Materials Letters 240 (2019) 258–261

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Flower-like MoS2 onto nitrogen-doped 3D graphene composite with

active material for supercapacitor electrodes
Zhisen Liu a,b, Aimiao Qin a, Bin Yang c, Denglei Wang a, Zhiyuan Zhang b
a
Key Lab New Processing Technology for Nonferrous Metals & Materials Ministry of Education, College of Materials Science & Engineering, Guilin University of Technology,
Guilin, China
b
Technology and Development Center for Petrochemical Pollution Control and Resources Utilization of Guangdong University, Guangdong University of Petrochemical
Technology, Maoming, Guangdong 525000, China
c
Maoming R&P Petrochemical Engineering Co., LTD., Maoming, Guangdong 525000, China

a r t i c l e i n f o a b s t r a c t

Article history: MoS2 and graphene composites are promising materials for high-performance supercapacitors. Here, we
Received 21 November 2018 prepared a novel flower-like MoS2 nanosheet/N-doped 3D graphene (MoS2/N-3DG) by hydrothermal
Received in revised form 26 December 2018 method. Electrochemical characterizations indicate that the specific capacitance of MoS2/N-3DG can
Accepted 2 January 2019
reach up to 301.2 F/g at 0.2 A/g and preserve 82% of the initial capacitance after 1000 cycles at 1 A/g.
Available online 9 January 2019
This result shows that MoS2/N-3DG can be applied in supercapacitors.
Ó 2019 Elsevier B.V. All rights reserved.
Keywords:
Composite materials
Functional
Supercapacitor
MoS2
N-doped graphene
Flower-like

1. Introduction Here, we demonstrate a facile strategy to prepare flower-like

MoS2 directly grown on the surface of N-doped 3D graphene (N-
Supercapacitor is widely used in medical and telecommunica- 3DG) by hydrothermal method. Electrochemical characterizations
tion devices and electric vehicles because of its advantages, such indicate that the specific capacitance of MoS2/N-3DG can reach
as high capacity, good cyclability, long service life, and environ- up to 301.2 F/g at 0.2 A/g and preserve 82% of the initial capaci-
mental friendliness [1–3]. Layered transition metal sulfides (espe- tance after 1000 cycles at 1 A/g.
cially MoS2) are suitable candidates for supercapacitors due to
their unique layered structures and high electrochemical activity
[4,5]. However, some drawbacks such as the inferior rate capabil-
2. Experimental
ity, capacity fading during the charge–discharge process. To over-
come these deficiencies, an effective solution is to combine MoS2
2.1. Preparation of MoS2/N-3DG composites
and other materials, such as conducting polymers [6], metal oxides
[7], and carbon materials [8]. Graphene has been extensively stud-
3DG and N-3DG were synthesized in accordance with previ-
ied as a promising supercapacitor due to its excellent electrical
ously reported methods [11]. Flower-like MoS2/N-3DG composites
conductivity [9]. Moreover, the porous graphene has excellent
were synthesized by hydrothermal method. Briefly, N-3DG (40 mg)
electrical conductivity for rapid electron transport and its porous
was added to 35 mL distilled water and sonicated for 0.5 h to form
structures can offer numerous active sites and short ion diffusion
a N-3DG suspension. Ammonium molybdatete trahydrate (211 mg,
distances, which improve the electrochemical performance of the
0.17 mmol) and thiourea (183 mg, 2.40 mmol) were dissolved in
materials. In particular, MoS2 directly grown on N-doped porous
30 mL distilled water and stirred for 0.5 h. The above-mentioned
graphene is a promising electrode material with remarkably
solution was added dropwise to the N-3DG suspension with con-
improved electrochemical performance for supercapacitors [10].
tinuous stirring for 0.5 h and transferred into 100 mL Teflon-lined
autoclave kept at 200 °C for 24 h. The product was collected,
washed with water, dried by lyophilizing at
60 °C and 18 Pa,
E-mail address: 2005032@glut.edu.cn (A. Qin) and marked as MoS2/N-3DG. For comparison, MoS2/3DG was syn-

https://doi.org/10.1016/j.matlet.2019.01.018
0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
 Z. Liu et al. / Materials Letters 240 (2019) 258–261 259

thesized via a similar procedure by using 3DG as the carrier
material.
2.2. Material characterization
The structure of the as-prepared samples was evaluated by XRD
(Rigaku, D/max 2500 v/pc) with Cu-Ka1 radiation. The morpholo-
gies were recorded by TEM (JEM-2010HR, acceleration voltage is
200 KV) and thermal FE-SEM (FEI, Quanta 400) equipped with an
energy-dispersive X-ray spectroscopy analyzer. The cyclic voltam-
metry (CV), electrochemical impedance spectroscopy (EIS), and
GCD of the individual electrode were evaluated using three elec-
trodes in 1.0 M NaSO4 aqueous solution. The working electrodes
were prepared by mixing of active materials (10 mg), ethanol
(900 lL), and 0.5 wt% Nafion (100 lL) to form a slurry. Then, the
slurry (10 lL) was dripped onto the glass carbon electrode
(0.785 cm2) and dried under an infrared lamp to remove the
solvent.

