Journal of Industrial and Engineering Chemistry 71 (2019) 191–200

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Facile synthesis of pristine FeS2 microflowers and hybrid rGO-FeS2

microsphere electrode materials for high performance symmetric
capacitors
Balamuralitharan Balakrishnana , Suresh Kannan Balasingamb ,
Karthick Sivalingam Nallathambic, Ananthakumar Ramadossd , Manab Kundue,
Jin Soo Baka , In Ho Choa , Prabakar Kandasamya , Yongseok Junb , Hee-Je Kima,*
a
School of Electrical and Computer Science Engineering, Pusan National University, Busan-46241, Republic of Korea
b
Department of Energy Engineering, Konkuk University, Seoul-05029, Republic of Korea
c
Department of Chemistry, Bharathiar University, Coimbatore-641046, India
d
Laboratory for Advanced Research in Polymeric Materials (LARPM), Central Institute of Plastic Engineering and Technology(CIPET), Bhubaneswar-751024,
India
e
SRM Research Institute, Department of Chemistry, SRM Institute of Science and Technology, Chennai-603203, India

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

Article history: Iron pyrite (FeS2) is an interesting mineral in the transition metal dichalcogenide group due to its high
Received 23 July 2018 abundance in the earth’s crust which can be used for various electrochemical energy storage applications,
Received in revised form 6 November 2018 such as batteries and supercapacitors; however, it suffers from low rate capability and poor cycle
Accepted 9 November 2018
performance, which hampers its use from large-scale commercial applications. In the present study, iron
Available online 17 November 2018
disulfide microspheres anchored onto a reduced graphene oxide matrix (rGO-FeS2 hybrid) were grown
using a superficial hydrothermal method. For comparison, rGO-free iron disulfide material was
Keywords:
synthesized under the same hydrothermal conditions, and uniformly distributed FeS2 micro-size flowers
Supercapacitors
Electrochemical energy storage
were formed. The energy storage capacity of both electroactive materials (FeS2 and rGO-FeS2 hybrid
rGO-FeS2 material) was tested for supercapacitor applications in a symmetric cell configuration. The pristine FeS2
Areal capacitance microflower electrode exhibited an areal capacitance of 70.98 mF cm
2 at 5 mV s
1. On the other hand,
Hydrothermal method the rGO-FeS2 hybrid microsphere electrode exhibited an enhanced areal capacitance of 112.41 mF cm
2 at
the same scan rate with an excellent capacitance retention of 90% over 10,000 cycles. The improved
electrochemical performance of the rGO-FeS2 hybrid material is due mainly to its improved electrical
conductivity, high surface area indicating an enhanced electron, and ion transfer mechanism. This study
suggests that the rGO-FeS2 hybrid electrode material has potential applications in energy storage devices.
© 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction and the type of electrolyte are the two important factors that can
increase the energy density of supercapacitors [1–3]. In general,
The electric vehicles demand extraordinary charge storage supercapacitors can be classified into two types based on their
capacity, compact, rapid charging, and long durable energy storage charge storage behavior: electrochemical double layer capacitors
devices. Supercapacitors (also known as ultracapacitors) are one (EDLCs), where ion adsorption/desorption occurs at the electrode/
type of energy storage device that nearly meet the above- electrolyte interface; and pseudocapacitors (involving fast-farada-
mentioned requirements, but their low energy density compared ic charge transport reactions) [4–7]. Carbon-based materials are
to that of conventional batteries is a major limitation. Increasing the best-known electrodes for the double-layer capacitance, but
the energy density of supercapacitors while retaining their high- they have low energy densities [8–14]. To solve this issue, various
power density is a great challenge in this research field. pseudocapacitance materials such as transition metal oxides
Undoubtedly, the inherent properties of an electrode material (TMOs), conducting polymers, and transition metal dichalcoge-
nides (TMDs) have been studied extensively as electroactive
materials [15–20]. Recently, TMDs-based pseudocapacitance
* Corresponding author. materials have attracted researchers mainly due to its higher

https://doi.org/10.1016/j.jiec.2018.11.022
1226-086X/© 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
192 B. Balakrishnan et al. / Journal of Industrial and Engineering Chemistry 71 (2019) 191–200

