Accepted Manuscript

Chlorine-doped reduced graphene oxide as an efficient and stable electrode for

supercapacitor in acidic medium

Karim Kakaei, Milad Hamidi, Somayeh Husseindoost

PII: S0021-9797(16)30423-4
DOI: http://dx.doi.org/10.1016/j.jcis.2016.06.058
Reference: YJCIS 21368

To appear in: Journal of Colloid and Interface Science

Received Date: 5 April 2016

Revised Date: 18 June 2016
Accepted Date: 26 June 2016

Please cite this article as: K. Kakaei, M. Hamidi, S. Husseindoost, Chlorine-doped reduced graphene oxide as an
efficient and stable electrode for supercapacitor in acidic medium, Journal of Colloid and Interface Science (2016),
doi: http://dx.doi.org/10.1016/j.jcis.2016.06.058

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Chlorine-doped reduced graphene oxide as an efficient and stable electrode for
supercapacitor in acidic medium

Karim Kakaei*1 , Milad Hamidi1 and Somayeh Husseindoost 1

1
Department of Physical Chemistry and Nano chemistry, Faculty of Science, University Of
Maragheh, P.O. Box. 55181-83111, Maragheh, Iran

Abstract

We demonstrate the efficient doping of reduced graphene oxide (RGO) by Chlorine and its
capacitive performance was alculated by cyclic voltammetry and charge–discharge cycling in
1M H2SO4 solution. In this regard, we are prepared RGO nanosheets through a simple, eco-
friendly and efficient electrochemical method, with selectively functionalized edges by
chlorine which involves added the RGO to the halogen-containing acid solution and
dispersed by ultrasonic. After synthesis, Cl-RGO is characterized using X-ray diffraction,
Raman spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, Energy-dispersive X-
ray (EDX) spectroscopy and tunneling electron microscopy. FTIR spectra show the chlorine-
containing functional groups. Energy-dispersive X-ray spectroscopy analysis confirmed the
presence of doped chlorine in RGO. Raman spectroscopy shows a high density of defects in
the RGO layer. Electrochemical charactristics of Cl-RGO are characterized by cyclic
voltammetery, galvanostatic charge/discharge and electrochemical impedance spectroscopy.
According to the galvanostatic charge/discharge analysis, Cl-RGO represents specific
capacitance (Cs) of 178.4 Fg -1 at current density of 1 A g-1, which is higher than that of RGO
(100.5 Fg -1) in H2SO4 solution.
Keywords: electro-synthesis, reduced graphene oxide, chlorine-doped, , supercapacitor,
electrochemical performance

* 1
Corresponding author. Tel.: +98-41-37276068, fax: +98-41-37276066

E-mail address: kakaei@maragheh.ac.ir , k_kakaei56@yahoo.com (Karim Kakaei)

1. Introduction

Electrochemical capacitors (ECs), are considered as one of the most promising candidate for
energy storage systems, due to their ability to store high energy, reversibility, high power
performance , high rate capability and very long life cycle [1-3].
Transition metal oxides/ hydroxides, conducting polymers and carbon materials are usually
investigated as electrode materials for supercapacitor [4-7]. Among them, different
carbonaceous materials such as activated carbon, amorphous carbons, mesoporous carbon
and carbon nanotubes have been used as materials of electrode [8-11].
Carbon based materials have received much attention in recent years due to their unique
structural stability, polarizability, excellent electrical conductivity, high surface area, low cost
and versatile forms of existence such as fibers, powders, sheets, tubes and etc[12, 13] .
Graphene as a new carbonaceous materials is a rapidly rising star in the field of materials
science and technology. This strictly two-dimensional material exhibits exceptionally high
electronic conductivity and large specific surface area, has been widely explored as electrode
materials in the fields of ECs [14, 15]. Numerous methods have been investigated to
synthesize graphene and graphene oxide materials such as mechanical cleavage of graphite,
epitaxial growth of GN films on substrate by vacuum graphitization and chemical
processing[16]. Although, as a result of ingesting expensive precursor, energy and time,
development of simple low-cost approaches for synthesis of graphene-based materials is still
a foremost challenge in research area . According to these parameters, eco-friendly or
environmental benignity and facile synthesis process, graphene and graphene derivatives
have studied as excellent materials for supercapacitor [12, 17].
Recently because of poor intrinsic capacitance of graphene numerous studies have been
conducted to introduce heteroatom into the graphene framework for modulating its electron
acceptor or donor properties and thus improving the capacitance and cyclic stability in
supercapacitor[18]. Graphene-doped with various heteroatoms such as oxygen, boron,
nitrogen, phosphor, sulfur and their mixtures have been investigated in order to study their
capacitive performance[19, 20]. Among the dopants, nitrogen-doped graphene has attracted a
great deal of attention because experimental studies showed that doping with nitrogen can
improve capacitance performance of graphene [21, 22]. However, the agglomeration due to
intensive p–p interaction is dramatically reduces the surface area, resulting in a lower
capacitance[23]. Yu et.al [12] have reported the synthesis of X-doped graphene (X= I, Br, )
through a method, which involves ball milling of graphite in the presence of hydrogen (H 2),
bromine (Br2) and iodine (I2) and tested as supercapacitor electrode. All the X-doped
graphene show excellent electrochemical performance in terms of specific and long term
stability. But, to the best of our knowledge after extensive literature survey, Cl-doped reduced
graphene oxide (Cl-RGO) has been unexplored in supercapasitor application. Therefore,
these Cl-RGO materials is expected to have remarkable potential as electrode material for
supercapacitor.

