Journal of Physics and Chemistry of Solids 130 (2019) 242–249

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Journal of Physics and Chemistry of Solids

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Investigation of cyclic voltammetry and impedance spectroscopy of T

thermally exfoliated biomass synthesized nickel decorated graphene
Rabina Bhujela, Bibhu P. Swainb,∗
a
Centre for Materials Science and Nanotechnology, Sikkim Manipal Institute of Technology, Sikkim Manipal University, Majhitar, 737136 India
b
Department of Physics, National Institute of Technology, Manipur, Langol, Imphal, 795004, Manipur, India

A R T I C LE I N FO A B S T R A C T

Keywords: The cyclic voltammetry and impedance spectroscopy of nickel decorated multilayered graphene (NiMGr) thin
Ni decorated graphene films were investigated by the thermal exfoliation of onion (Allium cepa) with different process temperature
Biomass synthesis from 600 to 1000 °C. The AFM images reveal the size distribution of Ni particles varies from 50 to 100 nm on the
AFM surface of graphene sheets. The diffraction planes (002), (111) and (200) are observed at 24, 44.3 and 51.6°
Impedance spectroscopy
corresponding Ni particles embedded with NiMGr sheets. The Raman parameter, ID/IG and I2D/IG ratio varied
from 0.94 to 0.8 and 2.52 to 1.38 respectively indicated the formation of NiMGr containing some defect states.
The areal capacitance of NiMGr varied from 12.19 to 22.9 μF/cm2 respectively, with different process tem-
perature from 600 to 1000 °C. The corrosion potential (Ecorr) and corrosion current density (Icorr)values are
−0.18 V and −13.29 A/cm2 respectively, for the NiMGr processed at 1000 °C, showing the highest corrosion
resistance against acidic solutions. These encouraging findings for NiMGr demonstrate its possibility in various
fields like supercapacitors as well as anti corrosion coatings.

1. Introduction
Graphene has been attracting remarkable attention of the re-
searchers owing to their multifunctional properties like excellent elec-
trical, thermal conductivity, high mechanical strength and young
modulus, high surface area with the ease of functionalization which,
allows their applications in various fields like in bioelectronics and
biosensing [1], supercapacitors [2], lubricants [3,4], electronics [5],
batteries [6], optics [7] as well as in many more emerging fields. Metal
such as Ni decorated with graphene (NiMGr) surface has ability to
enhance the surface reactivity and functionality which leads to improve
above applications. Hence tailoring and building new characteristics of
graphene to achieve unique properties has recently become an inter-
esting subject for research. Specifically, the electronic properties of
graphene have been improved by chemical functionalization and elec-
trochemical modification for their use in various electronic fields. Gao
et al. fabricated a ferromagnetic Fe/Fe3C NPs with a graphene shell
(ACT@Fe/Fe3C/graphene) and achieved a discharge capacity of
≈764 mAh g−1 [8]. Ray et al. investigated structural network of NiMGr
from lotus pellet [9]. Barakat et al. synthesized NiMGr from urea electro
oxidation [10] and evaluated various physical properties. Gao et al.
fabricated a ACT/NiS2−graphene cell with ultrahigh initial capacity of
∼1710 mAh g−1 at a rate of 0.01 C [11]. Zhang et al. investigated
NiMGr for H2 gas sorption [12]. Liu et al. synthesized NiMGr from one-
pot hydrothermal reduction of graphene oxide process for selective
isolation of polyhistidine-tagged proteins [13]. Lan et al. studied NiMGr
for their improved electrochemical performance as an
La0.7Mg0.3(Ni0.85Co0.15)3.5 electrode material [14]. Lu et al. successfully
accomplished NiMGr as an anode materials for Li ion batteries with an
enhanced electrochemical properties [15].
NiMGr exhibits high specific capacitance and excellent life cycle-life
stability resulting from fast electron transport, large active surface area,
and better structural stability [16]. However, above enhanced the
properties vary directly depending upon the synthesis techniques,
oxygen content present on graphene sheets as well as the micro-
structure of the NiMGr composites.
Therefore, the current report mainly focuses on the inexpensive,
facile and green synthesis of NiMGr samples by the thermal exfoliation
of allium cepa. The electrochemical properties were investigated using
the cyclic voltammetry, Tafel plot, electrochemical impedance spec-
troscopy and impedance vs. voltage plot using H2SO4 as an electrolyte
solution to obtain the capacitance of the NiMGr electrodes. The mor-
phological and structural analysis was done in order to investigate the
possible changes in the morphology and structure of NiMGr samples
which may affect the capacitive properties.