electrical conductivity than TMOs, multivalent redox states, good continuously for one hour. In a typical procedure, precisely 1.35 g of
specific capacitance, and excellent cyclic stability [19,21–31]. Until FeCl36H2O and 3 g of CH3CSNH2 were weighed and dissolved in
now, various TMDs such as MoS2, MoSe2, WS2, WSe2, CoS, NiS, FeS, 48 ml of DI water with constant stirring for 60 min to obtain
and CuS, have been assessed as electrode materials for super- uniform dissolution. Subsequently, 2 ml of hydrazine hydrate was
capacitor applications [32–48]. Among them, iron sulphide has added drop-wise to the resulting solution with constant stirring.
recently been explored as an electrode material for various energy Finally, the GO dispersion was added drop-wise to the above
conversion and storage devices, such as photovoltaics, batteries, precursor solution, followed by continuous stirring for 20 min to
and supercapacitors due to its natural abundance, low cost, good ensure a uniform dispersion of GO in the precursor solution. The
stability, narrow band gap (0.95 eV), high optical absorption resulting precursor was transferred to an 80 ml capacity Teflon-
coefficient (6  105 cm
1), multivalent redox activity, and eco- coated container, which was placed into a stainless-steel autoclave
friendly nature [49,50]. In particular, FeS2 exhibits the highest and sealed. The autoclave was heated in a hydrothermal apparatus
theoretical capacity of 890 mAh g
1, which makes it as a very at 200  C for 24 h. Once the hydrothermal reaction was finished, the
attractive, inexpensive energy storage material for lithium-ion autoclave was cooled naturally to room temperature. The resulting
batteries [51]. On the other hand, pure iron sulphide has some product was washed thoroughly with DI water followed by ethanol
inherent disadvantages, such as low surface area, large volume to eliminate the undesirable impurities and then dried in an
changes, and low specific capacitance, which confine their electric oven at 70  C for overnight. For comparative purposes,
electrochemical performance on the device scale. To overcome pristine FeS2 material was also synthesized using a similar method
these issues, a new type of electrode material known as hybrid without the addition of GO.
materials are attracting research attention to achieve improved
performance. Material characterization
In a hybrid material, a highly conducting carbon-based EDLC
material is mixed with a redox-active pseudocapacitive material. The surface morphology and elemental composition of the as-
The addition of carbon-based materials not only improved the synthesized material were examined by field emission scanning
electrical conductivity, but also enhanced the electrochemical electron microscopy equipped with energy dispersive X-ray spectros-
active surface area of the electrode materials. Reduced graphene copy (FE-SEM, SUPRA40VP). The surface area of the electroactive
oxide (rGO) is one of the most studied versatile carbon materials material was estimated by nitrogen adsorption and desorption
that can be merged with other TMDs or TMOs to obtain a large isotherms (Micromeritics ASAP 2020 V3.04G) and calculated using
surface area, high electrical conductivity in addition to outstanding the Brunauer–Emmett–Teller (BET) method. The crystal structure of
electrochemical properties, such as superior specific capacitance the as-synthesized material was confirmed by X-ray diffraction (XRD)
and extended cyclic stability. To the best of the authors’ knowledge, using Cu Kα emission (l = 1.5418 Å) over the 2u range of 10–80 at a
only a few studies have assessed the use of mixed iron sulphide scan rate of 2 min
1. The Raman spectra were recorded over the
(FeS2 [pyrite] and Fe3S4 [greigite]), FeS, and hybrid rGO-FeS wavelength range of 200 to 2000 cm
1 using a single-stage