2. Experimental section

2.1 Reduced graphene oxide (RGO) synthesis

RGO was synthesized from graphite rod according to previous works but we shall briefly
repeat the main features here [24-27]. Static potentials of 5 V using a DC power supply were
applied to the 2 graphite electrodes and exfoliation of graphite was occurred.
2.2 Preparation of Cl-RGO
Solution containing chlorine was ready by adding 0.1 mol/L of NaClO into 15 mL of H2SO4
10 mol/L in a glass bottle. In order to synthesis of Cl-RGO, 2.0 mg of RGO was added into
the halogen-containing acid solution and dispersed by ultrasonic for 40 min. Then the
solution was stirred at room conditions for 12 h. then the Cl-RGO was filtered and washed
with mixed of ethanol and water and finally dried at 450C[24].
2.3 Ink Preparation and electrode fabrication
A mixture containing a homogeneous suspension of Isopropanol (Merck), water, 5 wt %
Nafion solution as binder electrode were homogenized by sonication for 40 min, then painted
onto glassy carbon electrode. The mass of active materials coated on working electrode is
about 1.5 mg.
3. Results and discussion
The formation of C-Cl bonds was investigated with fourier transform infrared spectroscopy
(FT-IR). Fig. 1 shows FT-IR spectra of RGO and Cl-RGO samples. The characteristic
difference between non-chlorinated and chlorinated sample is the presence of C-Cl bond at
1182 cm-1 and 876 [24, 28]. The FT-IR spectra of these samples indicate weak peaks centered
at around 3445, 1625 and 1088 cm-1, which can be related to the vibrations of O-H, C=O and
C-OH functional groups, respectively[29]. Besides to C-Cl bonds, the other deference
between these two samples is in the amount of functional groups are especially in intensity of
C-O groups. This suggests that with the exception of the chlorine, the chemical structures of
both samples are comparable together.
Fig.2 shows XRD and Raman curves for Cl-RGO and RGO samples. The XRD patterns
(Fig.2a) of RGO appeared a sharp diffraction peak at 2θ= 26.470 attributed to the C (002)
peak corresponds to a graphene layer with a d-spacing of 3.36 Å. However, Cl-RGO has a
low-intensity and broad diffraction peak for C (0 0 2) in comparison with pure RGO which
suggests the short-range order in stacked graphene sheets[30].The (002) peak at 26.01 (2θ)
for Cl-RGO sample corresponds to a interlayer spacing of 3.52 Å.
Raman spectra of RGO and Cl-RGO in Fig. 2b displayed distinct G-band and D-band peaks,
which are characteristic of all carbon-based materials. It is obvious that D band is related to
the structural defects, while G band assigned to E2g vibration mode of sp2 carbon domains.
Because of addition of heteroatom to the RGO which involve the significant increase of
defect density, the D band of Cl-RGO well reveals that one pot reaction RGO is very
effective material to synthesis Cl-RGO in very short time. Fig.3a,b represents the TEM
images of RGO, which is more wrinkled structure.
Fig. 4(a) demonstrates the comparative CV curves of GC, RGO and Cl-RGO samples at a
scan rate of 50 mV s-1 in 1 M H2SO4 aqueous solution in the potential window between -0.2
to 1.1 V. From Fig. 4a, b, it can be seen that bare GC electrode cannot substantially
contribute in charge storage process in H2SO4. In the CV curves of the RGO and Cl-RGO
electrodes based on GC in the potential intervals from 0 to 0.8 V(Fig4b) show an
approximately rectangular feature which is typical of an electrochemical capacitor. By
comparing the area under the CV curve within the voltage window the difference in the
specific capacitance can be estimated, therefore the specific capacitance of Cl-RGO is higher
than that RGO. The presence of redox peaks and pseudocapacitive characteristic resulting
from the existence of residual oxygen groups such as caroxyl and carbonyl on the surface of
RGO sheets, which arises from the contribution of both faradaic and non-faradaic process in
the energy storage mechanism[31].
Figs. 5, 6 display the variation in specific capacitance of the fabricated electrodes as a
function of scan rates. It can be seen that the specific capacitance reduces with the increase of
scan rates from 10 to 100 mV s-1. The specific capacitance of Cl-RGO electrode (Fig6a,b) is
much higher than that of un-doped RGO (Fig5a,b) at the similar scan rates. On the other
hand, the specific capacitance of 101.F g-1 is obtained at 10 mV s-1 in 1 M H2SO4 aqueous
medium for RGO, compared to 179.6 for Cl-RGO. Even at 100 mV s-1, Cl-RGO still reveals
the specific capacitance of 155.1 F g-1, while only 81.2 F g-1 for pure RGO.
The galvanostatic charge/discharge is employed to determine the electrochemical capacitance
of RGO and Cl-RGO at current loads of 1, 0.5, 0.25 and 0.1 A/g.
The charge/discharge curves of the samples are given in Fig7. The charge/discharge profile
related to Cl-RGO and pure RGO electrodes shows symmetric triangle shape even at high
current load of 1.0 A/g, reflecting fast charge propagation with a small ohmic drop. The
charge/discharge duration increases with the current densities from 1 to 0.1 A/g. Moreover,
the charge-discharge duration of Cl-RGO is higher than that RGO , implying the higher
specific capacitance for Cl-RGO. This result is in accordance with those deduced from the
CV measurements[32].
The specific capacitance C (F g-1) of the 2 samples from the discharge process was
calculated according to the following formula[33]:

