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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet
Research paper
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 activities that are found to be critical for electronic applications [14].
To overcome these problems, the graphene and carbon nanotube hybrid
With the increasing requirements of wearable, portable and flexible fibers can be prepared by solution spinning, which can reduce the ag-
electronic products, the miniaturized, lightweight and flexible super- gregation of graphene nanosheets to obtain larger specific surface area,
capacitors, with high power density and high energy density, have at- and improve the electrochemical properties [15–17].
tracted significant attention as promising energy storage devices [1–6]. In this paper, the reduced graphene oxide/carbon nanotube hybrid
Flexible and binder-free electrode materials play an important role in fibers (G/CNTs) were prepared by a facile low temperature induced
future applications for high-performance supercapacitors. Flexible self-assembly strategy, and the synthesis process is shown in Fig. 1. The
electrodes have mainly been fabricated using carbon-based materials, G/CNTs are fabricated at different temperature of 90 °C and 120 °C
such as amorphous carbon, carbon nanotube (CNT) and graphene in until the hybrid fibers fully form, which is beneficial to controlling
previous published papers [1,7,8]. To meet flexibility and binder-free ordered and porous structure. The as-prepared G/CNTs exhibit large
requirements, carbon nanotube or graphene based 3D aerogels, 2D specific surface area of 149.85 m2 g−1, and good flexibility, which can
membranes, and 1D fibers electrode materials have been widely re- be conveniently woven into variety patterns. The G/CNTs deliver high
searched. The 1D fiber-typed electrodes have been developed to rea- specific capacitance of 195.1 Fg−1 after 500 cycles at a current density
lized wearable storage devices and smart textiles due to combining of 200 mA g−1, which is mainly ascribed to the designed structure and
easily with textiles [9,10]. synergistic effect between reduced graphene oxide and carbon nano-
The 1D linear graphene fibers, with good mechanical flexibility, tube. These reduced graphene oxide/carbon nanotube hybrid fibers will
wearable and electrical properties in contrast to graphene-based aero- be an ideal candidate of electrode materials for flexible and bendable
gels and membranes, can be fabricated by individual graphene na- supercapacitors, and the development can promote more engineering
nosheets [11]. In the synthesis processes, the graphene fibers tend to applications of graphene and carbon nanotube.
restack into graphite-like structure due to the aggregating nature
caused by strong π-π interactions, which destroy the excellent char- 2. Experimental
acteristics of the individual graphene nanosheets, such as high surface
area [5,12,13]. The flexible CNT fibers possess many combined ad- 2.1. Synthesis of materials
vantages including low density, high tensile strength and high electrical
conductivity. But the CNT fibers exhibit relatively low electrochemical 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. Synthetic Metals 232 (2017) 66–71
2.2. Characterization
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M. Zhang et al. Synthetic Metals 232 (2017) 66–71
a current density of 200 mA g−1. The specific capacitance (C, Fg−1) of G20/CNTs. GO has a typical characteristic peak located at 11.6° corre-
G/CNTs were calculated by C = (I × Δt)/(ΔV × m), where I is the sponding to d-spacing of 0.762 nm larger than that of nature graphite
discharge current (A), Δt is the discharge time (s), ΔV is the voltage (about 0.34 nm). The G6/CNTs, G10/CNTs and G20/CNTs display si-
difference in discharge (V) and m is the mass of the active materials milar diffraction peaks at about 25.9° assigned to aggregation of re-
within the electrode (g) [18,19]. duced graphene oxide nanosheets, which indicates the decreasing of
interlayer spacing and reduction of graphene oxides. It may be ascribed
3. Results and discussion to the desorption of oxygen-containing functional groups and H2O
molecules in three kinds of hybrid fibers [20,21].
Fig. 2 shows XRD patterns of Graphite, GO, G6/CNTs, G10/CNTs and FTIR spectra of Graphite, GO, CNTs, CO-CNTs, G6/CNTs, G10/CNTs
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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,
Fig. 5. Tensile strength of G6/CNTs, G10/CNTs, and G20/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
and G20/CNTs are shown in Fig. 3. It can be seen that a large number of up to 111 MPa, 161 MPa and 196 MPa, respectively, and they can also
oxygen-containing functional groups exist in the infrared spectra of GO, be conveniently woven into various patterns (Fig. 1). The tensile
such as CeO epoxy groups (1072 cm−1 and 1328 cm−1) and C]O strength and the various patterns imply good mechanical flexibility of
stretching of carbonyl and carboxyl groups (1766 cm−1) [22–24]. The G/CNTs, which is mainly ascribed to high degree of orientation of re-
infrared spectra of CO-CNTs also show similar characteristic peaks with duced graphene oxide nanosheets and carbon nanotube because of ca-
that of GO. In addition, almost all representative peaks relative to pillary forces and surface-tension-induced sheet interactions [25]. The
oxidized groups decreased dramatically in the FTIR of G/CNTs with reduced graphene oxide/carbon nanotube hybrid fibers show promising
different G and CNTs ratios, and even some of them disappeared en- application in energy storage devices and textile electronics.
tirely. These observations confirm the reducing of oxygen functional The cyclic voltammogram (CV) of the as-synthesized G6/CNTs, G10/
groups on the surface and edge of GO and CO-CNTs during synthesis CNTs and G20/CNTs are measured between −0.8 V and 0.2 V in 6 M
processes, which agrees with the XRD results. KOH solution to understand the electrochemical reaction and stability
The morphologies and structures of CNTs, CO-CNTs, G6/CNTs, G10/ in charge-discharge processes. Fig. 6a–c displays the CV curves of G6/
CNTs and G20/CNTs are shown in Fig. 4. SEM images of CNTs and CO- 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
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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Table 1
Electrochemical performance of some carbon nanotube and graphene binder-free hybrid electrodes for supercapacitors.
−2 −1
CNT/RGO fibers Glass pipeline, 750 °C for 15 min in argon. 1 M NaSO4 20 μA cm 200.4 Fg [4]
SWNT/rGO fibers Hydrothermal processes, ethylenediamine, 220 °C for 6 h 3 M KCl 73.5 mA cm−3 305 Fcm−3 [16]
CF-RGO-CNT fibers CVD, carbon fiber, H2 and Ar thermal reduction at 750 °C 1.5 M Li2SO4 100 mV s−1 203 Fg−1 [27]
GO-CNT/CC films Electrophoretic deposition (EPD) technique, carbon cloth, H2 thermal reduction 1 M H2SO4 1 Ag−1 151 Fg−1 [28]
CNT/graphene hybrid films Coating, under 10 MPa, at 80 °C for 24 h Organic electrolyte 1 Ag−1 50.5 Fg−1 [29]
RGO/CNT films Drying,180 °C for 3 h 1 M H2SO4 0.5 Ag−1 428 Fg−1 [30]
G20/CNTs Self-assembly, ascorbic acid, 90 °C for 2 h and 120 °C for 2 h 6 M KOH 0.2 Ag−1 243 Fg−1 This work
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