J Mater Sci: Mater Electron

Evolution of waste iron rust into a-Fe2O3/CNF and a-

Fe2O3/PANI composites as an efficient positive
electrode for sustainable hybrid supercapacitor
Rounak R. Atram1, Darpan V. Bhuse2,* , Vijaykumar M. Bhuse2, Ramdas G. Atram3, and
Subhash B. Kondawar1

1
Polymer and Nanotechnology Laboratory, Department of Physics, Rashtrasant Tukdoji Maharaj Nagpur University,
Nagpur 440033, India
2
Energy Materials Research Laboratory, Department of Chemistry, Government Institute of Science, Nagpur 440001, India
3
Department of Physics, Government Institute of Science, Nagpur 440001, India

Received: 2 February 2021 ABSTRACT

Accepted: 8 April 2021
Ó The Author(s), under
exclusive licence to Springer
Science+Business Media, LLC,
part of Springer Nature 2021
A green and sustainable approach to recycle the waste iron rust into a valuable a
modification of Fe2O3 via simple grinding and calcination for application in a
hybrid supercapacitor is reported. The a-Fe2O3 was coupled with carbon
nanofibers (CNFs) and conducting polymer, polyaniline (PANI), to form com-
posite hybrid supercapacitor electrode materials. The conventional hydrother-
mal, electrospinning, and in-situ polymerization processes were used to prepare
composites. Further, X-ray diffraction (XRD), transmission electron microscopy
(TEM), high-resolution transmission electron microscopy (HRTEM), selected
area electron diffraction (SAED), scanning electron microscopy (SEM), and
energy-dispersive x-ray (EDAX) spectroscopy were used to study the structural,
morphological, and compositional properties of the as-synthesized a-Fe2O3 and
its composites with CNF and PANI. The a-Fe2O3/CNF and a-Fe2O3/PANI
composites, coated on carbon rod, were used as electrodes in a three-electrode
system to study electrochemical impedance spectroscopy (EIS), cyclic voltam-
metry (CV), and galvanostatic charge–discharge (GCD) in 1 M H2SO4. The XRD
studies revealed the formulation of iron rust into a-Fe2O3 modifications with an
average of 28 nm crystallite size. Uniform dispersion of a-Fe2O3 over CNF of
400–500 nm diameter and excellent covering of PANI over a-Fe2O3 nanomate-
rials were the morphological features observed for a-Fe2O3 /CNF and a-Fe2O3 /
PANI composites, respectively. The electrochemical studies on a-Fe2O3/PANI
composites exhibit higher performance as against Fe2O3/CNF with respect to
specific capacitance, 192 Fg-1 (88.88 Fg-1); energy density, 11.28 Whkg-1
(3.084 Whkg-1); power density, 162 Wkg-1 (69.39 Wkg-1); and capacitance
retention of 80% (75%) after 5000 charge–discharge cycles. The heavy dispersion
of a-Fe2O3 over long CNF and PANI fibers with intimate contact resulted in