∗
Corresponding author.
E-mail addresses: bibhuprasad.swain@gmail.com, bpswain@nitmanipur.ac.in (B.P. Swain).

https://doi.org/10.1016/j.jpcs.2019.02.023
Received 24 October 2018; Received in revised form 25 January 2019; Accepted 19 February 2019
Available online 23 February 2019
0022-3697/ © 2019 Published by Elsevier Ltd.
R. Bhujel and B.P. Swain
2. Experimental details
The extracted onion peels (scientific name Allium cepa) were used
as raw material for the synthesis of Ni decorated graphene. At first, the
onion peels were dipped in an aqueous solution of nickel chloride for
12 h. To remove the moisture from the Ni-dipped onion peels, a 110 °C
temperature was applied for 3 h in an oven. To perform the thermal
exfoliation process in anaerobic condition, a silicon carbide resistance
vacuum furnace (made: V.B. Ceramics) was used. During the heating
process, Ar gas (IOLAR-I grade of BOC, India) was purged in the furnace
to make an inert atmosphere. The successive quality production of
NiMGr was achieved at the temperature 600–1000 °C at the ramp rate
of 5 °C per minute to fix temperature and maintain the same for 2 h. The
AFM characterization of the NiMGr was by Nanoscope III scanning
probe microscope and SEM characterization was performed with the
help of EVO MA18 with Oxford EDS (X-act). The Raman characteriza-
tion was done with the help of 532 nm laser at 1.5 mW power (Witec
Alpha 300 RS). The XRD characterization was done with the help of
PAN Analytical Spectris Technologies (PW 3040/60) and XPS analysis
was done with the help of VG ESCA-LABMK II with a Mg(Kα) X-ray
(1253.6 eV) source. The electrochemical properties of NiMGr were
analyzed with the help of CH Instruments, Inc. (Electrochemical
Anayzer CHI608E) by using Ag/AgCl as the reference electrode, Pt wire
as the counter electrode and NiMGr coated glassy carbon electrode as
the working electrode. The electrochemical impedance spectroscopy
was performed for all NiMGr in 0.5% H2SO4 solution to study the dif-
ferent electrochemical behaviors.
3. Results and discussion
Fig. 1 and Fig. 2 shows the 2D and 3D AFM images to study the
surface morphologies of NiMGr prepared at the processing tempera-
tures of 600, 700, 800, 900 and 1000 °C and the roughness assessment
of all NiMGr obtained at various process temperature is given in
Table 1A large number of Ni particles were distributed on the surface of
Ni-graphene composites processed at 800, 900 and 1000 °C while very
few number of Ni particles are present on the surface of NiMGr pro-
cessed at 600 and 700 °C. The incorporation of Ni particles inside the
Fig. 1. 2D AFM images of NiMGr synthesized with varying the process temperature from 600 to 1000 °C.
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Journal of Physics and Chemistry of Solids 130 (2019) 242–249
graphene layers increases with increasing the process temperature and
is maximum for 1000 °C processed Ni/Gr sample. The Ni-particles ag-
glomerated and formed clusters with the cluster size of ∼3.5 μm in case
of 800 and 900 °C processed NiMGr as observed in Figs. 1 and 2. The Ni
particles are uniformly distributed over the surface of graphene pro-
cessed at 1000 °C and have size in the range of 170.8–323.07 nm. The
average roughness (Ra) and root mean square roughness (Rq) decreases
from 58.7 nm to 20.9 nm and 76.8 nm–26.8 nm respectively as the
process temperature was increased from 600 to 1000 °C. This decrease
in the Ra of 1000 °C processed Ni/Gr sample further supports the uni-
form distribution of Ni particles on the graphene surface shown in
Table 1.
Fig. 3 shows the SEM image of 1000 °C processed NiMGr sample.
The SEM image clearly illustrates that the Ni nanoparticles are well
distributed over the graphene sheets, which confirms the successful
formation of Ni decorated graphene sample by the thermal exfoliation
process of onion. The SEM result is in agreement with the AFM image
shown in Figs. 1 and 2 for the 1000 °C processed NiMGr sample.
Fig. 4(a) shows the Raman spectra of NiMGrwith varying the pro-
cess temperature from 600 to 1000 °C. The asymmetric Raman sig-
nature from 1000 to 2000 cm−1 is obtained for first order phonon
scattering in multilayer graphene. For the detailed explanation and
understanding, the first order Raman spectra of all the NiMGr samples
were deconvoluted into three Gaussian peaks at 1166.2, 1351.9 and
1575.3 cm−1 corresponding to D*, D and G bands respectively [17,18].
The D peak corresponds to the extent of disorder present in the gra-
phene sheets and the in-plane vibration of sp2 hybridized C atoms of the
hexagonal C ring within the graphene sheets is shown by the G peak
which arises due to the vibration of LO phonon modes [18]. Further-
more, the D* peak is attributed to LA phonon modes which arises due to
the highly disordered morphology of sp3 hybridized amorphous carbon
structures, originated at the edges and holes of the graphene layers at
the H terminating edge of C]C chains [17]. With the variation in
processing temperature, the shape and height of the D and G band
seems to vary from the graphene samples. This variation could be due
to variation in the amount of the functional groups or defects remained
in graphene sheets and the amount of Ni doping during the exfoliation
process of onion cells. Moreover, a second order band in every NiMGr
R. Bhujel and B.P. Swain Journal of Physics and Chemistry of Solids 130 (2019) 242–249

