Journal of Alloys and Compounds 792 (2019) 250e259

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Electrochemical, bonding network and electrical properties of reduced

graphene oxide-Fe2O3 nanocomposite for supercapacitor electrodes
applications
Rabina Bhujel a, Sadhna Rai a, Utpal Deka b, Bibhu P. Swain c, *
a
Centre for Materials Science and Nanotechnology, Sikkim Manipal Institute of Technology, Sikkim Manipal University, Majhitar, Rangpo, Sikkim, 737136,
India
b
Department of Physics, Sikkim Manipal Institute of Technology, Sikkim Manipal University, Majhitar, Rangpo, Sikkim, 737136, India
c
Department of Physics, National Institute of Technology, Manipur, Langol, Manipur, 795004, India

a r t i c l e i n f o a b s t r a c t

Article history: A novel nanocomposite electrode material consisting of Fe2O3 and reduced graphene oxide (RGO/Fe2O3)
Received 13 February 2019 has been synthesized using a cost-effective chemical approach for its application in the field of energy
Received in revised form storage devices. The morphological and structural characterizations of the as-synthesized RGO/Fe2O3
30 March 2019
nanocomposite materials were done using scanning electron microscopy (SEM) and X-ray diffraction
Accepted 1 April 2019
Available online 3 April 2019
respectively. The electrochemical properties of the RGO/Fe2O3 nanocomposite were evaluated by cyclic
voltammetry and electrochemical impedance spectroscopy. The RGO5/Fe2O3 nanocomposite exhibited
higher specific capacitance (50 Fg-1) at a scan rate of 0.1 V/s in 0.5 M H2SO4 solution than the pristine
Keywords:
RGO/Fe2O3 nanocomposite
RGO. Moreover, the impedance spectroscopy showed that the value of charge transfer resistance (RCT)
Supercapacitor electrodes was 91.1 and 21.64 U for RGO1/Fe2O3 and RGO5/Fe2O3 respectively, indicating a decrease in the charge
Cyclic-voltametry transfer resistance and increased charge conductivity for RGO5/Fe2O3. This low-cost protocol provides an
Impedance spectroscopy alternative pathway for the large-scale production of various composite materials with controllable di-
mensions for energy storage and conversions.
© 2019 Published by Elsevier B.V.

1. Introduction
To fulfill the increasing demand of power and energy for the
various electronic devices, electric hybrid vehicles, storage devices
with high memory back up and renewable energy power plants,
the development of energy storage devices becomes more urgent
needs. Supercapacitors or the electrochemical capacitors are one of
the most important candidates for the next generation recharge-
able batteries due to their unique properties such as fast charging-
discharging capability, high power density, and long cycle life
[1e6]. The supercapacitors are two categories based on the charge
storage mechanism, one is electrical double layer capacitors (EDLC),
and the other is pseudocapacitors [7]. EDLC mainly uses activated
carbon materials having a high surface area to store the electrical
charge at the electrode/electrolyte interface, such as carbon fibers,
* Corresponding author.
E-mail addresses: bibhuprasad.swain@gmail.com, bpswain@nitmanipur.ac.in
(B.P. Swain).
carbon aerogels and carbon papers [8]. These capacitors have
excellent power density and stability, but suffer from low
capacitance.
Contrary to EDLC, pseudocapacitors usually exhibit high specific
capacitance due to the reversible Faradaic redox reactions taking
place between the active electrode material and the electrolyte in
the process of charging and discharging. The examples of pseudo-
capacitors are oxide and hydroxides of various transition metals
[9e11]. However, the low conductivity and poor stability of pseu-
docapacitors limit their usage. Therefore, these capacitors are
mostly blended with highly conducting carbon materials such as
carbon black, carbon nanotubes, reduced graphene oxide (RGO)
and graphene to enhance their conductivity to some extent [12].
Various transition metal oxides such as copper oxide (CuO) [13,14],
manganese oxide (MnO) [15], nickel oxide (NiO) [16], ruthenium
oxide (RuO2) [17], etc. have been used extensively as an electrode
material for supercapacitors. Bu et al. fabricated NiO/RGO com-
posites with the specific capacitance of 461 F g
1 and a high energy
density of 36.0 Wh kg
1 at the discharge current of 0.21 A g
1 in
6 M KOH electrolyte [18]. Xiang et al. fabricated a rGOeTiO2 NB

