed in chemical deposited films [28]. In
the discharging curve and ‘P’ is the power density. annealed sample (573 K), the O-H stretching bond was likely to be
shifted towards higher frequency with decreasing in intensity due
3. Results and discussion to the release of hydroxide to form oxide. The band at 1124 cm1 is
due to the formation of Zn-O-Fe bond, similar appearance was
3.1. Structural and chemical bond analysis reported by Changlin et al. [29].
Further, ZnFe2O4 scratched powder sample were characterized
Fig. 2(a) shows the X-ray diffraction pattern (XRD) of as- by Raman spectrophotometer and the resulting spectra is depicted
deposited (ZnFe hydroxide) and annealed ZnFe2O4 thin films on SS in Fig. 2(c). ZnFe2O4 Raman spectra exhibits much stronger five
substrate. XRD pattern of as-deposited thin film without heat active Raman modes (A1g + Eg + 3F2g) at 210, 271, 335, 476 and
treatment represents an amorphous structure that there was no 648 cm1 which revealed cubic spinel structure of ZnFe2O4 sample.
noticeable diffraction peaks other than SS substrate. After It has been reported that, Raman signal of cubic spinel ferrite at
annealing at 573 K for 1 hour, broad tiny peaks appeared 648 cm1(above 600 cm1) is reasonably considered to have A1g
corresponding to (311), (222) and (440) planes of zinc ferrite symmetry of oxygen in tetrahedral AO4 group while the other low
with cubic spinel structure (JCPDS, no. 89-4926) confirming the frequency modes at 271 cm1(E2g) and at 210, 335, 476 cm1 (F2g)
formation of ZnFe2O4. These tiny peaks are attributed to the i.e. (Eg + 3F2g) representing the characteristics of the octahedral
existence of fine grains. Annealing at 773 K, peak intensity becomes sites (BO6) [30].
stronger alongwith the presence of trace amount of a-Fe2O3 was
observed. 3.2. Surface morphological studies
Fig. 2(b) shows the FTIR spectra of as-deposited ZnFe hydroxide
and annealed ZnFe2O4 powder samples in the range of 4000– Fig. 3 (a) shows the FE-SEM image of SS substrate as reference.
400 cm1 where two lattice vibrations of metal-oxygen bond in the Fig. 3 (b) shows FE-SEM image of ZnFe2O4 thin film on SS substrate

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.
S.S. Raut, B.R. Sankapal / Electrochimica Acta 198 (2016) 203–211 207

where the formation of nanoparticles of ZnFe2O4 attached on the 3.3. Electrochemical supercapacitor studies of ZnFe2O4 thin film
surface of nanoplate is observed. The cross-sectional SEM image
indicates the porous structured film onto SS substrate with the The electrochemical performance of ZnFe2O4 thin film as a
average film thickness about 41 mm as shown in Fig. 3 (c). The working electrode was studied in a three electrode system. The
chemical composition of the particles scratched from the film was effect of mass loading on cyclic voltammetry was studied by
analysed by EDS. The strong peak of Zn, Fe and O elements were controlling the number of SILAR cycles [Fig. 5(a)]. For 20 SILAR
observed in the spectrum which shows the inclusion of elements in cycles, the response of ZnFe2O4 was very close to pseudocapacitive
formed compound [Fig. 3 (d)]. behavior with good reversibility represented by two noticeable
In order to get insight view about shape, size and distribution of peaks, whereas electrode for 25 SILAR cycles exhibits only
ZnFe2O4 nanostructures, TEM and high resolution TEM (HR-TEM) oxidation peak and not showing reversibility. Above 25 cycles,
images have been recorded. A TEM image clearly shows the the film peel off due to the development of tensile stress that tends
ZnFe2O4 nanoparticles of size 10–20 nm [Fig. 4(a)]. The electron to cause delamination as the film becomes thicker [31]. Hence
diffraction pattern of the ZnFe2O4 displays several concentric supercapacitor properties were studied for 20 SILAR cycle
diffraction rings, indicating the nanocrystalline nature of the deposited film in order to get good reversibility. For finding the
formed ZnFe2O4 [Inset, Fig. 4(a)]. Fig. 4(b) shows HR-TEM image of suitable electrolyte concentration, the cyclic voltammetry (CV) of
ZnFe2O4 where clear evidence of the lattice fringes with ZnFe2O4 thin film electrode was examined in three concentrations
interplanar spacing of 0.242 nm is observed which corresponds of NaOH electrolyte in the voltage range of 0 to 1.0 V at 5 mVs1
to (222) plane of ZnFe2O4 exhibiting cubic spinel structure which scan rate [Fig. 5(b)]. With variation in concentration from 0.1 to
well supports with the results obtained by XRD studies. 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 mVs1) 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 Fg1 at
a 5 mVs1 scan rate. In addition, the specific capacitance still
remains to 230 Fg1 at 100 mVs1 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 Whkg1 and 1.87 kWkg1, respectively at current
density of 2.72 Ag1. 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
Fig. 4. (a) TEM image of ZnFe2O4 (inset is electron diffraction pattern of ZnFe2O4) appeared in chemical bath deposition which can further reduce the
and (b) HR-TEM image of ZnFe2O4. 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 mVs1 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 mVs1 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 plot consist of experimental and fitted spectra, based on the
requirement for supercapacitor electrode; cycling stability of equivalent circuit proposed for ZnFe2O4 thin film electrode. Inset of
ZnFe2O4 thin film electrode was tested using CV measurements in Fig. 6(d) shows the small semicircle arc in high frequency region
1 M NaOH electrolyte at 50 mVs1 scan rate [Fig. 6 (c)]. It was and inclined line in the low frequency region. High frequency
observed that the ZnFe2O4 thin film electrode showed 72% intercept on real axis represents the Rs in combined resistance
capacitance retention over 1000 cycles of their initial capacitance. including ionic resistance of electrolyte, intrinsic resistance of
Decrease in specific capacitance might be due to the loss of substrate and contact resistance of the interface of active material/
electrical contact between the active materials and wetability issue current collector whereas semicircle arc corresponds to the Rct and
[38]. electrode/electrolyte interface [39]. The appearance of a CPE i.e.
Electrochemical impedance spectroscopy (EIS) measurement of constant phase elements may arise due to the porosity of the
ZnFe2O4 thin film electrodes were performed at open circuit electrode materials and W is the Warburg impedance which
potential in the frequency range from 0.1 Hz to 15 kHz in order to correlated with the frequency dependence of ion diffusion/
obtain the information of charge transfer resistance (Rct), solution transport into the pores on the surface of the electrode during
resistance (Rs) and capacitive behavior. Fig. 6(d) shows the Nyquist 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 mVs1 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 (Ag1) Specific Capacitance (Fg1) Energy Density (Whkg1) Power Density (Wkg1)
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 g1) Energy density (Wh kg1) Power density (W kg1) Ref.
NiO/MWNT PVA/LiClO4 0.6 to 0.6 24 at 5 mV s1 – – [41]
Co(OH)2 L-1 M KOH 0 to 1.2 44 at 5 mV s1 3.96 42(kW kg1) [42]
Fe3O4 L-1 M H2SO4 0 to 1 15 at 0.25 A g1 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 g1 4.5 277 Present work