Fig. 2. 3D AFM images of NiMGr synthesized with varying the process temperature from 600 to 1000 °C.

Table 1
Surface roughness of Ni decorated graphene prepared at different process
temperatures.
Process Temperature (OC) Average roughness Root mean square roughness
(Ra) (Rq) (nm)
(nm)

600 58.7 76.8

700 28.8 45.8
800 24.0 36.9
900 22.4 29.9
1000 20.9 26.8

Fig. 3. SEM image of NiMGr sample processed at 1000 °C.

Fig. 4. (a) Raman spectra, (b) second order deconvoluted Raman bandsand (c)
has been observed for the symmetry allowed overtone of G band, which
ID/IG& I2D/IG vs process temperature plot of NiMGr with varying the process
are useful for detecting the stacking order of graphene sheets in dif-
temperature from 600 to 1000 °C.
ferent NiMGr. It was observed that the second order peak is not very
sharp and is in the range of 2200–3400 cm−1 confirming the formation

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Table 2
Second order Raman peak position and FWHM of NiMGr at various tempera-
tures.
Process 2D D+G C
Temperature
(oC) Peak FWHM Peak FWHM Peak FWHM
Position (cm−1) Position (cm−1) Position (cm−1)
(cm−1) (cm−1) (cm−1)

600 2803.81 526.57 2973.89 101.23 3175.82 328.77

700 2673.96 402.83 2909.63 253.59 3125.16 198.72
800 2700.37 590.01 2927.46 206.74 3154.79 169.13
900 2685.72 463.42 2922.25 215.96 3086.80 600.90
1000 2676.19 463.7 2925.45 220.74 3105.28 473.59