Address correspondence to E-mail: bhusedarpan@gmail.com

https://doi.org/10.1007/s10854-021-05955-x

abundant active sites for electrochemical reactions leading to the obtained
result. The rust-derived a-Fe2O3 with PANI offers excellent stability to act as a
potential candidate for sustainable hybrid supercapacitor application.
1 Introduction
The past few decades have witnessed rapid devel-
opment in industrial automation, transportation, and
a huge upsurge of modern household appliances.
Ever-growing industrialization and urbanization,
however, demand a huge amount of electrical energy
to work with [1]. Today, most of the energy demands
of the world are fulfilled by using non-renewable
energy resources. The huge utilization of these
resources, however, leads to depletion and eventu-
ally finishes off the reservoirs, global warming, pol-
lution, and climate change [2]. At the outset, the
alternative renewable energy resources, although
clean, eco-friendly and abundant, demand an effi-
cient energy harvesting system and smart storage
devices to store the energy efficiently for later use.
Because of the global concern, the development of
efficient, clean energy devices utilizing natural
materials and/or materials with a greener synthetic
approach is especially challenging [3, 4]. In this
regards, the rapidly developing field of nanotech-
nology provides not only the exciting opportunities
to design materials having desired electronic, chem-
ical, mechanical, and morphological characteristics
but also the greener synthetic approach for applica-
tions in the fields of advanced energy storage (bat-
teries and electrochemical capacitors) [5, 6],
environmental remediation [7], photocatalysis [8, 9],
hydrogen production [10, 11], electronics and energy
conversions [12], sensors, etc., [13]
Recently, a lot of interest is developed to explore
energy storage materials for use in batteries, super-
capacitors, and fuel cells. The supercapacitor, among
them, have emerged as an eco-friendly and safe
means of energy storage device due to its character-
istics, such as comparatively small size, high power
density (5–10 kWkg-1), long cycle life ([ 500,000
cycles), long shelf life, high efficiency (95%), and
wide operating temperature range (-40 to ? 70 °C).
It is being considered as a future energy storage
system that probably complements or even replaces
conventional batteries and fuel cells [14].
J Mater Sci: Mater Electron
The basic energy storage mechanism of the super-
capacitor involves either charge separation at the
electrode–electrolyte interface (electric double-layer
capacitors, EDLC) or the Faradic redox reactions
between the electrolyte and the electrode material
(pseudo-capacitors). Carbon-based materials, such as
graphene, carbon nanofibers (CNFs), activated car-
bon (AC), and carbon nanotubes (CNTs), serve as the
main electrode materials in EDLC [15, 16] with one-
dimensional carbon mesoporous nanofibers being
popular [17].
So far, many efforts are being made to develop
carbon fibers using verities of methods involving
more or less complexity in preparation [18]. Electro-
spinning, one of the methods, working under pre-
cisely controlled conditions, has emerged as a
versatile, efficient, continuous and industrially viable
method to evolve long nanofibers with different
morphologies having extremely high aspect ratio and
large surface area to volume ratio [19]. Such fibers are
highly desirable for use in energy storage applica-
tions since they exhibit transportation directionally
and short ionic transport lengths [20]. The
hydrothermal method, on the other hand, is a facile,
low-cost method that has advantages, such as high
yield of the products, control over morphology, and
reproducibility. So far, several metal oxides and
hydroxides have been synthesized using a
hydrothermal technique for use as electrode materi-
als in supercapacitors [21].
The EDLC-based supercapacitors exhibit long cycle
life but produce relatively low specific capacitance,
whereas pseudo-capacitors have high specific
capacitance but show slow charge kinetics [22]. The
hybrid capacitor combines the characteristics of
EDLC and the pseudo-capacitor can exhibit features,
like high energy, power densities, and long cycle life
[23–25]. The pseudo-capacitor electrode materials, the
metal oxides, are often coupled with conducting
polymers for better electronic communications to
yield hybrid-type supercapacitor materials [26]. A
huge research literature is available on nanofibers
and or polymer-coupled metal oxides exhibiting
better performance in supercapacitance. For instance,
J Mater Sci: Mater Electron
single-type oxide systems, such as an electrospun-
TiO2/CNF exhibited a high specific capacitance of
280.3 Fg-1 at current density 1 Ag-1 [27],
hydrothermally grown V2O5/CNF composite exhib-
ited a high capacitance of 227 Fg-1 at current density
1 Ag-1 [28], and MnO2/CNF has achieved specific
capacitance of 311 Fg-1 at a scan rate of 2 mV/s [29]
and ZnO/CNF displayed specific capacitance of
178.2 Fg-1 [30]. Among single oxides, iron oxide
(Fe2O3) is considered as an important electrochemical
electrode material due to (i) its existence in several
morphologies and crystallographic modifications
[31], (ii) ease in variations in oxidation state (Fe2?-
$ Fe3?) (iii) outstanding theoretical specific capaci-
tance (3625 Fg-1), (iv) high thermal stability (v) high
corrosion resistance, (vi) abundance in nature and
environmental friendliness [32–34], and (vii) use as
positive as well as a negative electrode. Like many
other electrodes, Fe2O3 also suffers from poor elec-
trical conductivity leading to lower capability and
cycling stability [35]. However, the electrical con-
ductivity can be improved by introducing carbon/
conducting polymer materials into Fe2O3 forming
composites [36]. A good kind of literature is available
wherein a thermodynamically stable form of iron
oxide, a-Fe2O3 (Hematite), coupled with carbon
nanofiber via methods, like hydrothermal [27–39],
electrospinning [40, 41], vapor growth [42], gel tem-
plating [43], and mechanical press [44], has been
utilized as the efficient negative electrode in Li-ion/
Na-ion batteries and/or as supercapacitor in -1.2 to
0 V potential range. There are some reports where a-
Fe2O3-based, ternary-type hybrid materials have been
utilized as the positive electrode in aqueous elec-
trolytes [45, 46]. In all the cases, electrode material
fabrication methods have involved the use of toxic,
expensive chemicals and complicated chemical and
physical treatments that can lead to environmental
implications. There are only two reports available in
the literature on the greener synthesis of a-Fe2O3,
wherein a-Fe2O3 was obtained by chemical and
physical treatments on up-cycled industrial mill scale
waste [47] and in another case annealing of a mixture
of iron hydroxide and dextran chemicals at various
temperatures [48]. However, to the best of our
knowledge, there are no reports on the use of rust-
derived nano a-Fe2O3 for application as a hybrid
supercapacitor. The rusting process called corrosion
is a weathering phenomenon capable of giving
aggregates of nano-scaled iron oxide hydroxide, a
rusted product, thus can be a cheap means for getting
iron oxide nanomaterial [49]
In view of this, we propose a scalable, simple,
smart strategy to evolve nano-scaled a-Fe2O3 to
recycle huge iron rust waste available. The method is
truly greener, cost-effective and requires no chemi-
cals and other expensive treatments. The synthesized
a-Fe2O3 was further coupled with CNF and PANI to
get binary composite electrode material.
2 Experimental details
2.1 Materials
The materials used for the synthesis of PANI–CNT
were polyacrylonitrile (PAN, Mw = 150,000, Sigma-
Aldrich), ammonium persulfate (APS, AR grade, E
Merck), hydrochloric acid (HCl, Specific gravity
1.08 g/cc, Sigma-Aldrich), and aniline (Synthesis
grade, Sigma-Aldrich). All the chemicals were used
without further purification (except aniline, which is
doubly distilled and stored in an airtight container in
dark) and the solutions were prepared in doubly
distilled water or as otherwise stated.
For the preparation of electrodes, the carbon rods,
obtained from the exhausted AA-sized, alkaline,
battery cell (Eveready make) were used. The carbon
black (AR grade, Sigma-Aldrich) and polyvinylidene
fluoride (PVDF, AR grade, Sigma-Aldrich) were used
as conductivity enhancer and binder, respectively, to
prepare the electroactive material on the carbon rod.
The N-methyl pyrrolidone (NMP, AR grade, Sigma-
Aldrich) was used as a solvent to get a-Fe2O3/CNF
and a-Fe2O3/PANI deposit on the carbon rod. These
deposits were used for measuring electrochemical
properties. The N-N-dimethylformamide (DMF, AR
Grade, Sigma-Aldrich) was used as a solvent to make
the solution for electrospinning. A 0.1 M H2SO4
solution, prepared by appropriate dilution of H2SO4
(AR Grade Sp. gravity 1.840 g/ml, Sigma-Aldrich),
was used as an electrolyte for measuring CV, GCD,
and EIS characteristics of the composites.
2.2 Extraction of nano a–Fe2O3 from iron
rust
With the green and sustainable synthetic approach
and to recycle the waste iron rust, we collected the
rust from moderately rusted iron bars by hand