nanoparticles for supercapacitor applications. Chen et al. synthe- spectrometer (LabRAM HR Evolution; Horiba, Japan) with 532 nm
sized pyrite (FeS2) with greigite (FeS) impurity nanobelts via laser excitation. The chemical composition and oxidation state of
hydrothermal method and applied them to aqueous super- the elements were examined by X-ray photoelectron spectroscopy
capacitors in a three-electrode setup [52]. Zhao et al. synthesized (XPS, Thermo Fisher, UK) equipped with Al Kα radiation.
a mixture of three different phase FeS materials, in which
elemental iron and sulfur impurities are also present. On the Electrochemical measurements
other hand, their rGO-FeS showed superior supercapacitive
performance than that of the bare FeS [53]. However, symmetric The FeS2 and rGO-FeS2 hybrid electrodes were fabricated using
capacitors using phase pure FeS2 (pyrite) microflowers and hybrid a stainless steel (SS) plate current collector. The exact coating area
rGO-FeS2 microspheres synthesized by a simple one-step hydro- of the electrode was 1 cm
2. The as-synthesized electroactive
thermal method have not been reported. Herein, we report a facile material, carbon black, and poly (vinylidene fluoride) were mixed
synthesis method that does not require any high temperature post- in a mass ratio of 80:10:10. To this, N-methyl-2-pyrrolidone
annealing treatment which could exhibit a single-phase FeS2 solvent was added and ground to achieve a homogeneous slurry.
structure. The as-synthesized pristine FeS2 microflowers and The slurry was coated immediately onto the stainless steel current
hybrid rGO-FeS2 microspheres were used as electrode materials for collector using a brush. The electroactive material coated substrate
symmetrical supercapacitors. Interestingly, the long-term stability was then used as a single electrode. To fabricate a symmetrical cell,
of the rGO-FeS2 hybrid material-based symmetric capacitor two electrodes were sandwiched together using Whatman filter
showed approximately 90% capacitance retention, which is paper as a separator in the standard split cell. To this a few drops of
superior to its pristine FeS2 counterpart (48%). Overall, this article 1 M Na2SO4 solution was added as the electrolyte. The split test cell
brings new opportunities to the design of rGO-FeS2-based hybrid was assembled and then left to stand for a few hours to ensure
materials for enhanced electrochemical energy storage properties uniform soaking of the electrodes in the electrolyte solution prior
in supercapacitors. to the electrochemical measurements. The electrochemical prop-
erties of the as-prepared electrodes were measured using a single
Experimental channel BioLogic instrument (model, SP-150) at room tempera-
ture. The cyclic voltammetry (CV) curves were recorded at various
Synthesis of rGO-FeS2 hybrid materials and FeS2 microflowers scan rates (5, 10, 25, 50, 75, 100, 125, and 150 mV s
1) in a potential
window of 0 to 1 V. The electrochemical impedance spectroscopy
All precursors used in this experiment were of analytical grade (EIS) measurements were carried out over the frequency range of
and used as received. The precursors, iron (III) chloride hexahy- 100 kHz to 0.1 Hz with an AC amplitude of 10 mV. The galvanostatic
drate (FeCl36H2O), thioacetamide (CH3CSNH2), and hydrazine charge-discharge (GCD) curves were recorded at different current
hydrate (NH2 NH2H2O) were purchased from Sigma Aldrich. densities (0.2 to 0.6 mA cm
2) in the potential window of 0 to 1 V.
Graphene oxide (GO) was synthesized from natural graphite The long-term cycling stability of the symmetric cell was evaluated
powder using a modified Hummers method [21]. A 0.2 g sample of using GCD measurements at a high current density of 0.3 mA cm
2
GO was mixed with 23 ml of deionized (DI) water and sonicated for 10,000 cycles.
 B. Balakrishnan et al. / Journal of Industrial and Engineering Chemistry 71 (2019) 191–200 193