of multilayered graphene structure. The result shows similarity with the

previously reported results by Shams et al. for the graphene sample
prepared by the pyrolysis of camphor leaves at 1200 °C [19].
Fig. 4(b) shows the deconvolution of second order Raman peaks of
NiMGr with different processing temperature. The board Raman sig-
nature from 2200 to 3400 cm−1 was deconvoluted into three Lor-
entzian peaks for the detailed analysis of NiMGr. The peak at ∼2700,
∼2925 and ∼3154 cm−1 corresponds to the 2D, D + D’ or D + G and
C peaks respectively [17,18]. The details of Raman peak positions and
FWHM of 2D, D + G and C band were shown in the Table 2. The second
order peaks are the result of combination mode frequencies of primary
phonons. The double resonant process of D (LO) phonons gives rise to
2D bands, whereas the D and G (LO) phonon resonance gives the D + G
peak. The C peak corresponds to the CeH stretching mode of aromatic
carbon. The broadness of the second order Raman signature may be due
to the presence of impurity molecules or the multilayer structural de-
fects present in graphene sheets. Moreover, the low intensity of the
second order peak may be due to the formation of multilayered NiMGr.
The major observations from the deconvolution are.
(i) The 2D peak shifted towards the red region from 2803.81 to
2676.19 cm−1 with simultaneous decrease in FWHM from 526.57
to 463.7 cm−1 for all the NiMGr.
(ii) The FWHM of D + G band is increased from 101.23 to
220.74 cm−1by shifting the peak position towards the red region
from 2973.89 to 2925.45 cm−1 with an increase in the process
temperature.
(iii) The FWHM of C band increased from 328.82 to 473.59 cm−1 with
the respective peak position shifting towards the red region from
3175.82 to 3105.28 cm−1.
The peak shifting as well as variation in the FWHM may be caused
due to the following reasons (i) modification of the C structure of onion
cells in the hexagonal ring structure geometry of graphene with the
thermal exfoliation of onion cells and (ii) homogeneous distribution of
Ni particles on the graphene sheet at higher temperature (iii) decrease
in the number of graphene layers and increase in the number of
sp2defects with increasing the processing temperature from 600 to
1000 °C [20].
Fig. 4(c) shows the intensity ratios of ID/IG and I2D/IG of Raman
parameters of NiMGr with varying the process temperature from 600 to
1000 °C. The intensity ratio of ID/IG decreased from 1.85 to 1.38 with
the simultaneous decrease in I2D/IG from 1.89 to 0.8 as the process
temperature increased from 600 to 1000 °C. The decrease in ID/IG ratio
is indicative of the decrease in the number of defects within the NiMGr
sheets [19]. According to Tuinstra and Koenig ID/IG = C(λ)/La, where
the coefficient C (514 nm) ∼4.4 nm (λ ≡ 2πc/ωL is the excitation
wavelength) and La is the crystal size [20]. Therefore, the smaller the
value of ID/IG ratio greater is the size of graphene cluster and hence less
is the number of disorders present in the graphene sheets. Furthermore,
the decrease in I2D/IG ratio indicates decrease in the number of
Fig. 5. XRD patterns of NiMGr sample with varying the process temperature
from 600 to 1000 °C.
graphene layers for the NiMGr prepared at higher process temperature.
The ratio I2D/IG for high quality (defect free) single layer graphene is
equal to 2. But in our case a slight decrease of I2D/IG ratio is observed
from 1.89 to 0.8 with the increase in the process temperature is may be
due to the formation of multilayered graphene structure decorated with
Ni particles.
Fig. 5 shows the XRD spectra of NiMGr sample with varying the
process temperature from 600 to 1000 °C. The XRD band at ∼24.3°
with the corresponding plane of (002) is obtained for graphene sheets.
Similar band at ∼24° was also observed by Gotoh et al. for graphene
sheets [22]. Moreover, the peaks at 44.3 and 51.6° with the corre-
sponding planes of (111) and (200) are observed for Ni particles de-
corated on graphene sheets. Similarly the XRD patterns at 28.3 and
40.3° with the corresponding planes of (400) and (200) are assigned for
the NiO particles. Hence, the XRD result confirms the formation of Ni
decorated multilayer graphene sheets. It can be seen that the lower
temperature processed NiMGr samples does not have the XRD patterns
for NiO particles, but with an increase in the process temperature from
600 to 1000 °C the peaks for NiO particles becomes more and more
prominent. At higher temperature the oxygen containing functional
group present in the onion peels are expected to break and remove from
the carbon backbone and get attached with the Ni nanoparticles de-
corated on the graphene sheets. This results in the formation of some
NieO bond in the NiMGr samples.
Fig. 6 shows the wide scan XPS spectra of NiMGr samples with
varying the process temperature from 600 to 1000 °C. The photoelec-
tron binding energies at 284.1, 530, 851.6 and 876.5 eV corresponds to
the C (1s), O (1s), Ni (2p3/2) and Ni (2p1/2) respectively. Moreover the
small peaks arising at 69, 107.8, 636.7, 710.6, 777.6 and 932.9 eV are
assigned to the Ni (3p), Ni (3s), Ni (LMM), Ni (LMM1), Ni (LMM2) and
Ni (2s) respectively. The appearance of the carbon, oxygen and Ni peaks
confirms the formation of Ni decorated multilayer graphene by the
thermal exfoliation of allium cepa. The atomic percentage of C, O and
Ni in the NIMGr samples was calculated by applying the formula
Ai
Atomic % =
Si
A
∑ Si (1)
1
where Ai is the area under the XPS curve and Si is the relative sensitivity