peeling. The rust was ground for 4 h in a laboratory-
scale stainless steel ball mill (Sisco, India) at
60–80 rpm, then cooled to room temperature, and
washed several times with deionized water. It was
then dried naturally and subjected to annealing in a
Muffle furnace at 550 °C for 5 h. After the heat
treatment, the powder was cooled to room tempera-
ture and subjected again to another short cycle of
grinding (for an hour) followed by annealing at
550 °C (for an hour). Finally, after natural cooling, the
product was dried under a vacuum and stored in a
desiccator.
2.3 Fabrication of carbon nanofibers
(CNFs)
The CNF was fabricated using an Electrospinning
Assembly (ESPIN-NANO, PECO-Chennai). An elec-
trospinning solution was prepared by dissolving
polyacrylonitrile (10 wt %) in N–N-dimethylfor-
mamide (DMF) with a constant magnetic stirring for
2 h at 70 °C. The clear solution was loaded into a
10-ml electrospinning syringe. A constant high volt-
age of 20 kV was maintained between the tip of the
syringe needle and the base collector plate. The base
plate to needle tip distance was maintained at 15 cm.
The electrospinning process was carried out in a
closed chamber by injecting solution from a syringe
at a 0.8 ml/h flow rate. After electrospinning, the as-
prepared electrospun PAN fibers were removed and
subjected further to a horizontal quartz tube furnace
for carbonization. In this process, the PAN fibers
were heated for stabilization at 220 °C for an hour in
the air atmosphere then carbonized at 600 °C in the
nitrogen atmosphere for another hour and finally
kept at 400 °C in the nitrogen environment for the
next hour for activation. After natural cooling of
quartz tube furnace, the CNF was collected and
stored in a desiccator.
2.4 Preparation of a-Fe2O3/CNF composite
by hydrothermal method
The hydrothermal synthesis was carried out by using
a Teflon-lined hydrothermal autoclave (110 ml
capacity). A solution for the hydrothermal process
was prepared by sonicating 50 mg CNF in 50 ml of
deionized water for 3 h to get uniform dispersion. To
this dispersion, 100 mg of a-Fe2O3 was added and
stirred magnetically for an hour. This mixture was
J Mater Sci: Mater Electron
then transferred into a Teflon-coated stainless steel
autoclave and heated at 140 °C for 8 h. Finally, after
natural cooling of autoclave, the content was
removed, washed centrifugally, and finally dried at
70 °C overnight in a hot air oven to obtain a-Fe2O3/
CNF.
2.5 Preparation of a-Fe2O3/PANI composite
by in-situ polymerization
The a-Fe2O3/PANI composite was prepared by
polymerization of aniline in the presence of a-Fe2O3
nanoparticles (in-situ polymerization). For polymer-
ization, solutions A and B were prepared as follows:
Solution A was prepared by magnetically stirring the
mixture of (0.25 M, 5 ml) APS and (1 M, 25 ml) HCl
for an hour. This solution was filled in a burette.
Solution B was prepared by magnetically stirring the
mixture of aniline (0.25 M, 5 ml) and HCl solution
(1 M, 25 ml) for 30 min; 50 mg of a-Fe2O3 was added
to this solution and sonicated further for 30 min.
Solution B was then transferred to an ice bath of *
5 °C temperature. Solution A was then added
dropwise into solution B with continuous magnetic
stirring at such a rate that does not allow the tem-
perature to exceed 10 °C, and the stirring was con-
tinued for the next 6 h to complete the process of
polymerization. Finally, the product was removed
and centrifugally washed several times with deion-
ized water and dried at 80 °C overnight in a vacuum
oven to get a-Fe2O3/PANI composite.
2.6 Electrode preparation method
For electrochemical testing, the composite (a-Fe2O3/
CNF and a-Fe2O3/PANI) electrode materials coated
on carbon rods via the dip coat method were used as
electrodes.
A carbon rod was carefully removed from
exhausted AA-sized, alkaline type, and battery cell
(Eveready make) and washed thoroughly by water
several times and then sonicated for 30 min in dis-
tilled water. The dried rods were polished by sand-
paper (zero size) followed by successive washings
several times with water, alcohol, and acetone and
finally subjected to sonication for 30 min in acetone
solvent for 30 min. These rods were further dried at
110 °C in a vacuum for 2 h, cooled naturally, and
stored in a desiccator before electrode fabrication. A
coating solution was prepared by thoroughly
J Mater Sci: Mater Electron
sonicating a mixture of synthesized composites (a-
Fe2O3/CNF and a-Fe2O3/PANI), Acetylene black,
and PVDF in 85:10:5 weight percent ratio in N-methyl
pyrrolidone solvent to obtain a homogeneous dis-
persion. A clean rod was then dipped in this dis-
persion and drown off slowly to obtain a uniform
coating. Finally, the coated carbon rod was dried at
80 °C in an oven for 4 h and used as the electrode for
electrochemical measurements. The PVDF was used
as a binder, while carbon black to maintain electrical
conductivity. The exact weight of the active material
coated on the carbon rod was computed by the
weight difference technique.
2.7 Materials characterization
X-ray diffraction (XRD) measurements on a-Fe2O3,
CNF and a-Fe2O3/CNF, a-Fe2O3/PANI composites
were performed on Rigaku D/MAX-RB X-ray
diffractometer with Cu-Ka radiation at a scan rate of
1 min-1. The surface morphology and compositional
analysis of CNF, a-Fe2O3, a-Fe2O3/CNF, and a-
Fe2O3/PANI composites were investigated using
Scanning Electron Microscope (Carl Zeiss EVO-18)
equipped with energy-dispersive X-ray spectroscopy
(EDAX). The detailed morphology, microstructures,
and crystalline nature of a-Fe2O3 were further
investigated using transmission electron microscopy
(TEM, JEOL 3010), high-resolution transmission
electron microscope (HRTEM, Tecnai G2, F30), and
selected area electron diffraction (SAED). The elec-
trochemical performances of composite electrodes
were measured on AutoLab electrochemical work-
station (PGSTAT204) using a three-electrode system
at room temperature in 1 M H2SO4 electrolyte. For
electrochemical characterization, a-Fe2O3/CNF and
a-Fe2O3/PANI composites coated on graphite rod
were used as the working electrode, a platinum wire
as the counter electrode, and Ag/AgCl (calomel,
3.5 M KCl) as the reference electrode. The composite
electrodes were dipped in electrolytes at least for an
hour before actual measurements to establish the
equilibrium. The cyclic voltammetry was performed
at scan rate 5–100 mV/s in a potential range of 0–1 V
for a-Fe2O3/CNF and -0.5 to 0.8 V for a-Fe2O3/
PANI. The capacitance of the electrode was gal-
vanostatically measured in the potential range of
0–1 V for a-Fe2O3/CNF and -0.5 to 0.8 V for a-
Fe2O3/PANI at current density ranging from 1 to
10 Ag-1. Electrochemical impedance spectroscopy
was performed under open-circuit potential with
frequency ranging from 10-2 to 105 Hz.
3 Results and discussion
3.1 Evolution of nano a-Fe2O3
The understanding of the corrosion mechanism of
iron structures is necessary to explore the feasibility
of rust products to transform them into usable
nanomaterial forms by applying simple grinding and
annealing technics. Under ambient environmental
conditions, the process of rusting begins on the sur-
face of iron structures via the creation of local inho-
mogeneities in terms of the accumulated dust,
moisture, and oxygen, leading to the formation of
several local electrochemical/concentration cells. The
electrochemical reactions occurring at the cathode
and anode lead to the formation of Fe2? and OH-
ions, respectively. These ions further migrate toward
each other and meet in between the cathodic and
anodic areas to form a molecular, hydrous, Fe(OH)2,
FeOOH species as initial corrosion products. These
products further grow by accumulating more and
more Fe2? and OH- ions to form a cluster of loosely
held (via weak Vander-Waals and Hydrogen bond-
ings) nanosized particles [49, 50]. The corrosion pro-
duct being porous, permit the access of corrosive
environment (water and oxygen) to the local site,
thus continuing corrosion further but following the
exponential decay law. The natural aging and drying
could convert Fe(OH)2 and FeOOH products to
FeO.xH2O and Fe2O3 clusters. Simple annealing at
this stage was sufficient to evaporate residual coor-
dinated water to form a porous, anhydrous Fe2O3
cluster. The process of strong mechanical grinding of
these porous clusters finally breaks into nanoscale
range Fe2O3 as observed. It is to be noted that the
usual chemical way of nanomaterial synthesis
involves nucleation, growth, and termination steps,
that may result in hard grains and clusters with the
fear of inclusion of impurities.
3.2 X-ray diffraction (XRD)
The XRD patterns of the as-obtained a-Fe2O3, CNF, a-
Fe2O3/CNF, and a-Fe2O3/PANI are shown in Fig. 1.
The XRD pattern of the as-prepared a-Fe2O3 (Fig. 1,
pink curve) shows the presence of sharp diffraction