https://doi.org/10.1016/j.jallcom.2019.04.004
0925-8388/© 2019 Published by Elsevier B.V.
 R. Bhujel et al. / Journal of Alloys and Compounds 792 (2019) 250e259
electrode with a specific capacitance of 225 F g
1 at a current
density of 0.125 Ag-1 [19]. Khamlich et al. fabricated asymmetric
supercapacitor based on zinc hydroxyl chloride nanosheets and 3D
graphene-nickel foam composite with the specific areal capaci-
tance and electron charge transfer resistance (RCT) of 222 mF cm
2
(at the current density of 1.0 mA cm
2) and 1.63 U, respectively
[20]. Purushothaman et al. fabricated CuO/RGO hybrid super-
capacitor with the specific capacitance of 326 F g
1at a current
density of 0.5 A g
1. The capacitor also shows a high energy density
of 65.7 Whkg
1 at a power density of 302 Wkg-1 [21]. The above
research shows that the introduction of RGO in various metal ox-
ides enhances the conductivity of supercapacitors to many fold
times than the normal metal oxide capacitors. Owing to the supe-
rior magnetic properties [22], cost-effectiveness, natural synthesis
process [23] and environment-friendly nature, Iron oxide (Fe2O3) is
one of the most suitable and promising candidate materials for
application in supercapacitors.
In this report, RGO/Fe2O3 nanocomposites are fabricated by a
simple one-step and easy chemical synthesis procedure by varying
the GO‫׃‬Fe(NO3)3 wt % ratio from 1:1 to 1:5 respectively The elec-
trochemical activity of the as-prepared nanocomposites will be
studied by using H2SO4 as an electrolyte solution. The structural
analysis of the RGO/Fe2O3 nanocomposites will be done to examine
the structures and chemical networks present in the nano-
composite material. Moreover, the effect of shape and concentra-
tion of Fe2O3 will be investigated on the supercapacitor
performance.
2. Experimental
2.1. Materials
Graphite powder, potassium permanganate (KMnO4), sodium
nitrate (NaNO3) sulphuric acid (H2SO4), hydrogen peroxide (H2O2),
hydrochloric acid (HCl), ethanol (C2H5eOH), ferric nitrate
(Fe(NO3)3) and hydrazine hydrate (H2NeNH2) were purchased
from Merck. All chemicals are of analytical grade.
2.2. Preparation of graphene oxide (GO)
The synthesis of GO was carried out by following the modified
Hummers' method [24]. In a typical synthesis, 1 g of graphite
powder was mixed with 2.5 g of NaNO3 and 100 ml of conc. H2SO4.
After that 3 g of KMnO4 was added in the mixture with constant
stirring maintaining the ice bath temperature for 2 h. 100 ml of DI
Fig. 1. Schematic for the synthesis process of RGO/Fe2O3nanocomposites.
251
water was then added slowly to the resulting mixture and heated to
98  C. The heating and stirring were continued for 2 h. The mixture
turns brownish. At last, 10 ml of H2O2 was added to the mix to stop
the reaction. Finally, the mixture was centrifuged and washed with
a 5% HCl aqueous solution to remove metal ions, followed by
distilled water for removal of the acid. The resulting solid with
brown color was separated by ultrasonic treatment in water and
dried at 60+C for at least 10 h.
2.3. Preparation of RGO/Fe2O3 nanocomposites
The RGO/Fe2O3 nanocomposites were prepared by a direct one
step chemical reduction process. In a typical process, at first the
mixture of 0.1 g GO and Fe(NO3)3 with the weight varying from
(0.1e0.5 g) in 50 ml DI water was ultrasonicated for 1 h. A 10 ml of
H2NeNH2 was then added dropwise in the resulting mixture with
continuous stirring. The mixture was then subjected to heating at
90+C under vigorous stirring for 1 h. The black residue was then
filtered and cleaned with DI water, followed by ethanol several
times and air dried. The schematic of preparation step for RGO/
Fe2O3 nanocomposites is shown in Fig. 1.
2.4. Characterizations of the materials
The SEM characterization of RGO/Fe2O3 samples was done by
JEOL, JSM 5510. The XPS spectroscopic characterization was done
using (VG ESCA-LABMK II with a Mg(Ka) X-ray (1253.6 eV) source
and XRD characterization were done with the help of PAN Analyt-
ical Spectris Technologies (PW 3040/60). The current-voltage (IeV)
characteristics of RGO/Fe2O3samples were measured with the help
of KEYSIGHTB2901A precession source/measure unit. Finally, the
electrochemical properties of graphene samples were analyzed
with the help of CH Instruments, Inc. (Electrochemical Analyzer
CHI608E) by using Ag/AgCl as the reference electrode, Pt wire as
the counter electrode and RGO/Fe2O3 coated glassy carbon
electrode as the working electrode. The electrolytic solution
contained 0.5 M H2SO4 solution. The Raman spectra of RGO/
Fe2O3were characterized by.
3. Results and discussions
3.1. Morphological characterization
Fig. 2 shows the FESEM images of RGO, RGO1/Fe2O3, and RGO5/
Fe2O3 nanocomposites. The FESEM image of RGO shows the
252 R. Bhujel et al. / Journal of Alloys and Compounds 792 (2019) 250e259

Fig. 2. FESEM images of RGO, RGO1/Fe2O3 and RGO5/Fe2O3.