Calculation of capacitance

The areal capacitance of the symmetric Cdevice (Cdevice, F cm
2)

was calculated based on the CV measurements using the following
equation:
Z  
C F cm
2 ð1Þ
IðV Þdv

device¼ vADV

Where v is the scan rate (V s
1); A is the geometric area of an

R
electrode (cm
2); DV is the potential window (V); and I(V)dv is
the integral area (A.V) of the CV loop.
The Cdevice value was also calculated based on the GCD
measurements using the following equation:
 
C device¼ IDt F cm
2 ð2Þ
ADV
Fig. 2. XRD patterns of the synthesized pristine FeS2 microflowers and hybrid rGO-
where I is the discharge current (A); Dt is the discharge time (s); A FeS2 microsphere materials.
is the geometric area of an electrode (cm
2); and DV is the
potential window (V). [54,55], respectively. In case of the rGO-FeS2 hybrid material, an
The areal capacitance of a single electrode (Cs) was calculated additional rGO peak appeared at 24.58 2u, which was assigned to
using the following equation: the (002) plane of rGO.
Further confirmation of the synthesized pristine FeS2 and
Cs = 2x Cdevice (F cm
2) (3)
hybrid rGO-FeS2 material was obtained by Raman spectroscopy.
where Cdevice is the areal capacitance of the symmetric device Fig. 3 shows the Raman spectra of pristine FeS2 microflowers and
(F cm
2); which could be obtained from the CV and GCD curves rGO-FeS2 hybrid materials. Fig. 3a shows the Raman spectrum of
using equations 1 and 2, respectively; and Cs is the areal the pristine FeS2 material, in which the characteristic peaks at
capacitance of a single electrode (F cm
2). 344 cm
1, 375 cm
1, and 429 cm
1 corresponds to the Eg mode
vibration of sulfur atoms, Ag mode of S–S in phase stretching, and
Results and discussion Tg mode of FeS2, which can be described as a coupled liberation and
stretching or their combination [56–58]. The absence of peaks at
Fig. 1 shows a schematic diagram of the procedure for the 200–300 cm
1 indicates the lack of FeS and oxides in the
synthesis of pristine FeS2 and rGO-FeS2 hybrid materials. The synthesized sample, which further confirms the phase purity of
crystal structure and phase purity of the freshly prepared iron the FeS2 material [55]. Fig. 3b shows the Raman spectrum of the
disulphide microflowers and hybrid rGO-FeS2 microspheres were hybrid rGO-FeS2 microsphere material, which confirms the
examined by XRD. Fig. 2, shows the XRD patterns of pristine FeS2 presence of all three characteristic modes of FeS2 (Eg, Ag, and Tg)
microflowers and hybrid rGO-FeS2 microsphere materials. The with a small shift in the peak position. In addition to these peaks,
XRD peaks appears at 28.63 , 33.16 , 37.14 , 40.82 , 47.44 , 56.39 , two other high intensity peaks were also observed at 1353 and
59.09 , 61.78 , 64.38 , 76.64 and 79.07 2u, which were indexed to 1586 cm
1, which were assigned to the characteristic D and G
the (111), (200), (210), (211), (220), (311), (222), (023), (321), (331), bands of rGO in the rGO-FeS2 hybrid materials. The intensity of the
and (420) planes of the cubic phase FeS2 (JCPDS card no. 42-1340) D band is stronger than that of the G band suggesting that GO was

Fig. 1. Schematic diagram of the synthesis of (a) FeS2 microflowers and (b) hybrid rGO-FeS2 microsphere materials.
194 B. Balakrishnan et al. / Journal of Industrial and Engineering Chemistry 71 (2019) 191–200

Fig. 3. Raman spectra of (a) FeS2 microflowers and (b) hybrid rGO-FeS2 microsphere materials.

reduced to rGO via a high temperature hydrothermal process. The view (Fig. 4d) showed that FeS2 nanoparticles were aggregated
D/G band intensity ratio of the rGO-FeS2 hybrid material was 1.26, together to form micron-size spheres (Fig. 4d). To confirm the
which also confirms the effective reduction of GO to rGO, which led uniform distribution of FeS2 microspheres and rGO sheets, the
to increased disorder and defective rGO sheets [15,35,59,60]. These corresponding energy dispersive X-ray spectroscopy (EDS) images
results confirmed the formation of pristine FeS2 and rGO-FeS2 were mapped with the FE-SEM images as shown in Fig. 5. EDS
hybrid materials. revealed a sulfur to iron atomic ratio of approximately 2.20, which
The morphology of the as-synthesized pristine FeS2 and rGO- is close to the value of 2.
FeS2 hybrid materials was observed by FE-SEM, as shown in Fig. 4. a The high surface area and porosity of an electroactive material
and b present FE-SEM images of the pristine FeS2 electroactive has a great impact on the electrochemical energy storage activity
material, showing a microflowers structure with an average size of and provides the high specific capacitance. The nitrogen adsorp-
2.5 mm. Fig. 4b shows a high magnification image of a micro- tion-desorption isotherms and Barrett–Joyner–Halenda (BJH) pore
flower, wherein the petals are very thin and each petal size is in the size distribution analysis of pristine FeS2 microflowers and the
order of few hundred nanometers. Fig. 4c presents FE-SEM images rGO-FeS2 hybrid materials are presented in the supporting
of the rGO-FeS2 hybrid material, in which FeS2 microspheres were information (Supporting information Fig. S1). The BET surface
distributed uniformly over the surface of the rGO sheets. A closer area and mean pore diameter of pristine FeS2 microflowers were

Fig. 4. FE-SEM images of (a and b) pristine FeS2 microflowers and (c and d) hybrid rGO-FeS2 microspheres.
 B. Balakrishnan et al. / Journal of Industrial and Engineering Chemistry 71 (2019) 191–200 195

Fig. 5. FE-SEM image of pristine FeS2 microflower (a) and the corresponding mapping images for each elements (b–d). FE-SEM image of hybrid rGO-FeS2 microsphere
material (e) and the corresponding mapping images for each elements (f–i). The high magnification FE-SEM image of FeS2 microsphere is shown in (j), the corresponding
energy dispersive spectrum of FeS2 microsphere part is shown in (k) and the quantitative analysis of Fe & S elements from the spectrum is in shown in (l).