Fig. 1 XRD patterns of a-
Fe2O3 (pink), carbon fibers
(navy blue), a–Fe2O3/CNF
(red), and a–Fe2O3/PANI
(blue) composites. The XRD
pattern of a-Fe2O3 from
standard JCPDS data is shown
at the bottom with black lines.
(Color figure online)
lines matching exactly to those patterns exhibited in
JCPDS card No. 33-0664, confirming the presence of
only rhombohedral modification of a-Fe2O3 (JCPDS
data are displayed in the form of black vertical lines
in Fig. 1 for easy comparison). The presence of sharp
diffraction lines indicates good crystallinity of the a-
Fe2O3 sample. Comparing the observed XRD pattern
with the data in the JCPDS card, we could conve-
niently assign the diffraction peaks observed at 2h
values of 24.10, 33.20, 35.60, 40.90, 49.50, 54.10, 57.60,
62.40, and 64.00 degrees as the reflections originating
from (012), (104), (110), (113), (024), (116), (018), (214),
and (300) planes of a-Fe2O3, respectively [21]. The
average crystallite size of the as-prepared Fe2O3
nanoparticles was about 28 nm, calculated from the
Debye–Scherrer equation (Eq. 1) based on the mea-
surements of the FWHM of the strongest (110) peaks:
t ¼ 0:9k=B cos h; ð1Þ
where B is the broadening of diffraction line mea-
sured at half its maximum intensity (in radians) and
t the diameter of crystal particle, h the diffraction
angle, and k is the wavelength of X-ray used [51]. We
J Mater Sci: Mater Electron
observed no diffraction peaks corresponding to any
impurities/contaminant indicating the high purity of
the sample obtained. The XRD patterns of CNF
(Fig. 1, navy blue curve) display a characteristic,
broad peak due to (111) plane of carbon material
exhibiting interlayer packing of hexagonal carbon
sheets. When a-Fe2O3 was coupled with CNF, we
observe no change in the crystalline phase of a-Fe2O3
and the XRD peak pattern of a-Fe2O3/CNF composite
(Fig. 1, red curve) keeps the characteristics peak
patterns of both the material phases, viz, a-Fe2O3 and
CNF, except the diminishing in the intensity of (111)
peak of CNF phase which can be attributed to bind-
ing of a-Fe2O3 with CNF in the composite. A similar
observation was found in the case of the XRD pattern
of a-Fe2O3/PANI composite (Fig. 1, blue curve)
which displays a prominent peak corresponding to
polyaniline (Emeraldine hydrochloride, JCPDS No
49-2500) and those corresponding to a-Fe2O3.
J Mater Sci: Mater Electron