formation of a wrinkled layer-like structure with irregular turns.
The stacking and twisting of the RGO sheets are due to the defor-
mation undergoing during the exfoliation and the restacking pro-
cesses. The SEM images of RGO1/Fe2O3 and RGO5/Fe2O3 clearly
shows the distribution of spherically shaped Fe2O3 nanoparticles
over the RGO sheets. The size of Fe2O3 nanoparticles is in the range
of 16e188 nm with the average particle size of ~54 nm for RGO1/
Fe2O3 nanocomposite. Similarly, for the RGO5/Fe2O3 nano-
composite, the Fe2O3 nanoparticles size ranges in between 20 and
29.4 nm with the mean nanoparticle size of ~65 nm. The magnified
SEM images of RGO1/Fe2O3 and RGO5/Fe2O3 shows an increasing
amount of Fe2O3 nanoparticles distribution over the surface of RGO
due to the increase in the wt% ratio of Fe(NO3)3 from 1 to 5. The
FESEM result, therefore, confirms the formation of RGO1/Fe2O3 and
RGO5/Fe2O3 nanocomposites. Moreover, the image of RGO5/Fe2O3
shows tightly bound Fe2O3 nanoparticles with the RGO sheet
confirming a good bonding between the Fe2O3 nanoparticles with
the RGO sheet.
3.2. Structural characterization
3.2.1. X-ray diffraction
Fig. 3(a) shows the XRD diffraction patterns of RGO and RGO/
Fe2O3 nanocomposites with the GO and Fe(NO3)3 wt % varying from