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R. Bhujel and B.P. Swain Journal of Physics and Chemistry of Solids 130 (2019) 242–249

Fig. 6. Wide scan XPS spectra of NiMGr sample with varying the process
temperature from 600 to 1000 °C.

factor which is 0.23 and 0.66 and 2.69 for C (1s) and O (1s) and Ni
(2p3/2) respectively. It can be seen from Fig. 6 that with the increment
in the processing temperature from 600 to 1000 °C the atomic % of C, O
and Ni varied from 71.7 to 64.22%, 23.3–34.6% and 4.9–1.154% re-
spectively. The increase in the oxygen content in NiMGr sample pro-
cessed at higher temperature may be caused due to the trapping of
removed oxygen atom from the onion peels by the Ni nanoparticles
decorated in the graphene sheets. The XPS result is in accordance with
the XRD result explained earlier. This increase in the oxygen fictiona-
lization might affect the electrochemical properties of NiMGr samples.
Fig. 7 (a) shows the cyclic voltametric curve of NiMGrwith varying
the process temperature from 600 to 1000 °C to analyze the electro-
chemical properties at the scan rate of 0.1–0.5 V/s. The CV curve of all
the NiMGrhas quite distorted loop with a quasi rectangular shape due to
the oxidation reduction reaction taking place on the surface of the Fig. 7. (a) Cyclic voltammetric curve of NiMGr with varying the process tem-
NiMGr electrode as because Ni acts as a catalyst on the graphene sur- perature from 600 to 1000 °C. (b) Specific capacitance vs process temperature
face which enhances the redox reactions taking place on the surface of plot of all NiMGr at different scan rates.
graphene sheets. Xu et al. reported that the number of layers and
thickness of NiMGrhas a great impact on the oxidation and reduction the NiMGr with varying the scan rate from 0.1 V/s to 0.5 V/s. The in-
behavior of graphene, which leads to an increase in the oxidation and tegrated area of the CV curve increases with increasing the scan rate
reduction currents. Moreover, the distorted hysteresis loop indicates the from 0.1 to 0.5 V/s for all the graphene suggesting a good capacitive
presence of pseudo capacitaive capacitive behavior [23]. As shown in behavior due to the rapid charge propagation capability the pseudo-
Fig. 7 (a) hump arises for all the NiMG at (± 0.3 V), which slightly in- capacitive behavior as observed for the NiMGr, indicating the stability
creases with the increase in process temperature from 600 to 1000 °C. of capacitance of the graphene electrodes [26]. The areal capacitance of
This increase in the peak intensity is mainly due to an increase in the Ni the as-prepared electrode was calculated from the CeV curves using the
concentration on graphene at higher temperatures, which further leads following equation:
to an increase in the reduction of various functional groups like car-
bonyls and hydroxyls on the surface of NiMGr [24,25]. It is observed Ca = I
that by changing the scan rate from 0.1 to 0.5 V/s the current as well as S × ⎡ dv ⎤ (2)
⎣ dt ⎦
the size of the CV curve increases for all the NiMGr suggesting a rapid
charge propagation capability of pseudo-capacitance [26]. where Ca is the areal capacitance (F), I is the integrated area of the CV
Furthermore, with the increase in the process temperature from 600 curve, dv/dt is the scan rate, S is the surface area of the electro active
to 1000 °C, the width of the hysteresis loop increases indicating an in- material. From Fig. 7(b) its clear that the areal capacitance increases
crease in the adsorption of the graphene samples. The greater is the from 12.19 μF/cm2 to 22.9 μF/cm2with increasing the process tem-
number of pores available on the surface, the higher will be the contact perature from 600 to 1000 °C temperature at the scan rate of0.5 V/s.
surface area with the electrolyte, and hence there is more availability of The areal capacitance of all the Ni/Gr samples with varying the scan
the redox-reaction active sites [27]. Moreover, the increased number of rate from 0.1 V/s to 0.5 V/s are listed in Table 3.
Ni particles and hence the defects on the surface of NiMGr might be the Fig. 8 shows the polarization curves of the NiMGr samples synthe-
other reason for the enhancement of the redox reactions. Fig. 7 (b) sized at different process temperatures of 600, 700, 800, 900 and
shows the area under the CV curve versus process temperature plot for 1000 °C. It is clear from the results that the NiMGr processed at 1000 °C
has a lower corrosion current density of −13.295 A/cm2 and higher

