Synthetic Metals 232 (2017) 66–71

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Research paper

A facile method to synthesise reduced graphene oxide/carbon nanotube MARK

hybrid fibers as binder-free electrodes for supercapacitors
⁎
Mei Zhang, Yunming Jia, Hongwei Li , Jianming Wang
College of Materials Science and Engineering, Beijing Institute of Fashion Technology, Beijing 100029, China

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

Keywords: The reduced graphene oxide/carbon nanotube hybrid fibers (G/CNTs) were prepared by a facile chemical re-
Reduced graphene oxide duction and self-assembly strategy at low temperature. SEM images indicate a certain degree of reduced gra-
Carbon nanotube phene oxide nanosheets and carbon nanotube orientation along the main axis of the obtained hybrid fibers. The
Self-assembly reduced graphene oxide/carbon nanotube hybrid fibers exhibit large surface area of 149.85 m2 g−1 and good
Flexibility
mechanical strength. The electrochemical performances of hybrid fibers as flexible and binder-free electrodes are
Supercapacitors
evaluated by using a three-electrode system, and it displays high specific capacitance of 243.0 Fg−1 at a current
density of 200 mA g−1, which is mainly ascribed to porous structure and large specific surface area. The as-
synthesized reduced graphene oxide/carbon nanotube hybrid fibers will be potential candidate for flexible and
binder-free electrodes for supercapacitors.

1. Introduction
With the increasing requirements of wearable, portable and flexible
electronic products, the miniaturized, lightweight and flexible super-
capacitors, with high power density and high energy density, have at-
tracted significant attention as promising energy storage devices [1–6].
Flexible and binder-free electrode materials play an important role in
future applications for high-performance supercapacitors. Flexible
electrodes have mainly been fabricated using carbon-based materials,
such as amorphous carbon, carbon nanotube (CNT) and graphene in
previous published papers [1,7,8]. To meet flexibility and binder-free
requirements, carbon nanotube or graphene based 3D aerogels, 2D
membranes, and 1D fibers electrode materials have been widely re-
searched. The 1D fiber-typed electrodes have been developed to rea-
lized wearable storage devices and smart textiles due to combining
easily with textiles [9,10].
The 1D linear graphene fibers, with good mechanical flexibility,
wearable and electrical properties in contrast to graphene-based aero-
gels and membranes, can be fabricated by individual graphene na-
nosheets [11]. In the synthesis processes, the graphene fibers tend to
restack into graphite-like structure due to the aggregating nature
caused by strong π-π interactions, which destroy the excellent char-
acteristics of the individual graphene nanosheets, such as high surface
area [5,12,13]. The flexible CNT fibers possess many combined ad-
vantages including low density, high tensile strength and high electrical
conductivity. But the CNT fibers exhibit relatively low electrochemical
activities that are found to be critical for electronic applications [14].
To overcome these problems, the graphene and carbon nanotube hybrid
fibers can be prepared by solution spinning, which can reduce the ag-
gregation of graphene nanosheets to obtain larger specific surface area,
and improve the electrochemical properties [15–17].
In this paper, the reduced graphene oxide/carbon nanotube hybrid
fibers (G/CNTs) were prepared by a facile low temperature induced
self-assembly strategy, and the synthesis process is shown in Fig. 1. The
G/CNTs are fabricated at different temperature of 90 °C and 120 °C
until the hybrid fibers fully form, which is beneficial to controlling
ordered and porous structure. The as-prepared G/CNTs exhibit large
specific surface area of 149.85 m2 g−1, and good flexibility, which can
be conveniently woven into variety patterns. The G/CNTs deliver high
specific capacitance of 195.1 Fg−1 after 500 cycles at a current density
of 200 mA g−1, which is mainly ascribed to the designed structure and
synergistic effect between reduced graphene oxide and carbon nano-
tube. These reduced graphene oxide/carbon nanotube hybrid fibers will
be an ideal candidate of electrode materials for flexible and bendable
supercapacitors, and the development can promote more engineering
applications of graphene and carbon nanotube.