3.35 m2 g
1 and 14.40 nm, respectively. Interestingly, the BET peak at 284.60 eV was assigned to the presence of non-oxygenated
surface area and the mean pore diameter of the rGO-FeS2 hybrid C-C bonds of sp2 hybridized carbon atoms. The absence of oxygen
material was approximately 16.94 m2 g
1 and 3.76 nm, respective- functional groups in the C 1 s spectrum (C–O, C¼O, and O–C¼O)
ly. The specific BET surface area of the rGO-FeS2 hybrid materials confirmed the complete removal of oxygenated functional groups
was five times higher than that of the pristine FeS2 microflowers. In during the high temperature hydrothermal process [60]. The FeS2
addition, the pore size distribution of the rGO-FeS2 hybrid material microflower material also showed similar Fe 2p and S 2p spectra,
further showed that the dominant pore size distribution was in the which confirms the formation of pristine FeS2 material (See
mesoporous range. This confirms that the introduction of rGO Supporting information Fig. S2). These results further confirm the
could enhance the specific surface area and mesoporous nature of formation of pristine FeS2 and rGO-FeS2 hybrid materials [66].
the hybrid material significantly. The increased BET surface area The electrochemical performance of the as-synthesized pristine
and mesoporous nature of rGO-FeS2 hybrid material plays a FeS2 microflowers and hybrid rGO-FeS2 microsphere electroactive
significant role, which enlarges the electrode–electrolyte interface materials were assessed in a symmetric-cell configuration using a
resulting in higher charge storage performance compared to the 1 M aqueous Na2SO4 electrolyte. The geometric specific capaci-
pristine FeS2 microflowers [61]. tance of the device (Cdevice) and the corresponding areal
The chemical composition and surface electronic state of the as- capacitance of a single electrode (Cs) were measured by cyclic
synthesized pristine FeS2 microflowers and hybrid rGO-FeS2 voltammetry (CV) and galvanostatic charge-discharge (GCD)
microsphere materials were verified by XPS. Fig. 6a shows the measurements. Fig. 7a presents the comparative CV curves of
survey spectrum of the rGO-FeS2 hybrid material. The XPS results pristine FeS2 microflowers and hybrid rGO-FeS2 microspheres-
confirmed the presence of Fe 2p, S 2p, and C 1 s in the rGO-FeS2 based symmetric cells measured at a scan rate of 25 mV s
1.
hybrid material. The peaks at 707.80 and 720.65 eV were attributed Compared to the pristine FeS2 microflower-based symmetric cell,
to Fe 2p3/2 and Fe 2p1/2, which are the characteristic peaks of the +2 the rGO-FeS2 hybrid material-based symmetric cells showed a
oxidation state of iron atoms (Fe2+) (Fig. 6b) [62,63]. The presence higher integrated cyclic voltammetry area and more pronounced
of a Fe–O peak at 711.63 eV may be due to surface adsorbed O2 [64]. redox peaks. This enhanced performance of the rGO-FeS2 hybrid
Fig. 6c shows the S 2p core level spectrum, in which the peaks material-based symmetric cell may be due to the synergetic effects
observed at binding energies of 162.38 and 163.47 eV corresponds of the higher active surface area of rGO and the redox active
to the S 2p3/2 and S 2p1/2 peaks, respectively which confirms the property of the FeS2 microspheres. In addition, the microflower
presence of the S2
states in the FeS2 material. Fig. 6d presents the structure of FeS2 provides an open porous structure for the easy
C 1s core level spectrum of the rGO-FeS2 hybrid materials [65]. The access of electrolyte ions to the entire surface of active materials.
196 B. Balakrishnan et al. / Journal of Industrial and Engineering Chemistry 71 (2019) 191–200

Fig. 6. High-resolution X-ray photoelectron spectra of hybrid rGO-FeS2 microsphere materials: (a) survey; (b) Fe 2p; (c) S 2p; (d) C 1s.