Fig. 3. (a) XRD of RGO/Fe2O3nanocomposites, and (b) lattice strain of RGO/Fe2O3nanocomposites, (c)Raman spectra of RGO/Fe2O3 nanocomposites with the GO and Fe(NO3)3 wt %
ratio varying from 1:1 to 1:5 respectively.
 R. Bhujel et al. / Journal of Alloys and Compounds 792 (2019) 250e259
11‫ ׃‬to 15‫׃‬. The 2q diffraction patterns for RGO was observed at 24.6
and 44.7 with the corresponding planes of (002) and (110) and
absence of 2q at ~10 , indicated the complete reduction of GO into
RGO as reported earlier by Latif et al. [25]. The interlayer spacing in
the RGO was calculated by applying the formula
nl
d¼
2 sinq
The calculated values showed that the interlayer spacing in the
RGO is 3.6 Ao. The result shows similarity with the earlier reported
work by Bhujel et al. [26]. The d spacing between the RGO sheets in
RGO/Fe2O3 nanocomposites varied from 3.59 to 3.72 Å with
increasing the Fe(NO3)3 wt % ratio from 1 to 5. The incorporation of
more number of Fe2O3 nanoparticles in between the RGO sheets is
responsible for opening up the interlayer spacing between the
layers of RGO.
The 2q diffraction patterns for Fe2O3 nanoparticles are at 24.01,
33.42, 35.91, 40.98, 49.92, 54.21, 57.54 and 62.97 with the corre-
sponding crystal planes of (012), (104), (110), (113), (024), (116),
(018) and (214) respectively for the hematite phase of iron which
confirms the formation of RGO/Fe2O3 nanocomposites. Moreover,
the XRD diffraction patterns of RGO/Fe2O3 indicated the rhombo-
hedral structure of a-Fe2O3 (JCPDSno.33-0664). From the XRD
patterns, it can be seen that no characteristic GO peak is present,
confirming the complete reduction of GO in the RGO/Fe2O3 nano-
composites. Similarly, Dong et al. reported similar XRD results for
RGO/Fe2O3 nanocomposites [27].
The highly intense peak at 35.91 corresponding to (110) plane is
used to calculate the crystallite size of Fe2O3 by using the Debye
Scherrer formula, i.e.
D ¼ 0:9l=bCosq
Where D is the crystallite size of Fe2O3, l is the X-ray wavelength, b
is the FWHM of the most intense XRD peak in radians and q is the
value of diffraction angle. The crystallite size varied from 10.03 to
11.79 nm with increasing the Fe(NO3)3 wt % ratio from 1 to 5. The
density of Fe2O3 nanoparticles increased with increases of con-
centration of Fe(NO3)3 solution lead to the formation of the greatest
crystallite size of Fe2O3 nanoparticles in RGO5/Fe2O3 nano-
composite. This is due to the cluster by cluster deposition process of
Fe2O3 nanoparticles, whereas in the case of RGO1/Fe2O3 the crys-
tallite size is smaller as a result of the ion by ion deposition process.
The crystallite size of Fe2O3 nanoparticles and the strain present in
the RGO/Fe2O3 nanocomposite film were further calculated by
applying the Williamson-Hall formula,
bCosq ¼ Kl=ðDÞ þ 4εSinq;
where ε is the slope of the fitted straight line as shown in Fig. 3(b),
which gives the strain present in the nanocomposite. The lattice
strain, ε in RGO/Fe2O3nanocomposites film varied from 0.0011 to
0.0066 with the positive slope, corresponding to the presence of
tensile strain. The increase in the strain may be caused due to in-
crease in the number of Fe2O3nanoparticles in the RGO sheets.
Fig. 3(c) shows the Raman spectra of RGO/Fe2O3 nano-
composites. The Raman spectra of RGO/Fe2O3 nanocomposites
show the presence of a D band at 1315.2 cm
1which corresponds to
the presence of sp3 defect states and the G band obtained at
1561.16 cm
1is ascribed to the in-plane vibration of sp2 hybridized
C atoms of the hexagonal C ring of RGO sheet. The second order 2D
band is observed at 2658.4 cm
1for the symmetry allowed over-
tone of G band, which are useful for detecting the stacking order of
graphene sheets in different graphene samples, moreover the
presence of D þ G peak at 2904.39 cm
1is due to the resonance of D
253
and G (LO) phonon modes. The value of ID/IG increased from 1.65 to
1.7 for the RGO/Fe2O3nanocompositeswith increasing the GO and
Fe(NO3)3 wt % ratio from 11‫ ׃‬to 15‫׃‬. The increase in the ID/IG ratio is
due to the incorporation of more number of Fe2O3nanoparticles
resulting in the loss of three-dimensional ordering of C atoms,
which further leads to an increase in the number of defect states in
the RGO sheet. Also the Raman characteristic peak at
(1)
638 cm
1corresponds to the presence of Fe2O3 nanoparticles in
RGO/Fe2O3nanocomposites confirming the successful synthesis of
RGO/Fe2O3nanocomposites. Xiao et al. obtained an ID/IGratio of 1.29
for Fe2O3/rGO sample, which is comparable to our reported result
[28]. The Raman shift 157.7 and 225.4 cm
1corresponding to Fe2O3
and 302 and 399 cm
1 corresponds Fe3O4 nanoparticles. This
Raman spectra indicated both Fe2O3 and Fe3O4 nanoparticles with
graphene.
3.3. Bonding and networks present in RGO/Fe2O3composites
3.3.1. X-ray photoelectron spectroscopy
Fig. 4(a) shows the wide scan XPS spectra of RGO/Fe2O3 nano-
composites with the iron oxide RGO wt. % was varying from 1‫׃‬1to
15‫׃‬. The binding energies at 285, 532.5 and 711 eV corresponds to
the C (1s), O (1s) and Fe (2p) orbitals respectively [29]. The atomic
percentage of C, O, and Fe in the RGO/Fe2O3 nanocomposite was
calculated by applying the formula
Ai
S
Atomic % ¼ P i A (4)
i
Si
(2)
Where Ai is the area under the XPS curve and Si is the relative
sensitivity factor which is 0.23 and 0.66 and 1.97 for C (1s) and O
(1s) and Fe (2p3/2) respectively. The calculated values of atomic
percentage for C and O and Fe varied from 69.4 to 56.6 at.%,
28.4e40.1 at.% and 2.2e3.3 at.% respectively by increasing the wt. %
of Fe(NO3)3 from 1 to 5 in RGO/Fe2O3 nanocomposites. The XPS
results are in favor of the SEM and XRD results. The values for all the
composites are listed in Table 1.
Fig. 4(b) shows the high resolution deconvoluted C (1s) core
orbital spectra of RGO/Fe2O3 nanocomposites with the varying GO
and Fe(NO3)3 wt% ratio of 11‫ ׃‬to 15‫׃‬. The core orbital of C (1s) was
deconvoluted into six peaks to analyze the different functional
groups of carbon present in the samples. The binding energies at
283, 284.4, 286, corresponds to the carbon C (1s) orbital hybridi-
zation to iron orbital (CeFe), carbon orbital sp2 hybridization to
(3) carbon orbital (C]C), and carbon orbital sp3 hybridization to car-
bon orbital (CeC) respectively. The binding energy of carbon orbital
sp hybridization to oxygen orbital CeO, carbon orbital sp2 hybrid-
ization to oxygen orbital (C]O), and carbon orbital sp3 and sp2
hybridization to carbon orbital (O]CeO) bonds were found at the
287.3, 289.4 and 290.44 eV respectively. The result shows similarity
with the earlier reported work by Furlan et al. [30] for iron carbide
thin films.
Fig. 4(c) shows the deconvolution of O (1s) core orbital into six
Lorentzian peaks to study the O environment in RGO/Fe2O3 nano-
composites. The binding energies at 530.66, 531.13, 532.2 and
533.15, 534.1 and 535.05eV are assigned to oxygen hybridization to
iron orbital (OeFe2), oxygen orbital hybridization with iron orbital
(OeFe), oxygen orbital hybridization with carbon orbital (OeC),
oxygen orbital hybridized with oxygen-induced carbon orbital
(OeCeO), OeOeC or OeOeH and O]O bonds respectively. The
significant observations obtained by the O (1s) core orbital are as
follows.
254 R. Bhujel et al. / Journal of Alloys and Compounds 792 (2019) 250e259

Fig. 4. (a) XPS spectra of RGO/Fe2O3nanocomposites, (b) deconvoluation of C (1s) orbital, (c) deconvolution of O (1s) orbital, and (d) deconvoluation of Fe (2p) orbital with the GO
and Fe(NO3)3 wt % ratio varying from 11‫ ׃‬to 15‫׃‬.