frequency spike. The Rs and Rct values of the fitted EIS spectra of process is due to the slight degradation of the gel electrolyte and
ZnFe2O4 thin film electrode are 0.8 V cm2 and 1.05 V cm2, ZnFe2O4. In addition to this, electrochemical impedance analyses
respectively. of ZnFe2O4-SSS supercapacitor device were performed at open
circuit potential in the frequency range from 0.1 Hz to 100 kHz.
3.4. Electrochemical properties of solid-state symmetric (SSS) Nyquist plot consist of experimental and fitted spectra based on
supercapacitor device the equivalent circuit proposed for ZnFe2O4-SSS supercapacitor
device shows the half semicircle at high frequency because of the
Solid-state symmetric (SSS) supercapacitor device was fabri- faradaic charge transfer resistance and 45 phase angle in the low
cated by using ZnFe2O4 thin films as a flexible electrode frequency region, corresponding to the Warburg region and related
(2.3  2 cm2) sandwiched by polyvinyl alcohol (PVA) LiClO4 gel to the diffusion of electrolyte ions within the pores of the electrode
electrolyte. The cyclic voltammograms (CV) of the flexible [Fig. 8 (d)]. The plot demonstrates a very small equivalent series
ZnFe2O4-SSS device within the potential windows of 0 to +1.0 V resistance of 0.58 V cm2 and the charge transfer resistance of
at different scan rates (2 to 100 mVs1) are demonstrated in 4.43 V cm2 [inset Fig. 8 (d)]. A relatively high charge transfer
Fig. 7(a). The CV curves maintain their shape and current under the resistance is due to the resistive nature of the device and low ionic
CV curves increases with the scan rate which reveals the capacitive conductivity of the solid electrolyte [46].
performance of ZnFe2O4-SSS device.
The variation of specific capacitance with scan rate is shown in 4. Conclusions
Fig. 7(b). The maximum specific capacitance of the ZnFe2O4-SSS
supercapacitor device is found to be 26 Fg1 at 2 mVs1 scan rate Successive ionic layer adsorption and reaction (SILAR) method
based on the total mass (1.80 mg) of active material in two was employed successfully for the synthesis of ZnFe2O4 thin films.
electrodes. The estimated values of specific capacitance are found The film exhibited a maximum specific capacitance of 471 Fg1 at
to be decreases from 26 to 10 Fg1 with increase in scan rate (2– 5 mVs1 scan rate, with 53.22 Whkg1 energy density and
100 mVs1). 1.87 kWkg1 power density at current density of 2.72 Ag1 in
The galvanostatic charge-discharge of ZnFe2O4-SSS super- 1 M NaOH electrolyte. Furthermore, ZnFe2O4-SSS supercapacitor
capacitor device at different current density was studied in order device was fabricated using PVA–LiClO4 gel electrolyte. The device
to find out the energy density, power density and device exhibits an excellent electrochemical performance with potential
performance [Fig. 8 (a)]. The Ragone plot relating to energy windows of 1.0 V having good energy and power density as well as
density and power density is shown in Fig. 8 (b). ZnFe2O4-SSS long cycle life. Used SILAR method is simple, low cost and
supercapacitor device exhibited a maximum specific capacitance applicable for large scale production of electrode materials
of 32 Fg1, high energy density of 4.47 Whkg1 with power density towards supercapacitor application.
of 277 Wkg1 at 1 Ag1 current density. Table 1 provides the values
of specific capacitance, energy density, power density at different Acknowledgements
current density of ZnFe2O4-SSS supercapacitor device. The
obtained energy density 4.47 Whkg1 is higher than previously BRS would like to thank the DST-SERB project, Govt. of India
reported symmetric supercapacitor based on graphene @ carbon (Do. No: SB/S2/CMP/032/2013; 4/06/2013) and SSR thanks to VNIT,
cloth (1.64 Whkg1) [40]. Inset Fig. 8(b) shows the photoimage of Nagpur for Fellowship.
glow up of light emitting diode (LED) by using series combination
of two ZnFe2O4-SSS supercapacitor device. Table 2 summarizes References
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