2. Experimental
2.1. Synthesis of materials
Natural graphite power with 20–30 μm were received from Qingdao

⁎
Corresponding author.
E-mail address: clylihongwei@bift.edu.cn (H. Li).

http://dx.doi.org/10.1016/j.synthmet.2017.07.010
Received 3 April 2017; Received in revised form 25 May 2017; Accepted 18 July 2017
Available online 10 August 2017
0379-6779/ © 2017 Elsevier B.V. All rights reserved.
M. Zhang et al.
Fig. 1. Scheme of G/CNTs synthesis processes.
Fig. 2. XRD patterns of Graphite, GO, G6/CNTs, G10/CNTs, and G20/CNTs.
Fig. 3. FTIR spectra of Graphite, GO, CNTs, CO-CNTs, G6/CNTs, G10/CNTs and G20/
CNTs.
Ruisheng Graphite Co., Ltd. Other chemicals were of analytical grade
and used as received from Sinopharm Chemical Reagent Co., Ltd.,
without further purification. Using graphite power, the graphite oxides
(GO) suspension (GO dispersed in water) with high concentration were
prepared by modified Hummers method, which could keep a long time
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Synthetic Metals 232 (2017) 66–71
at room temperature. The mixtures of 3.6 g carbon nanotube, 90 ml
H2SO4 and 30 ml HNO3 was put in an ultrasonic bath for 2 h, it was
transferred into oil bath at 120 °C for 2 h, the carboxylic carbon na-
notube (CO-CNTs) were obtained from carbon nanotube (CNTs), then
the CO-CNTs were washed by deionized water to form uniform CO-
CNTs suspension. As shown in Fig. 1, graphene oxide and carboxylic
carbon nanotube were combined by a facile chemical reduction and
self-assembly strategy at low temperature, the preparation of reduced
graphene oxide/carbon nanotube hybrid fibers (G/CNTs) could be di-
vided into three steps: first, the obtained GO solution was diluted to
7 mg ml−1, and the mixed suspension of GO and CO-CNTs was put in an
ultrasonic bath for 30 min. Second, 0.12 g reducing agent (ascorbic
acid) was added into the mixed suspension and make the mixtures well-
distributed. Third, the obtained mixtures were sealed into the specified
diameter glass tube by using PTFE membrane and put it in an oven at
90 °C for 2 h, and the gel-fibers were preliminarily formed, then the
temperature increased to 120 °C until fibers fully formed. The synthesis
process of hybrid fibers was continually accompanied by the volatili-
zation of water. The forming of hybrid fibers is mainly due to capillary
forces and surface-tension-induced sheet interactions. The G/CNTs with
different mass ratio values of 6:1, 10:1 and 20:1 could be named G6/
CNTs, G10/CNTs, G20/CNTs, respectively. The graphene oxides were
reduced by ascorbic acid to obtain reduced graphene oxide under the
same synthesis processes.
2.2. Characterization
The structures and morphologies of G/CNTs were characterized by
Field emission scanning electron microscopy (FESEM, JEOL JSE-
7500F). The tensile strength of G/CNTs were evaluated by Dynamic
Mechanical Analyzer (DMA, Q800). The Brunauer-Emmet-Teller (BET)
surface area of the as-synthesized samples were measured using a sur-
face area detecting instrument (Kubo X1000) analyzer by N2 physi-
sorption at liquid nitrogen temperature. In addition, other auxiliary
information of the products was observed by X-ray diffraction (XRD, X
Pert MDP) and Fourier transform infrared spectra (FTIR, Nicolet Nexus
670).