Fig. 2 SEM images of a CNF, b a-Fe2O3, c a-Fe2O3/CNF, d a-Fe2O3/PANI, EDX spectrum of e a-Fe2O3/ PANI and f a-Fe2O3/ CNF

3.3 Scanning electron microscopy (SEM)
and energy-dispersive X-ray
spectroscopy (EDX)
The SEM images of CNF, a-Fe2O3, a-Fe2O3/CNF, and
a-Fe2O3/PANI are shown in Fig. 2a–d respectively,
while Fig. 2e, f displays EDAX of a-Fe2O3/ PANI and
a-Fe2O3/CNF respectively. Figure 2a shows the
morphology of carbon nanofibers with the presence
of a continuous interconnected network of fibers with
an average diameter of 400–500 nm. The CNF was
able to maintain its length and continuity in structure
even after carbonization, giving a large aspect ratio
and moderate interconnectivity among the fibers.
Such type of structure is highly desirable for use in
supercapacitor applications as it provides trans-
portation directionality with short ionic length dur-
ing charge storage [30]. Figure 2b shows the SEM
image of the as-prepared a-Fe2O3, displaying nano-
cluster, made up of a large number of interconnected
a-Fe2O3 nanoparticles having somewhat irregular
shapes. The SEM image of a-Fe2O3/CNF composite
in Fig. 2c shows the quite heavy decoration of a-
Fe2O3 particles over carbon fibers with some segre-
gated a-Fe2O3 nanoparticles forming tiny plate-like
clusters. The fiber network as observed in Fig. 2b was
also observed in Fig. 2c indicating that no new mor-
phology is generated in the process. The SEM of a-
Fe2O3/PANI (Fig. 2d) displays quite uniform, thick
distribution of PANI as a homogeneous layer over a-
Fe2O3 particles. This is especially required as PANI/
CNF provides the conducting surface over the poorly
conducting iron oxide. This intimate and heavy
junction between a-Fe2O3 and conducting CNF/
PANI is essential for a fast redox reaction occurring
during the electrochemical process. The EDAX pat-
tern of a-Fe2O3/CNF is displayed in Fig. 2f. The
presence of carbon, iron, and oxygen peaks and the
absence of any other elements/impurities confirm the
purity of a-Fe2O3/CNF composites. Similarly, the
EDAX pattern of a-Fe2O3/PANI (Fig. 2e) displays the
presence of nitrogen in addition to carbon, iron, and
oxygen without impurities.
3.4 TEM, HRTEM, and SAED of a-Fe2O3
The detailed morphology and microstructure of the
as-prepared iron rust have been further investigated
by TEM and HRTEM. Figure 3a, b shows TEM ima-
ges of the as-prepared iron rust at different
J Mater Sci: Mater Electron
resolutions. The images revealed that iron rust was
made up of aggregations of nanoparticles with sizes
ranging from 20 to 50 nm, the average matching
roughly with those obtained using the Scherrer for-
mula (28 nm). Further, the interplanar distance
measured out in the HRTEM image of 0.25 nm
(Fig. 3c) can be indexed to the lattice fringes of a-
Fe2O3(110) planes, which is prominently consistent
with the results of XRD. Figure 3d shows the SAED
pattern of a-Fe2O3NP’s with bright spots in the
diffraction circles confirming the crystalline nature of
a-Fe2O3 nanoparticles.
3.5 Electrochemical performance of a-
Fe2O3/CNF and a-Fe2O3/PANI
The electrochemical measurements on a-Fe2O3/CNF
and a-Fe2O3/PANI were performed in 1 M H2SO4
electrolyte using a three-electrode cell configuration
comprising a platinum rod as the counter electrode,
Ag/AgCl as the reference electrode, and individual
composites (a-Fe2O3/CNF and a-Fe2O3/PANI) dip
coated on graphite rod as the working electrodes. The
potential window was kept between 0 and 1 V for a-
Fe2O3/CNF and -0.5 to 0.8 V for a-Fe2O3/PANI.
Figure 4a, c displays CV profile before cycling,
while Fig. 4b, d displays CV profile after 5000 cycles
for a-Fe2O3/CNF and a-Fe2O3/PANI at 5, 10, 20, 30,
40, 50, 75, and 100 mV/s scan rates, respectively. The
approximately symmetrical, rectangular appearance
of the CV profile with distinct redox peaks demon-
strates the presence of pseudo-capacitive behavior.
As revealed from the SEM (Fig. 3a and b), the excel-
lent interconnectivity established between a-Fe2O3
nanoparticles and CNF greatly improves the electri-
cal conductivity, and provides large surface areas
with good interfacial contact and hence better elec-
tronic communication resulting in the observed
electrochemical performance (Fig. 4a). The a-Fe2O3/
PANI exhibited a much larger capacitive current of
180 mA (Fig. 4c) than Fe2O3/CNF (3 mA) (Fig. 4a) as
against bare a-Fe2O3, which did not show any com-
parable current. The highest electrochemical perfor-
mance of a-Fe2O3/PANI has resulted from the
excellent interconnectivity among PANI fibers and
nano-scaled a-Fe2O3 leading to the synergistic effect
between the two components. CV curves for a-
Fe2O3/PANI display well-defined pairs of redox
peaks during the anodic and cathodic sweeps. These
redox peaks confirm the active participation of both
J Mater Sci: Mater Electron