The electrochemical reaction of the Fe atoms (from FeS2) with the 150 mV s
1; this capacitance retention value is promising when
electrolyte ions, indicates pseudocapacitance behavior, as shown compared with the pristine FeS2 microflower-based symmetric
in Eq. (4) [15]. cell. This highlights the good rate capability of the rGO-FeS2 hybrid
electrode material. The good rate capability was attributed mainly
FeS2 + xNa+ + xe
$ NaxFeS2 (4)
to the presence of FeS2 microspheres that were dispersed
+
where x is the mole fraction of inserted Na ions. uniformly over the surface of the rGO matrix, which enhances
Fig. 7b presents the CV results of the pristine FeS2 microflower- the electrical conductivity and the electrochemical active surface
based symmetric cell at different scan rates from (5 to 150 mV s
1) area for the efficient accessibility of electrolyte ions.
over the potential window of 0 to 1 V. The areal capacitance of the Fig. 7d presents the relationship between the specific capaci-
pristine FeS2-based symmetric cell was 35.48 mF cm
2, and the tance of a single electrode vs scan rate. The obtained specific
calculated single electrode areal capacitance was 70.97 mF cm
2 at capacitance of the rGO-FeS2 hybrid electrode is approximately 1.5
a scan rate of 5 mV s
1. Compared to the pristine FeS2 microflower- times higher than that of the pristine FeS2 microflower-based
based symmetry cell, the hybrid rGO-FeS2 microsphere-based electrode. In addition, the performance of the rGO-FeS2 hybrid
symmetric cells exhibited a higher areal capacitance of 56.20 mF electrode was remarkably high compared to that reported for other
cm
2. The corresponding areal capacitance of a single electrode TMDs. For example, an amorphous MoSx-coated carbon fiber paper
was calculated to be 112.41 mF cm
2. In addition, the rate single electrode showed a specific capacitance of 40.8 mF cm
2 at a
capability of the rGO-FeS2 hybrid material-based symmetric cell scan rate of 5 mV s
1 [33]. In contrast, the present rGO-FeS2 hybrid
was tested at various scan rates from 5 to 150 mV s
1 between the electrode showed 2.13 times higher specific capacitance than the
potential windows of 0 to 1 V, as shown in Fig. 7c. The CV curves amorphous MoSx and 2.43 times higher capacitance than the
clearly showed a proximate quasi rectangular shape, which hybrid graphene-MnSe2 (46.2 mF cm
2 at 5 mV s
1). [60] In
affirmed the ideal EDLC behavior of the electrode and a pair of addition, the areal device capacitance of the present work
redox peaks of the iron (Fe2+) ions, indicates the pseudocapaci- (Cdevice = 33.85 mF cm
2 @ 25 mV s
1) was 7 times higher than
tance behavior. From the CV measurements, it was observed that the previously reported VS2 Ultrathin nanosheet-based symmetric
increasing the scan rate led to an increase in the area of the CV capacitors (4.76 mF cm
2 @ 20 mV s
1) [67,68]. The enhanced
curves and the peak current density. Approximately 83% capaci- electrochemical performance of the as-prepared hybrid rGO-FeS2
tance was retained when the scan rate was increased from 75 to microsphere electrode material was attributed mainly to the
 B. Balakrishnan et al. / Journal of Industrial and Engineering Chemistry 71 (2019) 191–200 197

Fig. 7. (a) CV curves of the FeS2 microflowers and hybrid rGO-FeS2 microspheres-based symmetric cells measured at a scan rate of 25 mV s
1, (b and c) CV curve of FeS2
microflowers and rGO-FeS2 hybrid material-based symmetric cells measured at different scan rates from 5 to 150 mV s
1, and (d) Relationship between the areal specific
capacitance of a single electrode vs scan rate.