2.3. Electrochemical testing
The electrochemical performance of the as-synthesized G/CNTs
were performed in 6 M KOH solution as flexible and binder-free elec-
trode materials in a three-electrode system, using Pt as a counter
electrode and Hg/HgO as a reference electrode. The galvanostatic
charge-discharge performance were conducted on LAND instrument at
M. Zhang et al.
a current density of 200 mA g−1. The specific capacitance (C, Fg−1) of
G/CNTs were calculated by C = (I × Δt)/(ΔV × m), where I is the
discharge current (A), Δt is the discharge time (s), ΔV is the voltage
difference in discharge (V) and m is the mass of the active materials
within the electrode (g) [18,19].
3. Results and discussion
Fig. 2 shows XRD patterns of Graphite, GO, G6/CNTs, G10/CNTs and
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Synthetic Metals 232 (2017) 66–71
Fig. 4. FESEM images of CNTs (a), CO-CNTs
(b), G6/CNTs (c–d), inset of (c): graphene
fibers, G10/CNTs (e–f) and G20/CNTs (g–h).
G20/CNTs. GO has a typical characteristic peak located at 11.6° corre-
sponding to d-spacing of 0.762 nm larger than that of nature graphite
(about 0.34 nm). The G6/CNTs, G10/CNTs and G20/CNTs display si-
milar diffraction peaks at about 25.9° assigned to aggregation of re-
duced graphene oxide nanosheets, which indicates the decreasing of
interlayer spacing and reduction of graphene oxides. It may be ascribed
to the desorption of oxygen-containing functional groups and H2O
molecules in three kinds of hybrid fibers [20,21].
FTIR spectra of Graphite, GO, CNTs, CO-CNTs, G6/CNTs, G10/CNTs
M. Zhang et al.
Fig. 5. Tensile strength of G6/CNTs, G10/CNTs, and G20/CNTs.
and G20/CNTs are shown in Fig. 3. It can be seen that a large number of
oxygen-containing functional groups exist in the infrared spectra of GO,
such as CeO epoxy groups (1072 cm−1 and 1328 cm−1) and C]O
stretching of carbonyl and carboxyl groups (1766 cm−1) [22–24]. The
infrared spectra of CO-CNTs also show similar characteristic peaks with
that of GO. In addition, almost all representative peaks relative to
oxidized groups decreased dramatically in the FTIR of G/CNTs with
different G and CNTs ratios, and even some of them disappeared en-
tirely. These observations confirm the reducing of oxygen functional
groups on the surface and edge of GO and CO-CNTs during synthesis
processes, which agrees with the XRD results.
The morphologies and structures of CNTs, CO-CNTs, G6/CNTs, G10/
CNTs and G20/CNTs are shown in Fig. 4. SEM images of CNTs and CO-
Fig. 6. CV curves of G6/CNTs (a), G10/CNTs (b) and G20/CNTs (c) at different sweep rates (20 mV s−1, 30 mV s−1, 40 mV s−1, 50 mV s−1, 80 mV s−1, 100 mV s−1); (d) CV curves of G6/
CNTs, G10/CNTs and G20/CNTs at 50 mV s−1.
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Synthetic Metals 232 (2017) 66–71
CNTs display similar morphologies (Fig. 4a and b), indicating the oxi-
dizing agent of H2SO4 and HNO3 don’t destroy structure and
morphologies of CNTs. As shown in Fig. 4c–h, the surfaces of hybrid
fibers are rather smooth at the microscale and the diameter is 200 μm.
Reduced graphene oxide nanosheets and CNTs together tend to restack
into ordered microstructures, and the cross-section of G/CNTs displays
the stacked reduced graphene oxide and CNTs that are aligned along its
main axis, which is ascribed to controllable synthesis process at dif-
ferent temperature of 90 °C and120 °C. The aligned CNTs interposed as
spacers between reduced graphene oxide nanosheets, which are bene-
ficial for the growing of the ordered and well-developed porous archi-
tecture, the increasing of active sites and large specific surface area
[15]. With the increasing of reduced graphene oxide nanosheets in
hybrid fibers, the G/CNTs display more compact lamellar structures,
providing flexibility and a certain degree of mechanical strength.