Fig. 3 a, b TEM images of a-Fe2O3, c HRTEM image of a-Fe2O3, d SAED pattern of a-Fe2O3

a-Fe2O3 and PANI. The sustenance redox reaction
executed by a-Fe2O3/PANI composite during cyclic
voltammetry has been proposed based on the facile
electron exchange between Fe3? and Fe2? (as it
exhibits variable oxidations states easily, requires no
mediators) [32] and various forms of PANI [52] as
under as follows:
Oxidation:
Feþ2 OFeþ4 O2 ! Feþ3 OFeþ4 O2 þ e
leucoemeraldine base (fully reduced)
! pernigraniline base (fully oxidised) þ e
(via emeraldine base/salt (EB/ES) intermediate
formation).
Reduction: Feþ3 OFeþ4 O2 þ e ! Feþ2 OFeþ4 O2 (4)
pernigraniline base (fully oxidised) þ e
! leucoemeraldine base (fully reducedÞ: ð5Þ
A couple of well-defined redox peaks were
observed within 0.2–0.8 V potential window due to
ð2Þ reversible interconversions as proposed above. This
coupled with the excellent homogeneity between
PANI and nanosized a-Fe2O3 particles resulted in a
ð3Þ
fast faradic process giving high pseudo-capacitance
and hence much higher specific capacitance. It is

Fig. 4 Cyclic voltammograms at different scan rates for a-Fe2O3/CNF a before cycling and b after 5000 cyclings; and for a-Fe2O3/PANI
c before cycling and d after 5000 cyclings
evident that with the increase in the sweep rate, the
peak current notably increases keeping the CV pro-
files intact. A slight potential shift of the redox peaks
can be ascribed to the internal charge transfer resis-
tance [53]. With the increase of scan rate, the specific
capacitance was found to diminish gradually as usual
and considered as normal behavior due to faster
diffusion of ions at a lower scan rate than higher [54].
After 5000 cycles (Fig. 4b, d), the area under the curve
has decreased for a-Fe2O3/CNF and a-Fe2O3/PANI
electrodes, indicating a decrease in specific capaci-
tance of both materials.
The fundamental behavior of the electrode material
was further explored through electrochemical impe-
dance spectroscopy (EIS). Figure 5a, b shows the
Nyquist plot of a-Fe2O3/CNF and a-Fe2O3/PANI
within the frequency range of 0.01–105 Hz at open-
circuit potential before cycling (black curve) and after
J Mater Sci: Mater Electron
5000 cycles (red curve), respectively. EIS spectra of a-
Fe2O3/CNF exhibit one depressed semicircle (Fig. 5a)
in the high-frequency range and a sloped straight line
in the low-frequency region corresponding to char-
acteristic charge transfer process (Rct) and Warburg
resistance (W) due to diffused limited process,
respectively. The absence of a linear portion in the
low-frequency range before and after cycling indi-
cates the presence of negligible surface Warburg
resistance in the electrolyte. This behavior is associ-
ated with the poor conductivity of a-Fe2O3 making
the charge transfer resistance too high so that elec-
trochemical reaction becomes slow, thus making the
diffusion process not a rate control step, as a conse-
quence, the Warburg impedance becomes insignifi-
cant leading to the absence of line portion at the low-
frequency region [1]. Besides, a slow rise in the
Faradic interfacial charge transfer resistance with
J Mater Sci: Mater Electron
Fig. 5 Electrochemical impedance spectroscopy (EIS) a for a-
Fe2O3/CNF before cycling (black) and after cycling (red); b for a-
Fe2O3/PANI before cycling (black) and after cycling (red).
cycling (red curve) has been observed. This is asso-
ciated with the partial deterioration of nanostructure
and the corrosion of the current collector during a
redox reaction, leading to observed lower conduc-
tivity after cyclings [32]. A notable reduction in
semicircle diameter for a-Fe2O3/PANI (Fig. 5b, black
curve) than for a-Fe2O3/CNF displays outstanding
electrical conductivity of a-Fe2O3/PANI, contributing
to much superior electrochemical performance. A
straight line versus a high angle to the Z’ axis before
and after cycling has been noticed, suggesting the co-
existence of abundant ion diffusion pathways and
their rapid movements in the active material leading
to differential capacitance [34, 54].
Galvanostatic charge–discharge curves at different current
densities; c for a-Fe2O3/CNF and d for a-Fe2O3/PANI. (Color
figure online)
Figure 5c, d shows GCD curves of a-Fe2O3/CNF
and a-Fe2O3/PANI recorded at different current
densities, respectively. A perfect triangular-shaped
charge/discharge curve in GCD implies the presence
of a pure EDLC-type capacitance. However, the GCD
curves of both the electrodes exhibit a plateau at
about 0.3–0.4 V as well as triangular behavior, indi-
cating the presence of a pseudo-capacitive faradic
feature. The specific capacitance of both the com-
posites has been calculated from GCD curves at dif-
ferent current densities using Eq. (6):
i  Dt
Cs ¼ ð6Þ
m  DV