following reasons. (i) rGO nanosheets with the combination of a behaviour. This observation is also consistent with the CV results.
uniform distribution of FeS2 microspheres with a high surface area [67,68] A similar trend was also observed for the rGO-FeS2 hybrid
(when compare to pristine FeS2 microflowers), which facilitates a material-based symmetric devices (See Fig. 8c). The areal specific
large electrochemically active surface area for the effective capacitance of the symmetrical device was calculated using
adsorption of ions from the electrolyte. (ii) The FeS2 microspheres equation 2 and the corresponding single electrode capacitance
consist of an agglomeration of nanosize seed-like structure that was calculated using equation 3. Based on the discharge time from
help to improve the surface redox reaction of FeS2 with Na+ ions the GCD curve, the specific capacitance of the rGO-FeS2 hybrid
intercalation. (iii) The presence of rGO nanosheets further electrode was calculated to be approximately 52.8 mF cm
2 at a
enhances the electrical conductivity and reduces the overall current density of 0.2 mA cm
2, which was 1.7 times higher than
resistance of the rGO-FeS2 hybrid electrode. that of the pristine FeS2 microflower electrode (31.52 mF cm
2) and
The electrochemical properties of the electrodes were tested by 1.6 times higher than of the hybrid G-MnSe2 electrode (33 mA
galvanostatic charge/discharge (GCD) techniques. Fig. 8a presents cm
2) [60]. When the current density was increased from 0.2 to
the GCD curves of the pristine FeS2 microflowers and hybrid rGO- 0.6 mA cm
2, the specific capacitance of a single electrode
FeS2 microsphere-based symmetrical cells measured at a current decreased due to the insufficient time and less diffusion of
density of 0.2 mA cm
2. The rGO-FeS2 hybrid electrode showed a electrolyte ions (Na+ ions) to the inner part of the electrode surface.
prolonged discharge time and higher specific capacitance than the Interestingly, the capacitance retention of the rGO-FeS2 hybrid
pristine FeS2 microflower-based symmetric cells. This is due to the electrode was approximately 49% when the current density was
higher surface area of the electrode material, which extends the increased from 0.2 to 0.6 mA cm
2; this capacitance retention
electrode/electrolyte interface, resulting in a higher Cs value. The value was higher that of the pristine FeS2 microflower electrode
GCD performance of the pristine FeS2 microflowers and hybrid (35.25%). The enhanced specific capacitance of the rGO-FeS2 hybrid
rGO-FeS2 microspheres-based symmetric cells was measured at electrode was attributed to the high surface area and high electrical
different current densities from 0.2 to 0.6 mA cm
2 in an aqueous conductivity of the rGO nanosheets. Fig. 8d shows the relationship
1 M Na2SO4 electrolyte. Fig. 8b presents the GCD curves of the FeS2 between the specific capacitance of a single electrode and the
microflower-based symmetric cell measured at different current current density for both materials (pristine FeS2 microflowers and
densities. The GCD curves clearly show that the triangular shape hybrid rGO-FeS2 microspheres). Supporting information Fig. S3
charge-discharge profile with a slight deviation in linearity which presents a Ragone plot of the rGO-FeS2 hybrid materials and FeS2
confirms the pseudocapacitance contribution in addition to EDLC microflower-based symmetric cells. The energy density (E) and
198 B. Balakrishnan et al. / Journal of Industrial and Engineering Chemistry 71 (2019) 191–200

Fig. 8. (a) GCD curve of FeS2 microflowers and rGO-FeS2 hybrid material-based symmetric cells measured at a current density of 0.2 mA cm
2, (b and c) GCD curve of FeS2
microflowers and rGO-FeS2 hybrid material-based symmetric cells measured at different current densities, and (d) the relationship of areal specific capacitance vs current
density.

Fig. 9. (a) Long-term stability of the FeS2 microflowers and rGO-FeS2 hybrid material-based symmetric cells measured at a high current density of 0.3 mA cm
2. (b) EIS spectra
of FeS2 microflower-based symmetric cells (green line), rGO-FeS2 hybrid material-based symmetric cells measured before the long-term stability test (first cycle, blue line)
and after 10,000 cycles (red line).
 B. Balakrishnan et al. / Journal of Industrial and Engineering Chemistry 71 (2019) 191–200 199