Fig. 5 has compared the typical stress-strain curves of G6/CNTs,
G10/CNTs and G20/CNTs to better reflect the mechanical properties
(Fig. 5). The tensile strength of G6/CNTs, G10/CNTs and G20/CNTs are
up to 111 MPa, 161 MPa and 196 MPa, respectively, and they can also
be conveniently woven into various patterns (Fig. 1). The tensile
strength and the various patterns imply good mechanical flexibility of
G/CNTs, which is mainly ascribed to high degree of orientation of re-
duced graphene oxide nanosheets and carbon nanotube because of ca-
pillary forces and surface-tension-induced sheet interactions [25]. The
reduced graphene oxide/carbon nanotube hybrid fibers show promising
application in energy storage devices and textile electronics.
The cyclic voltammogram (CV) of the as-synthesized G6/CNTs, G10/
CNTs and G20/CNTs are measured between −0.8 V and 0.2 V in 6 M
KOH solution to understand the electrochemical reaction and stability
in charge-discharge processes. Fig. 6a–c displays the CV curves of G6/
CNTs, G10/CNTs and G20/CNTs at different sweep rates of 20 mV s−1,
30 mV s−1, 40 mV s−1, 50 mV s−1, 80 mV s−1 and 100 mV s−1. With
M. Zhang et al.
Fig. 7. (a) Galvanostatic charge-discharge curves of G6/CNTs, G10/CNTs, and G20/CNTs
at a current density of 200 mA g−1; (b) Cycle performance of G6/CNTs, G10/CNTs, and
G20/CNTs at a constant current density of 200 mA g−1.
the increasing of scan rate, the G6/CNTs, G10/CNTs and G20/CNTs still
maintain similar rectangular shape, and indicate a good capacitive
behavior and kinetic performance for G20/CNTs electrodes, which is
probably due to the fast ion transportation derived from high electrical
conductivity and high specific surface area of G20/CNTs [3,26]. As
shown in Fig. 6d, the G20/CNTs shows the highest current output under
same sweep rate of 50 mV s−1, implying the largest specific capaci-
tance. The results demonstrate the G20/CNTs have good flexibility and
electrochemical stability as electrodes for supercapacitors.
The electrochemical performance of G6/CNTs, G10/CNTs and G20/
CNTs were evaluated in 6 M KOH solution in a three-electrode system.
As shown in Fig. 7a, the galvanostatic charge-discharge curves of G/
CNTs remain linear and symmetrical shape, indicating their double-
layer capacitor behavior during charge and discharge processes with a
wide current range. The specific capacitance of G6/CNTs, G10/CNTs and
G20/CNTs can be calculated from charge-discharge curves at a current
density of 200 mA g−1. The specific capacitance of G6/CNTs, G10/CNTs
and G20/CNTs are 196.2 Fg−1, 222.5 Fg−1 and 243.0 Fg−1, suggesting
the dramatically improved specific capacitance of G/CNTs electrodes
Table 1
Electrochemical performance of some carbon nanotube and graphene binder-free hybrid electrodes for supercapacitors.
Materials Preparation method
CNT/RGO fibers Glass pipeline, 750 °C for 15 min in argon.