eq.1

Where I is the constant discharge current (A), Δt is the discharge time (s), ΔV is the potential
change during discharge process, and m is the mass of material in the samples (total weight of
RGO and Cl-RGO casted on the electrodes) (g).
The specific capacitances of RGO and Cl-RGO electrodes at the current density of 1 A/g are
obtained 100.5 and 178.4 F g−1.
The electrochemical impedance spectroscopy (EIS) of the RGO and Cl-RGO electrodes were
measured in the frequency range of 100 kHz to 100 mHz at open circuit voltage with an ac
perturbation of 5mV before cycling and after 5th and 300th cycle ( Fig. 8a,b). As can be seen
that the impedance spectra are almost similar in form, composed of a semicircle at the high-to
medium frequencies and a straight line at low frequency before and after cycling in both
samples. The semicircle at high frequency shows charge-transfer resistance and arises due to
intrinsic resistivity of the electrode material, whereas the straight line is related to the
diffusion resistance through the bulk of the material. After 5th and 300th cycle the charge
transfer resistance for RGO increases from 6.2 to 6.8 and 7.4 and the diffusion limitation is
also raised, which is may be attributed to the crack of composite during charge/discharge
process[34]. In Cl-RGO electrode the charge transfer resistance before CV and after 5th and
300th cycle increases from 3.44 to 4.10 and 5.12 Ώ and also the Warburg resistance, which
can be visualized in Nyquist curve by the extent of deviation towards x-axis at the end of
semicircle is enhanced. It could be suggested that the Cl-RGO electrode displays a more
vertical line than RGO at low-frequency, indicating better capacitive process and lower
diffusion resistance of ions[32].
4. Conclusions
Cl doped RGO as electrode materials for supercapacitors had been prepared by functionalized
edges by chlorine which involves added the RGO to the halogen-containing acid solution and
dispersed by ultrasonic. The presence of Cl in RGO is investigated by XRD, EDX, Raman
and FT-IR. The incorporation of Cl into RGO can inhibit the agglomeration of graphene
sheets and improve the electrolyte–electrode accessibility. On the other hand the introduction
of Cl-atoms into RGO can increase electron mobility, leading to a larger space charge
capacitance. Cl- RGO exhibits the specific capacitance of 178.4 F g-1 from charge/discharge
profile, which is higher than that of pure RGO material (100.5 F g-1). Furthermore, the
specific capacitance even at 100 mV s -1 exhibited of 170.1 F g-1.
Therefore, the Cl-RGO with high specific capacitance and good cycling stability are quite
suitable and promising electrode materials for high performance supercapacitors.

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Captions

Fig.1 (a) FTIR spectra of RGO, Cl-RGO (b) EDX spectra of RGO, Cl-RGO (C) inset
enlarged spectrum in the 2-5 KeV

Fig.2 (a) XRD spectra of RGO, Cl-RGO (b) Raman spectra of RGO, Cl-RGO

Fig.3 Typical TEM image of RGO

Fig.4 CV curves at 50 mVs-1 for GC , RGO and Cl-RGO in 1 M H2SO4 aqueous medium
between (-0.2 to 1.1 V vs Ag/AgCl) (b) between (0 to 0.8 V vs Ag/AgCl)

Fig.5 (a) CV curves at different scan rates for RGO in in 1 M H 2SO4 aqueous medium
between (-0.2 to 1.1 V vs Ag/AgCl) (b) between (0 to 0.8 V vs Ag/AgCl)

Fig.6 (a) CV curves at different scan rates for Cl-RGO in in 1 M H2SO4 aqueous medium
between (-0.2 to 1.1 V vs Ag/AgCl) (b) between (0 to 0.8 V vs Ag/AgCl)

Fig.7 the charge-discharge curves at various current densities for RGO and Cl-RGO

Fig.8 Nyquist plots of complex-plane impedance in 1M H2SO4 electrolyte using a three-

electrode configuration in 1M (a) Cl-RGO (b) RGO
Graphical abstract