Table 1
The composition of C, O and Fe at.% estimated from XPS, lattice spacing, crystallite size and lattice strain evaluated from XRD with different RGO and Fe2O3 nanocomposites.

GO:Fe(NO3)3 C O Fe Scherrer Analysis Williamson Hall Analysis

o
(wt. %) (at.%) (at.%) (at.%) Lattice spacing (d) (A ) Crystallite Size (D) (nm) Crystallite Size (D) (nm) Lattice strain

1:1 69.4 28.4 2.2 3.59 10.03 11.55 0.0011

1:2 63.2 34.3 2.5 3.62 9.91 10.34 0.0027
1:3 62.8 34.4 2.8 3.66 11.04 12.83 0.0029
1:4 60 37 3 3.72 11.33 17.32 0.0034
1:5 56.6 40.1 3.3 3.72 11.79 26.14 0.0066

(a) The bonding of oxygen with iron confirms the formation of
iron oxide/RGO composites.
(b) The FWHM of OeFe2 and OeFe bond in O (1s) core orbital
increased from 1.65 to 2.06 eV and 0.67e0.71 eV respectively
as the wt. % ratio of GO/Fe(NO3)3 increased from 1:1 to 1:5,
indicating an increase in the concentration of charge transfer
from Fe to O in the RGO/Fe2O3 nanocomposites.
(c) The bond intensities of OeC, OeCeO, OeOeC or OeOeH and
O]O bonds remained constant in all the RGO/Fe2O3
 R. Bhujel et al. / Journal of Alloys and Compounds 792 (2019) 250e259
nanocomposite samples, indicating no as such changes in the
structure of RGO layers.
Fig. 4 (d) shows the deconvolution of Fe (2p) core orbital into
nine Lorentzian peaks. The spectrum exhibits two main spin-orbit
peaks of Fe (2p3/2) and Fe (2p1/2) with the respective binding en-
ergies of 711 and 725 eV confirming the characteristic of Fe2þ in the
presence of Fe2O3 particles in the nanocomposite. The peaks of
deconvoluted Fe (2p3/2) core orbital with the binding energies of
711, 716, 719 eV are assigned to iron 2p orbital hybridized with 2p
iron orbital (FeeFe), iron 2p orbital hybridized with carbon 1s
orbital (FeeC) and iron 2p orbital hybridized with oxygen 1s orbital
(FeeO) bonds respectively. The presence of a satellite peak at 719
confirms the presence of Fe3þ within Fe2O3/rGO nanocomposites.
With an increase in Fe2O3 concentration, an additional peak is
observed at around 713 eV, which can be assigned to the bonding of
two 2p orbitals of iron with one carbon 1s orbital (Fe2eC). Similarly,
the deconvoluted Fe (2p1/2) core orbital shows the presence of
FeeFe, Fe2eC, FeeC, FeeO and FeeO2 bonds with the correspond-
ing binding energies of 722, 726, 731, 735 and 738 eV respectively.
The FeeFe bond confirms the presence of zero metallic valence
iron. The FeeC and Fe2eC bonds correspond to Fe3þ and Fe2þ
respectively. The Fe2eC bonds are only seen when the concentra-
tion of iron oxide in RGO/Fe2O3 nanocomposite with the GO‫׃‬Fe2O3
ratio of 14‫ ׃‬and 15‫׃‬. The presence of Fee O and FeeO2 are the
characteristic of Fe2þ and Fe3þ respectively. The presence of Fe2þ
and Fe3þ in the core orbital spectra of Fe (2p) confirms the presence
of Fe2O3 nanoparticles in the RGO/Fe2O3 nanocomposite films [31].
3.3.2. FTIR spectroscopy
Fig. 5 shows the FTIR spectroscopy of GO and all RGO/Fe2O3
nanocomposites. The FTIR spectroscopy was characterized to study
the changes in the functional groups during the reduction and
composite formation of GO. The spectrum of GO shows some
similarity with the earlier reported results by Sarkar et al. [32]. The
broadband at ~3401 cm
1 corresponds to the OeH stretching pre-
sent in GO sample. The transmission at 2924, 1714, 1610.25, 1206,
1039 and 857.3 cm
1 correspond to asymmetric eCH2 stretching,
C]O stretching, eCOOH stretching, C]C stretching of the aromatic
ring, epoxy CeO stretching or alkoxy CeO stretching and eCeH
stretches, respectively. After completing the reduction process of
GO, it was observed that the oxygen-containing functional groups
are either disappeared completely or reduced considerably. In RGO/
Fe2O3 composites the signatures appearing in 3427, 1714 and
1221 cm
1 corresponds to the presence of the oxygen-containing
Fig. 5. FTIR spectra of RGO/Fe2O3nanocompositeswith the GO and Fe(NO3)3 wt % wt. %
ratio varying from 11‫ ׃‬to 15‫׃‬.
255