SWNT/rGO fibers Hydrothermal processes, ethylenediamine, 220 °C for 6 h
CF-RGO-CNT fibers CVD, carbon fiber, H2 and Ar thermal reduction at 750 °C
GO-CNT/CC films Electrophoretic deposition (EPD) technique, carbon cloth, H2 thermal reduction
CNT/graphene hybrid films Coating, under 10 MPa, at 80 °C for 24 h
RGO/CNT films Drying,180 °C for 3 h
G20/CNTs Self-assembly, ascorbic acid, 90 °C for 2 h and 120 °C for 2 h
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Synthetic Metals 232 (2017) 66–71
with the increasing of reduced graphene oxide nanosheets and possess
better specific capacitance than that of pure graphene fibers
(109.4 Fg−1) reported in our previous paper. At the same time, the
hybrid fibers display high specific capacitance in the first charge-dis-
charge cycle and the specific capacitance reduce suddenly in the sub-
sequent cycles, which may be attributed to the impurity in synthesis
process or the occurrence of side reaction. In Fig. 7b, the electro-
chemical stability of G/CNTs are evaluated at a constant current density
of 200 mA g−1, and the specific capacitance of G6/CNTs, G10/CNTs and
G20/CNTs remain respectively 166.3 Fg−1, 185.2 Fg−1 and 195.1 Fg−1
after 500 charge-discharge cycles. The specific capacitance only has a
slight change during long cycles and the result demonstrates the hybrid
fibers possess stable electrochemical properties. According to previous
reports, the electrochemical performance of some carbon nanotube and
graphene binder-free hybrid electrodes, have been listed in Table 1
[4,16,27–30]. In general, the G/CNTs show good electrochemical per-
formance due to ordered and porous structure, and synergistic effect
between CNTs and reduced graphene oxide nanosheets [28]. The re-
duced graphene oxide and carbon nanotube hybrid fibers can be widely
utilized as flexible and binder-free electrode materials for energy sto-
rage.
To further understand good properties, the specific surface areas of
G20/CNTs, reduced graphene oxide nanosheets and CNTs, and pore size
characterization of G20/CNTs were performed by nitrogen adsorption-
desorption isotherm measurements (Fig. 8). As shown in Fig. 8a, the
calculated Brunauer-Emmet-Teller (BET) specific surface areas of G20/
CNTs, reduced graphene oxide and CNTs are 149.85 m2 g−1,
105.15 m2 g−1 and 128.16 m2 g−1 (Fig. 8a, c–d). The specific surface
areas of G20/CNTs is higher than that of reduced graphene oxide na-
nosheets and pure graphene fiber (75.91 m2 g−1) synthesized under
same condition [11]. It may be attributed to the more fluffy, porous
structure and synergistic effect because of the CNTs interposed between
reduced graphene oxide nanosheets [28]. Fig. 8b show BJH pore size
distribution plots of G20/CNTs, and it exhibits main pore size is cen-
tered at around 2.9 nm. The fluffy structure with mesopores can ef-
fectively facilitate ions and electrons diffusion to active sites with less
resistance, leading to the improved electrochemical performance as
flexible and binder-free electrode materials for supercapacitors.
4. Conclusions
In summary, the G/CNTs were prepared by a facile chemical re-
duction and induced self-assembly strategy at low temperature (90 °C
and 120 °C), which is benefit to fabricating the orientated and well-
developed porous architecture. The as-synthesized G20/CNTs not only
have excellent flexibility, but also have a high specific capacitance and
good cycle stability. The specific capacitance of G20/CNTs reach
243.0 Fg−1 at a current density of 200 mA g−1 and still remain
195.1 F g−1 after 500 charge-discharge cycles. This is mainly ascribed
to the ordered, porous structure and large surface area. Apart from
supercapacitors, the G/CNTs could be utilized widely in different fields,
including separation, catalysis, and adsorption. This work we propose
will promote the development of graphene and carbon nanotube ma-
terials.
Electrolyte Scan rate Capacitance Refs.
−2 −1
1 M NaSO4 20 μA cm 200.4 Fg [4]
3 M KCl 73.5 mA cm−3 305 Fcm−3 [16]
1.5 M Li2SO4 100 mV s−1 203 Fg−1 [27]
1 M H2SO4 1 Ag−1 151 Fg−1 [28]
Organic electrolyte 1 Ag−1 50.5 Fg−1 [29]
1 M H2SO4 0.5 Ag−1 428 Fg−1 [30]
6 M KOH 0.2 Ag−1 243 Fg−1 This work
M. Zhang et al.
Acknowledgments
We acknowledge financial support from the General Program of
Science and Technology Development Project of Beijing Municipal
Education Commission of China (SQKM201610012002), The Talent
Project of Beijing Institute of Fashion Technology (2015A-18), The
Beijing Municipal Key Laboratory Program (2015ZK-4).
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