where Cs is the specific discharge capacitance, i is the
current density, Dt is the discharge time, and DV is
the potential during discharge.
The a-Fe2O3/PANI composite possesses a high
specific capacitance of 192.29 Fg-1 at low current
density (1 Ag-1), while the specific capacitance for a-
Fe2O3/CNF was drastically decreased from 88.88 to
5.43 Fg-1 at the current density of 1–5 Ag-1. It is to be
noted that Fe2O3 decorated carbon nanotubes (CNTs)
synthesized using the microwave-assisted technique
reported the capacitance 204 Fg-1 at 0.5 Ag-1 current
density exhibiting an energy density of 28.3 Whkg-1
at a power density of 1Wkg-1 [55]. The relationship
between specific capacitance and current density of a-
Fe2O3/PANI composite material is superior at lower
Fig. 6 a C.V curves for a-Fe2O3/CNF (black) and a-Fe2O3/PANI
(red) at 5 mV/S; b Specific capacitance of a-Fe2O3/CNF (red) and
a-Fe2O3/PANI (black) as a function of current densities; c Ragone
J Mater Sci: Mater Electron
current density. All the curves clearly show the same
trend of the slowly decreasing nature of specific
capacitance with the increments in the discharge
current density. As displayed in Fig. 5c, d, a-Fe2O3/
PANI exhibited a longer discharge time (520 s) than
a-Fe2O3/CNF composites (330 s) at 1 Ag-1.
Figure 6a displays the CV comparison of a-Fe2O3/
CNF and a-Fe2O3/PANI at a scan rate of 5 mV/s. It is
observed that a-Fe2O3/PANI exhibits a much higher
area enclosed by a curve than Fe2O3/CNF, indicating
a high capacitive nature of a-Fe2O3/PANI than that
of Fe2O3/CNF composites. The characteristic transi-
tion redox peaks of PANI are visible at a scan rate of
5 mV/s. Figure 6b shows the relationship between
the specific capacitance at different current densities.
The specific capacitance of a-Fe2O3/CNF and a-
plot of a-Fe2O3/CNF(black) and a-Fe2O3/PANI (red) d Cycling
stability of a-Fe2O3/CNF (black) and a-Fe2O3/PANI (red) over
5000 cycles at a current density of 1 Ag-1. (Color figure online)
J Mater Sci: Mater Electron
Fe2O3/PANI composite was 88.88 and 192.29 Fg-1 at
1 Ag-1 current density, respectively. The specific
capacitance was drastically decreased to 5.43 Fg-1 for
a-Fe2O3/CNF (at a current density of 5 Ag-1) and to
84.04 Fg-1 for a-Fe2O3/PANI composite (at a current
density of 10 Ag-1), respectively. The decreasing
trend in specific capacitance with the increments in
the current density is observed for both composite
materials. The active surface of the electrodes may be
probably becoming inapproachable for charge
stockpile during the charge–discharge process,
resulting in the comparatively inadequate Faradic
redox reaction at higher discharge current densities,
which accounts for the abatement of specific capaci-
tance [56]. It is to be noted that Fe2O3 nano-spindles,
synthesized chemically via hydrothermal route, as
the positive electrode in 0.5 M K2SO4 electrolyte
showed a specific capacitance of 159 Fg-1 at 0.1 Ag-1
current density [46]. The results are much compara-
ble with mill scale-derived Fe2O3 sprayed on large
area iron/aluminum current collector electrode
(method reported as a greener synthetic route) which
gave 92 Fg-1 capacitance at 5 mVs-1 scan rate with
20% loss after 5000 cycles [47]. A dextran-based
template-free chemical method reported as a greener
method could exhibit better capacitance of 295 Fg-1
with loss of 15% capacitance in 1500 GCD cycles [48].
A chemical-free, simple mechanically press method
adopted for the synthesis of a-Fe2O3/Ni foil/C
reported having 40.07 Fg-1 capacitance and 20%
retention loss in just 500 cycles [57]. A facile, low-cost
hydrothermal method has been used to synthesize
binary nanocomposites gave 121.25 and 294 Fg-1
specific capacitance with 72.3% (after 2000 cycles)
and 82% (after 1000 cycles) capacity retention for a –
Fe2O3/C [58] and a-Fe2O3/ ordered porous C
nanocomposites [54], respectively. An expensive,
self-assembly chemical method was used to derive a-
Fe2O3/C reported to give a Csp value of 200 Fg-1 but
exhibited poor retention capacity [59]. An attempt to
make a thin film of PANI over a-Fe2O3 nanoparticles,
however, exhibited poor performance [60], whereas
microwave irradiation-synthesized composites,
although exhibited good specific capacitance of
204 Fg-1, showed poor retention capacity of 67% in
just 1000 cycles [61]. The electrodeposited binary
core–shell NW a-Fe2O3/ PANI also exhibited poor
performance in terms of volume capacitance
(2.02 mF/cm) [62]. The comparison of the literature
reported data with our findings is gathered in
Table 1. It displays the data for only binary oxides (a-
Fe2O3) coupled with either PANI or form of carbon
(CNF, C etc.), obtained via various methods, includ-
ing facile, less expensive, and waste-derived/greener
methods. It is observed that although the waste-
derived or green method of synthesis exhibits abso-
lute capacitance lower than more expensive synthetic
methods, the cost per kilowatt performance and the
life cyclability can be competitive for large grid-scale
storage applications.
The performance of a supercapacitor is expressed
in terms of the energy density and power density,
which can be calculated from Eqs. 7 and 8
respectively:
ðDVÞ2
E ¼ Cs ð7Þ
2
E
P¼ ð8Þ
Dt
where Cs is the Specific Capacitance, DV is the
potential window, and Dt is the discharge time. The
Ragone plot, the plot of specific energy (Wh/Kg)
versus the specific power (W/Kg), is shown in Fig. 6c
for a-Fe2O3/CNF and a-Fe2O3/PANI electrodes. For
a-Fe2O3/CNF composite, the increase in specific
power from 69.39 to 410.63 Wkg-1 tend to decrease
the specific energy from 3.08 to 0.1 Whkg-1, whereas
a-Fe2O3/PANI showed specific energy of
-1 -1
11.28 Whkg at a specific power of 162.44 Wkg
with a maximum specific power density of
1623.78 Wkg-1 at a specific energy of 4.93 Whkg-1;
the results confer good power characteristics of a-
Fe2O3/PANI than of a-Fe2O3/CNF. The higher
power output makes the material promising for
applications where high-power output, as well as
high energy capacity, is required. The cycling stabil-
ity is considered as an effective element of superca-
pacitor for realistic application purposes. Figure 6d
demonstrates long-term cycling properties of the a-
Fe2O3/CNF (black curve) and a-Fe2O3/PANI (red
curve) composite tested by continuous GCD mea-
surements at a current density of 1 Ag-1 for 5000
cycles. The specific discharge capacitance of a-Fe2O3/
CNF and a-Fe2O3/PANI electrodes drops by 25% and
20% of the initial capacitance, respectively, after 5000
cycles, displaying an excellent cycling performance
for both the electrodes. The loss after 5000 cycles is
attributed to the stacking and agglomeration of active
sites in the process.
 J Mater Sci: Mater Electron