Fig. 1. SEM images of 3DG (a), N-3DG (b), MoS2/3DG (c, d), and MoS2/N-3DG (e, f).

Fig. 2. TEM (a) and HR-TEM (b) images of MoS2/N-3DG. EDX spectrum of MoS2/3DG and MoS2/N-3DG (c). Element mapping images of N, S, and Mo components (d).
260 Z. Liu et al. / Materials Letters 240 (2019) 258–261
Fig. 3. CV curves (a) and GCD curves (b) of MoS2/N-3DG and MoS2/3DG. Nyquist plots (c) and cycle performance test at 1 A/g (d) of MoS2/N-3DG and MoS2/3DG.
3. Results and discussion
As shown in Fig. 1a and b, the 3D hollow structures are reported
after thermal treatment and the diameter of the structures
(approximately 3 lm) is consistent with the diameter of PS nano-
spheres [11]. As shown in Fig. 1c and d, MoS2 presents short and
loose structures. By contrast, MoS2/N-3DG shows MoS2 sheets
anchored on the surface of N-3DG and crossed into a uniform 3D
flower-like structure with a thickness of 10–25 nm and a diameter
of 200–400 nm (Fig. 1e and f). As illustrated in Fig. 2a, the TEM
images of MoS2/N-3DG show a nanoflower structure. Meanwhile,
Fig. 2b displays the typical structure of nanosheets with a lattice
spacing of 0.65 nm dispersed on the surface of N-3DG. This coher-
ent and predominant interface between MoS2 and N-3DG can lead
to efficient electron transfer within the composite and improve the
overall electrochemical performance [12]. The EDX result (Fig. 2c)
reveals that the main elements of MoS2/N-3DG are C, N, O, Mo, and
S. As shown in Fig. 2d, the mapping result verifies that N, S, and Mo
are evenly distributed in the sample.
The CV curves of MoS2/3DG and MoS2/N-3DG are presented in
Fig. 3a with a scanning rate of 100 mV/s in the potential window
of 0–1.2 V. Without the obvious redox peaks means fast charg-
ing/discharging of electrode, and the charge storage mechanism
of MoS2/N-3DG and NaSO2 can be explained by the adsorption
and desorption of Na+ ion through the surface of MoS2 interlayer
spacing, which can be expressed as follows [13]:
MoS2 þ Naþ þ e $ MoS2 Na
The GCD curves of MoS2/N-3DG under various current densities
are displayed in Fig. 3b. The specific capacitance of MoS2/N-3DG
can reach up to 301.2 F/g at 0.2 A/g, which is higher than those
of MoS2/3DG (212.3 F/g), N-3DG (52 F/g), MoS2 [14]. This value is
also higher than other MoS2-based electrode, like MoS2/graphene
composites (240 F/g at 0.2 A/g) [15]. Therefore, the nitrogen func-
tional group increases the specific capacitance. ESI measurements
were performed in the frequency range of 100 kHz –0.1 Hz, as
shown in Fig. 3c. The value of charge transfer resistance of MoS2/
N-3DG is approximately 17 X, which is similar to that of MoS2/3-
DG. In low frequencies, the curve of MoS2/N-3DG approximates a
vertical line, which indicates a better capacitive behavior than that
of MoS2/3DG.
Cycle performance tests for MoS2/N-3DG and MoS2/3DG were
conducted at a current density of 1 A/g for 1000 cycles. As shown
in Fig. 3d, MoS2/N-3DG maintains 82.0% of its initial capacitance
after 1000 charge–discharge cycles, whereas MoS2/3DG retains
only 74.3%. This result demonstrates that MoS2/N-3DG has
enhanced cycling performance compared with MoS2/3DG.
4. Conclusions
A novel 3D flower-like MoS2/N-3DG was prepared using one-
pot hydrothermal method. Then, the morphology and electro-
chemical performance were investigated. MoS2/N-3DG exhibits
excellent specific capacitance (301.2 F/g at 0.2 A/g) and great elec-
trochemical reversibility (preserving 82% of the initial capacitance
after 1000 cycles at 1 A/g). This enhanced performance is attribu-
ted to the morphology and the N-doped graphene. The material
prepared in this study is a promising electrode material for
supercapacitors.
Conflict of interest
None.
 Z. Liu et al. / Materials Letters 240 (2019) 258–261 261

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