functional groups OeH, eC]O, OeOeH respectively, which have
smaller intensities as compared to the GO. The peaks at 2924 and
1556 cm
1 corresponds to the presence of eCH2 and eC]C bonds
respectively in every RGO/Fe2O3samples. Moreover, the strong
signatures at 553.3 and 466 cm
1 are assigned to the Fe3þ-O2 bond
in the FeO6 octahedron and FeO4 tetrahedron, respectively [33]. The
peak intensity for Fe3þ-O2 bond increases considerably from RGO1/
Fe2O3eRGO5/Fe2O3 due to an increase in the percentage of Fe2O3
nanoparticles in RGO5/Fe2O3 nanocomposite. Also, the reduction of
peak intensities at 1221 and 1714 cm
1 for all RGO/Fe2O3 composite
materials confirm the reduction of GO to RGO. The FTIR results are
in agreement with the XPS results explained earlier.
3.4. Electrochemical properties
3.4.1. Cyclic voltammetry
Fig. 6 (a) shows the CV curves of RGO/Fe2O3 nanocomposites
with the GO‫׃‬Fe2O3 wt.% ratio varying from 11‫ ׃‬to 1:5 respectively, to
optimize the supercapacitor behavior of RGO/Fe2O3 nano-
composites with increasing the Fe2O3 weight ratio. The CV curves
obtained for RGO/Fe2O3 nanocomposites show a distorted vol-
tammogram consisting of a pair of redox peaks at 0.25 and 0.4 V
respectively, which is attributed to the integration of electrical
double layer capacitance of RGO with the redox activity of the Fe2þ/
Fe3þ redox couple. It was found that by increasing the wt. % of
Fe(NO3)3 the CV curves start to distort from the rectangular
behavior. The distorted rectangular shape is attributed to the
presence of oxidation reduction peaks in the CV curves indicating
that the capacitance characteristics is mainly due to the Faradaic
redox reactions, which corresponds to the reversible conversion of
Fe2þ/Fe3þ. It was observed from the FESEM images that at higher
concentration the number of Fe2O3 nanoparticles increases within
the RGO sheet. These excessive numbers of Fe2O3 nanoparticles
increase the electrolytic ionic carriers due to which the capacitive
performance will be enhanced. The deviation of the samples from
the rectangular behavior was expected due to the contribution of
pseudo-capacitance behavior of the Fe2O3 nanoparticles. The CV
scans were carried out with the incremental scan rates of 0.1e0.5 V/
s for all samples within the potential window of
0.2e1 V. The
current obtained for RGO/Fe2O3 nanocomposites are higher than
that of the pristine RGO indicating enhanced charge storage capa-
bilities of RGO/Fe2O3 nanocomposites. Therefore, to analyze the
capacitive property the specific capacitance of RGO/Fe2O3 nano-
composites was calculated by using the following equation,
Vðb
1
Cm ¼ IdV (5)
mvðVb
Va Þ
Va
Where Cm (Fg
1) is the specific capacitance, I (A) is the corre-
sponding current of the CV curve, m (g) is the mass of active
electrode materials; v (V s
1) is the scan rate; Va and Vb (V) are high
and low potential limit of the CV tests. At the scan rate of 0.1 V/s, all
the samples obtained better results. The values of specific capaci-
tance varied from 5.85 to 50 Fg-1 for RGO1/Fe2O3 to RGO5/Fe2O3
respectively with varying the Fe2O3 concentration.
The electrochemical properties of all the samples were further
investigated by varying the scan rate from 0.1 V/s to 0.5 V/s in the
potential window range of
0.2e1 V. It can be seen from Fig. 6 (a)
that with increasing the scan rates, the area under the CV curve
increases indicating a good capacitive behavior of RGO/Fe2O3
nanocomposites [26]. From the specific capacitance versus scan
rate plot in Fig. 6 (b) it was found that the capacitance decreases for
all samples at higher scan rates due to a decrease in the charges
Fig. 6. (a) Cyclic voltammetry and (b) specific capacitance of RGO and RGO/Fe2O3nanocomposites with the GO and Fe(NO3)3 wt % ratio varying from 1:1 to 1:5 (c) Galvanostatic
charging discharging curve of Fe2O3, RGO and RGO/Fe2O3 nanocomposites with the GO and Fe(NO3)3 wt % ratio of 1:1 to 1:5.
 R. Bhujel et al. / Journal of Alloys and Compounds 792 (2019) 250e259 257