Table 1 Comparison of results obtained for binary-type a-Fe2O3 and PANI or carbon nanocomposites obtained by various methods

Sr Electrode materials (binary Source Specific capacitance Capacitance Energy density Ref
type) (Fg-1) retention Whkg-1

1 Core-shell MnO2/Fe2O3/C Nano Chemical (hydrothermal) 159 (0.1 Ag-1) 97.4% (5000 – 46
spindlese cycles)
2 a-Fe2O3/C Scrap mill wasted 92 (1 Ag-1) 80% (500 4 47
cycles)
3 Mesh-like Fe2O3a/Dextran Template-free chemical 295 (0.5 Ag-1) 88.9% (1500 37 48
derived) C (greener route)d cycles)
4 Nano a-Fe2O3/Ni foil/Carbon Mechanical pressd 40.07 (10 mV/s)h 80% (500 – 57
blacke cycles)
5 a-Fe2O3/C nanocomposites One-pot hydrothermal 121.25 (5 Ag-1) 72.3% (2000 – 58
cycles)
6 a-Fe2O3/Ordered multimodal Hydrothermal 294 (1.5 Ag-1) 82% (1000 – 54
porous carbon Cycles)
7 mesoporous a-Fe2O3/Polymer- Self-assemblyf (chemical) 204 (0.5 Ag-1) 20wt 95% (380 39.4 59
derived carbone % Fe2O3 cycles)
8 Thin films a-Fe2O3/PANI Chemical 218.66 (0.5 A/g) 87% (1000 32.35 60
composite cycles)
9 Core shell a-Fe2O3/CNTg Microwave irradiation 204 (0.5 Ag-1) 67% (1000 28.3 61
cycles)
10 Core-Shell Nanowire array a Electrodeposition 2.02 mF/cm3b 95.77% 0.35c 62
Fe2O3/PANI (10000cycles)
11 a-Fe2O3/PANI Waste derived 192.29 (1 A/g) 80% (5000 11.28 This
cycles) work
12 a-Fe2O3/CNF Waste derived 88.88 (1 A/g) 75% (5000 3.084 This
cycles) work
a
Orthorhombic modification of hematite
b
Volumetric capacitance
c
Volumetric energy density
d
Waste derived/greener route
e
Ternary composites
f
Block copolymer/iron oxide nanocomposites were prepared by carbonization of poly(t-butyl acrylate)-block-polyacrylonitrile (PtBA-b-
PAN), and nano 4-hydroxylbenzoic acid-activated Fe2O3 hydrophobic nanomaterial
g
Exhibited pure EDLC-type super capacitance
h
Calculated from the area enclosed by CV

4 Conclusions electrodes showed a maximum specific capacitance

The decorations of waste iron rust-derived a-Fe2O3
on CNF and PANI were successfully done by using
electrospinning, hydrothermal, and in-situ polymer-
ization methods to evolve Fe2O3/CNF and Fe2O3/
PANI composite materials. The electrochemical
characterizations were done by using cyclic voltam-
metry (CV), galvanostatic charge–discharge (GCD),
and electrochemical impedance spectroscopy (EIS).
The a-Fe2O3/CNF and Fe2O3/PANI as positive
of 88.88 and 192.29 Fg-1 at 1 Ag-1 scan rate and the
energy density of 3.08 and 11.28 Whkg-1 with the
power density of 69.39 and 162.44 Wkg-1, respec-
tively. A loss of 25% for a-Fe2O3/CNF and 20% for
Fe2O3/PANI in specific capacitance has been regis-
tered after 5000 continuous charge/discharge cycles,
indicating a highly stable cycling performance. The
facile, low-cost evolution of waste iron rust into
useful a-Fe2O3 nano-material and its subsequent uti-
lization in supercapacitors exhibited better
J Mater Sci: Mater Electron

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