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R. Bhujel and B.P. Swain Journal of Physics and Chemistry of Solids 130 (2019) 242–249

Table 3 (ii) A large potential difference between the graphene and Ni possess
Areal capacitance of Ni decorated graphene samples in μF/cm2 as obtained by an inert physical behavior which is further responsible for the im-
the area of the CV curve. provement of corrosion resistance by NiMGr processed at 1000 °C.
Process Temperature OC 0.1 V/s 0.2 V/s 0.3 V/s 0.4 V/s 0.5 V/s A similar study was also done by Jabbar et al. for the NiMGr
composite coatings deposited at different bath temperatures [28].
1000 21.60 23.75 23.75 22.96 22.90
900 22.34 24.20 23.80 23.80 21.20
Fig. 9(a) shows the Nyquist plots of NiMGr prepared by varying the
800 10.60 25.50 22.90 24.50 23.90
700 12.90 15.78 15.83 15.89 14.80 process temperature from 600 to 1000 °C. A perfect semicircle is ob-
600 13.12 13.95 13.12 14.0 12.19 tained for all the NiMG in the frequency range of 1–100000 Hz. The
semicircle is assigned to the charge transfer impedance of each Ni/Gr
samples. The inserted schematic equivalent circuit diagram inside
Fig. 9(a) represents Re, RCT, and Cdl, are attributed to the sum of the
resistance offered by the bulk electrolyte, electrode and the contact
between the electrode and the current collector [29]. The double layer
capacitance is represented as Cdl. The estimated charge transfer re-
sistance of NiMGr vary from 23.98 to 134.15 Ohms with increasing the
process temperature from 600 to 1000 °C. Therefore, the smallest
semicircle was obtained for NiMGr processed at 600 °C, due to its lowest
conductivity. Hence, NiMGr processed at 600 °C can be used as an ex-
cellent scaffold for the growth of different electroactive materials on it
for fast electron transport [30]. Moreover, the NiMGr synthesized at
1000 °C has the greater impedance, indicative of better anti corrosive
property than the NiMGr synthesized at low temperatures. The dia-
meter of the semicircle explains the anti-corrosion property, larger
diameter gives better corrosion resistance. Hence, NiMGr processed at
1000 °C possess the superior anti corrosive property [28]. Fig. 9(b)
shows the frequency responses of impedances of the NiMGr samples
synthesized by varying the process temperature from 600 to 1000 °C.
The result shows that the impedance increased from 27.2 to 147.02
Ohms as the process temperature increased from 600 to 1000 °C re-
spectively. The increase in impedance, in turn, is due to an increase in
the resistance (Re + RCT) offered by the NiMGr electrodes as the pro-
cess temperature increased from 600 to 1000 °C as listed in Table 3. The
impedance at lower frequency region, i.e. below 103 Hz with the cor-
responding phase angle of ∼φ = 0° gives the value of total resistance
offered by the electrode and electrolyte Re + RCT. In the frequency
range of 103 to 2 × 104 Hz with the corresponding maximum phase
angle, the value of impedance in this region is attributed to a capacitor
in parallel with a resistance due to the charge transfer process (RCT) for
Fig. 8. Tafel plot of all NiMGr processed at the temperature of 600–1000 °C.
a reversible reaction as reported earlier by Casero et al. [31]. The im-
pedance at higher frequency region, i.e. > 105 Hz, is attributed to the
electrolytic resistance (Re) between the reference and the working
corrosion potential of −0.18 V than the other NiMGr processed at electrode. The estimated values of Re and RCT for all Ni/Gr samples are
lower temperatures, indicative of improved corrosion resistance by the listed in Table 3. From the Bode plot as well minimum impedance was
NiMGr prepared at 1000 °C. The data of Icorr and Ecorrfor all the NiMGr reflected by the 600 °C processed NiMGr with the Re,RCT and φmax
samples as determined from the polarization curve is listed in Table 4. values of 5.84 Ohm, 21.36 Ohm and −33.59° respectively.
The reasons responsible for the improved corrosion resistance offered Fig. 10(a) shows voltage dependent impedance of NiMGr with dif-
by the NiMGr prepared at 1000 °C are as follows‫׃‬ ferent process temperature varying from 600 to 1000 °C. The im-
pedance Z remains constant at positive voltages from 0 to 1 V however,
(i) The uniform distribution of Ni particles on the graphene sheets impedance increases with increasing negative voltage and maximum
during the exfoliation process of onion cells at higher temperature impedance was observed at −0.65 V, except for NiMGr processed at
fills the cavities and holes, which further prevents the adsorption of 600 °C showing no maxima. The impedance voltage plot of NiMGr is
ions present in the electrolytic solution responsible for the corro- almost linear over the whole voltage range having a minimum im-
sion of electrodes. pedance. The maxima at −0.65 V varied from 4.1 to 17.87 Ohm as the