transfer rate through the electrochemical double layer formed in
the interface between the electrode and the electrolyte and also
due to the inactivity of inner active sites of the active electrode
material [33].
3.4.2. Galvanostatic charging-discharging
Galvanostatic charging-discharging (GCD) measurements of
Fe2O3, RGO and RGO/Fe2O3nanocomposites are performed in order
to confirm the superior capacitance behavior of RGO/Fe2O3 nano-
composites. Fig. 6(c) shows nearly triangular shaped charge-
discharge profiles for all the samples at different current densities
varying from 0.1 to 0.5 Ag-1, confirming the good capacitive char-
acteristics of the as synthesized RGO/Fe2O3 nanocomposites. The
specific capacitance of Fe2O3, RGO and RGO/Fe2O3 nanocomposites
electrodes was calculated from the charge/discharge curves using
the equation given below
I Dt
Csc ¼
mDV
impedance Z0 , and Y-axis is the negative imaginary impedance Z00 )
and the Bode plot which is the frequency response of impedance.
Fig. 7(a) shows the Nyquist plots of RGO and all the RGO/Fe2O3
nanocomposites within the frequency range of 1e106 Hz. The
Nyquist plots of all samples show semicircular curves for the
samples which denote the charge transfer resistance (RCT) within
the material, and the diameter of semicircle provides the magni-
tude of RCT [34]. The well-defined semi-circle of the RGO/Fe2O3
nanocomposite implies that the charge transport through these
composites is an activation controlled process. Fig. 7 (a) shows that
the RCT of RGO5/Fe2O3 nanocomposite is 21.64 U which is least
among all. The decrease in RCT corresponds to higher super
capacitive property as a result of the synergistic effect between the
Fe2O3 and RGO [35]. Moreover, the inserted schematic equivalent
circuit diagram inside Fig. 7(a) represents, Re, RCT and Cdl corre-
sponding to the resistance offered by the electrolytic solution, the
electron transfer resistance of electrode and the double layer
capacitance. From the Nyquist plot itself, the capacitance of the
(6)
interfacial reaction can be determined by using the formula

where I is the discharge current, Dt is the discharge time after IR t

drop, and m is the mass of active sample on the electrode in the cell. Cdl ¼ (7)
RCT
The values of specific capacitance for Fe2O3, RGO and RGO1/Fe2O3,
RGO3/Fe2O3, andRGO5/Fe2O3 nanocomposites were 0.14, 16.45, Where
31.66, 39.29 and 86 Fg
1at the current density of 0.1 Ag-1 respec-
tively. From both the CV and GCD analysis it was observed that the 1
specific capacitance of RGO/Fe2O3 nanocomposites is much higher t¼ (8)
umax
than that of Fe2O3 and RGO separately. Moreover, the highest
specific capacitance was also achieved by RGO5/Fe2O3 nano- Where t is the time constant and umax ¼ frequency where the
composites, due to the more efficient charge transfer rate resulting imaginary impedance is maximum. The time constant for the
from good electrolyte diffusion within RGO5/Fe2O3 nanocomposite. diffusion process varied from 12.5  10
2 to 2.5  10
2 s and hence
The good interaction between the maximum number Fe2O3nano- the value of specific capacitance of interfacial reaction varied from
particles facilitates a rapid electron transfer between the Fe2O3and 2.6  10
4 to 11.55  10
4 F/cm2 with increasing the
RGO sheets resulting in the high specific capacitance of the RGO5/ GO‫׃‬Fe(NO3)3 wt % from 1:1 to 1:5 respectively. The Value of Re, RCT,
Fe2O3nanocomposite. The values of specific capacitance for all the and Cdl of all the samples are inserted in Table 2. The trend of
samples obtained at different current densities are depicted in capacitance obtained from the Nyquist plot is by the specific
Table 3. capacitance obtained by the CV and GCD analysis.
Fig. 7 (b) shows the Bode plot of RGO/Fe2O3 nanocomposites
3.4.3. Electrochemical impedance spectroscopy with the GO‫׃‬Fe(NO3)3 wt% ratio of 1:1, 1:3 and 1:5 respectively. The
To extract the kinetic information and interfacial properties of result showed that with increasing the concentration of Fe2O3
electrode materials, a nondestructive and easy method, i.e., EIS is nanoparticles in RGO/Fe2O3 nanocomposite the value of impedance
utilized for all the RGO/Fe2O3 nanocomposite materials. The data of is observed to decrease from 97.75 to 31.05 U. The maximum
EIS is obtained in the form of Nyquist plot (where X-axis is the real impedance obtained at the lower frequency region (i.e., 1e106 Hz)

Table 2
Different parameters obtained from Bode and Nyquist plots of RGO/Fe2O3nanocomposites with the GO and Fe(NO3)3 wt % ratio varying from 1:1 to 1:5.

GO‫׃‬Fe(NO3)3 Nyquist Analysis Bode Analysis

(Wt. %) Re (U) RCT (U) C x 10
4 (F/cm
2) R e ( U) RCT (U) Phase (4max) (o)

1:1 7.9 91.1 2.6 7.5 89.83
50.5

1:2 7.9 73.92 4.8 7.5 74.55
44.27
1:3 7.9 58.93 7.1 7.5 59.3
38.05
1:4 7.9 38.43 9.3 7.5 40.3
33.55
1:5 7.9 21.64 11.55 7.5 22.5
31.05

Table 3
The values of specific capacitance obtained from Galvanostatic charging discharging curve at different current densities.