power density (P) were calculated using the following equations. The lower Rct value of the rGO-FeS2 hybrid material-based
[60]: symmetric cell indicates the high electrical conductivity and good
synergistic effects of the rGO and FeS2 electrode materials. In
0:5xCdevice xV 2  
E¼ Wh m
2 ð5Þ addition, in the low-frequency region, an almost perpendicular line
3:6 (almost perpendicular to the real-axis) was observed, which
indicates the enhanced capacitive behavior compared to the
pristine FeS2 microflower-based symmetric cells. Compared to the
Ex 3600   pristine FeS2 microflowers, the hybrid rGO-FeS2 microsphere-
P¼ W cm
2 ð6Þ based symmetric cells exhibited lower Rs and Rct values, because it
Dt
represents the high electrical conductivity of the electrode
where Cdevice is the areal capacitance of the device calculated from material. After 10,000 cycles, the Rct value of the hybrid rGO-
the GCD measurements (F cm
2); V is the potential window (V); FeS2 microsphere-based symmetric cells increased from 2.48 to
and Dt is the discharge time (s). 2.81 V. These results show that the hybrid rGO-FeS2-microsphere
The hybrid rGO-FeS2 microspheres-based symmetric cell exhib- based electrode material is one of the most promising candidates
ited an energy density of 7.80 mWh cm
2 (equivalent to Cdevice = owing to its high areal capacitance and excellent cyclic stability
56.20 mF cm
2 for a device) at a corresponding power density of [22,71,72].
212.90 mW cm
2, and it retained half of its energy density (3.5 mWh
cm
2) even at a higher power density of 466.6 mW cm
2. For the FeS2
microflowers, the maximum energy density of 4.92 mWh cm
2 Conclusions
(equivalent to Cdevice = 35.48 mF cm
2 for a device) was obtained at a
power density of 154.25 mW cm
2, which is much lower than that of In summary, we have reported the facile synthesis of pristine
the hybrid rGO-FeS2 microspheres. FeS2 microflower and hybrid rGO-FeS2 microsphere electroactive
A long-term stability test is one of the most significant materials. Their electrochemical energy storage properties were
measurements to assess the viability of a long life-span of the assessed for supercapacitor applications in a symmetric cell
electrode materials for commercial use. The cycling stability of the configuration. The hybrid rGO-FeS2 microsphere-based symmetric
pristine FeS2 microflowers and hybrid rGO-FeS2 microspheres- cells exhibited improved electrochemical performance in terms of
based symmetric cells was measured at a constant current density a high areal specific capacitance (112.41 mF cm
2 at a scan rate of
of 0.3 mA cm
2 for 10,000 cycles, as shown in Fig. 9a. The 5 mV s
1) and good cyclic stability (90% capacitance retention for
capacitance retention of the pristine FeS2-based symmetric cell 10,000 cycles) compared to its pristine FeS2 counterpart. The
decreased continuously in the first 5000 cycles and reached 52% of improved electrochemical performance of the hybrid rGO-FeS2
its initial capacitance. From 5000 to 10,000 cycles, the capacitance microsphere electrode was attributed primarily to the synergistic
retention was relatively constant with approximately 48% capaci- effects of both EDLC (rGO material) and pseudocapacitance (FeS2
tance retained at the 10,000th cycle. The drastic capacitance loss material) charge storage properties, which provide tremendous
for the first 5000 cycles may be due to the poor conductivity of the electrochemical performance and in turn high charge storage
pristine FeS2 electroactive material during the repeated charge- capacity. The particle size reduction from the micro to nanometer
discharge process. In contrast to this observation, the hybrid rGO- scale will improve further the surface area of electroactive material
FeS2 microspheres-based symmetric device was relatively un- and in turn the charge storage properties, which is under
changed for the first 1500 cycles (it retained 98% of its initial progression. Our primary results of rGO-FeS2 hybrid materials
capacitance) and then decreased slightly for up to 6500 cycles are expected to be of interest to the energy storage research
(retains 95% of its initial capacitance). At the end, the capacitance community.
decreased gradually and it retained 90% its initial capacitance value
for the last few hundred cycles. The gradual capacitance loss for the Acknowledgements
last few thousand cycles may be due to the loss of loosely attached
electroactive material on the substrate during the repeated charge- The Basic Research Laboratory through the National Research
discharge process.[69] However, the excellent capacitance reten- Foundations of Korea funded by the Ministry of Science, ICT and
tion of 90% and the long-term stability of the rGO-FeS2 hybrid Future Planning (NRF-2015R1A4A1041584). In addition, this
electrode material confirms the promising application of this research was also supported by the Ministry of Trade, Industry.
material for real-time devices.
EIS is one of the key factors to scrutinize the internal resistance Appendix A. Supplementary data
and capacitive behavior of supercapacitors.[68,70] Fig. 9b presents
the Nyquist plots for the pristine FeS2 microflowers and rGO-FeS2 Supplementary data associated with this article can be found, in
hybrid material-based symmetric cells (at the initial stage and the online version, at https://doi.org/10.1016/j.jiec.2018.11.022.
after 10,000 cycles of long-term stability test). The resulting
Nyquist plot describes the following results. (i) A high-frequency References
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