Table 4
Different Parameters Obtained From Bode, Nyquist, Tafel, Impedance-Voltage plot and XPS analysis.
Bode plot Nyquist plot Tafel Plot Voltage dependent

Re (Ω) RCT (Ω) φmaxin ( )

O
Re (Ω) RCT (Ω) ωmax (Hz) Ecorr (V) 2
ICorr (A/cm ) Z (Ω) ϕ

600 °C 5.84 21.36 −33.59 5.95 23.98 −10.04 −0.21 −9.59 4.1 −4.53
700 °C 5.29 35.31 −54.76 5.3 30.08 −20.51 −0.34 −9.09 29.32 −27.59
800 °C 4.34 25.86 −48.74 10.2 77.06 −25.61 −0.15 −8.96 8.83 −21.00
900 °C 11.51 134.33 −56.89 7.15 123.09 −52.01 −0.21 −9.78 16.25 −60.16
1000 °C 11.28 135.74 −59.59 7.44 134.15 −61.16 −0.18 −13.29 17.87 −65.22

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R. Bhujel and B.P. Swain
Fig. 9. (a)Nyquist plot and (b) Bode plot of NiMGr, by varying the process temperature from 600 to 1000 °C.
Fig. 10. (a)Impedance vs Voltage and (b) Phase vs Voltage plot for NiMGr processed at various temperature of 600–1000 °C.
process temperature increased from 600 °C to 1000 °C. This indicates
with the reverse voltage the diffusive charge accumulated at the in-
terface of the electrode hence the relative capacitance and resistance
increases with increasing of voltage. The increase of impedance from
-1 V and reaching a maximum at −0.65 V indicates a decrease of the
capacitive behavior, while on the negative side the value of impedance
slowly decreases and becomes constant at 0 V indicating an increase in
the capacitive behavior of NiMGrin this region.
Fig. 10(b) shows the phase versus voltage plot of graphene elec-
trodes within the voltage range of −1 to 1 V. The phase remained
unchanged at 0–1 V whereas the phase decreased and showed a
minimum at −0.65 V. The minima of phase varied from −4.53 to
−65.22° for the NiMGr as the process temperature increased from 600
to 1000 °C.
4. Conclusion
Biomass synthesis of NiMGr samples were successfully synthesized
by the thermal exfoliation of onion peels with varying the process
temperature from 600 to 1000 °C. The Ni particles of 50–100 nm are
distributed over the surface of NiMGr sheets. The areal capacitance
varied from 12.19 to 22.9 μF/cm2 for the scan rate of 0.5 V/s with the
process temperature varying from 600 to 1000 °C, showing maximum
capacitance for the 1000 °C processed graphene samples. A minimum
corrosion rate was observed for the graphene sample processed at
1000 °C and having the Ecorr and Icorr values of −0.18 V and −13.29 A/
cm2 respectively, therefore high temperature processed graphene are
better corrosion resistant material than the low temperature processed
ones. From the AC impedance spectroscopy, maximum impedance was
offered by the 1000 °C processed graphene sample at the initial voltage
of −0.1 V. These encouraging findings for Ni decorated graphene
samples demonstrates its possibility in various fields like
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Journal of Physics and Chemistry of Solids 130 (2019) 242–249
supercapacitors as well as anti-corrosion coatings.
Acknowledgement
One of the authors Ms. Rabina bhujel acknowledges Dr. Ramdas Pai
and Mrs. Vasanthi Pai endowment fund (Ref: SMU/ENDOW/2016-17/
292/002) for providing the financial support for conducting this re-
search work. We thank to Prof. Rajiv Dusane, Department of
Metallurgical Engineering and Materials Science, Indian Institute of
Technology Bombay for Raman Characterization of Ni decorated
Graphene nanocomposites.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.jpcs.2019.02.023.
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