Current density in (Ag
1) Specific Capacitance (Csc in Fg
1)

Fe2O3 RGO RGO1/Fe2O3 RGO3/Fe2O3 RGO5/Fe2O3

0.1 0.14 16.45 31.66 39.29 86

0.2 0.25 13.55 25.02 49.98 41.66
0.3 0.17 12.02 20.64 26.64 138.5
0.4 0.19 11.8 15.26 27.1 34.8
0.5 0.12 14.5 13.5 16.08 30.44
258 R. Bhujel et al. / Journal of Alloys and Compounds 792 (2019) 250e259
Fig. 7. (a) Nyquist plot, (b) Bode plot of RGO/Fe2O3nanocomposites with the GO and
Fe(NO3)3 wt % ratio varying from 1:1 to 1:5.
and 4 ~ 0 which corresponds to the value of Re þ RCT, i.e., the total
resistance offered by the RGO/Fe2O3 nanocomposite electrode
concerning the H2SO4 solution. The impedance at lower frequency
region, i.e., below 103 Hz with the corresponding phase angle of
~4 ¼ 0 gives the value of total resistance offered by the electrode
and electrolyte Re þ RCT. Within the frequency range of 103 to
2  104 Hz with the corresponding maximum phase angle, the
value of impedance in this region decreases rapidly which is
attributed to a capacitor in parallel with a resistance due to the
charge transfer process (RCT) for a reversible reaction as reported
earlier by Casero et al. [36]. The impedance at higher frequency
Fig. 8. Current-voltage characteristics of RGO and RGO/Fe2O3nanocomposites with
theGO and Fe(NO3)3 wt % ratio varying from 1:1 to 1:5.
region is again approximately constant at 105e106 Hz, which is
attributed to the electrolytic resistance (Re) between the reference
and the working electrode. The estimated values of Re and RCT for all
RGO/Fe2O3 nanocomposite samples are listed in Table 2. From the
Bode plot as well minimum impedance was for RGO5/Fe2O3
nanocomposite with the Re, RCT and 4max values of 7.5 Ohm, 22.5
Ohm and
27.19 respectively.
3.5. Electrical properties
Fig. 8 shows the current-voltage characteristic curve of RGO and
RGO/Fe2O3 nanocomposites with varying the Fe2O3 content within
the composite material. The current (I) versus voltage (V) curves
obtained for all RGO/Fe2O3 nanocomposite follow Ohms law where
I a V whereas RGO shows diode characteristics. The conductivity of
RGO/Fe2O3 nanocomposites higher than as compared to that of
RGO sample. This current increase in RGO/Fe2O3nanocomposite
samples occurs may be due to the formation of RGO nanocomposite
with Fe2O3 nanoparticles. The RGO5/Fe2O3 sample contains the
number of iron-containing groups attached with the layers of RGO,
which helps to enhance the electrical conductivity due to the
synergistic effect produced by the Fe2O3 and RGO to each other and
the highest conductivity was observed for the RGO5/Fe2O3
nanocomposites.
4. Conclusion
A cost-effective chemical approach was utilized for the syn-
thesis of RGO/Fe2O3 nanocomposites. The increase in the Fe(NO3)3
concentration results in the introduction of more number of Fe2O3
nanoparticles in the RGO5/Fe2O3 nanocomposite films. The RGO5/
Fe2O3 nanocomposite exhibited higher specific capacitance (50 Fg-
1
) at the scan rate of 0.1 V s
1 in 0.5MH2SO4 solution than the
pristine RGO. Moreover, the impedance spectroscopy showed that
the value of RCT varied from 91.1 to 21.64 U as the Fe(NO3)3 wt %
ratio increased from 1 to 5 respectively, indicating a decrease in the
charge transfer resistance and increased charge conductivity for
RGO5/Fe2O3 nanocomposites. This enhancement in the specific
capacitance is expected due to the presence of more number of
iron-containing groups attached with the layers of RGO, which
helps to enhance the charge transfer rate as well as the electrical
conductivity due to the synergistic effect produced by the Fe2O3
and RGO to each other. Therefore, a straightforward and low-cost
protocol will provide an alternative pathway for the large-scale
production of various composite materials, including the RGO/
Fe2O3 nanocomposites with controllable dimensions for energy
storage and conversions.
Acknowledgment
One of the authors Ms. Rabina Bhujel acknowledges Dr. Ramdas
Pai and Vasanti Pai endowment fund for the financial support to
perform this entire research work. The authors thank to Prof. (Dr.)
Rajiv Dusane, Department of Metallurgical Engineering & Materials
Science for Raman characterization at IIT Bombay.
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