Journal of Alloys and Compounds xxx (xxxx) xxx

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Construction of uniform SnS2/ZnS heterostructure nanosheets

embedded in graphene for advanced lithium-ion batteries
Canpei Wang, Yingying Zhang, Yongsheng Li, Yan Zhang, Yutao Dong***, Dan Li**,
Jianmin Zhang*
College of Chemistry, Zhengzhou University, Zhengzhou, 450001, People’s Republic of China

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

Article history: Lithium-ion batteries have been broadly used in energy storage systems and power batteries. However,
Received 6 August 2019 the current research on LIBs anodes still faces key problems such as low specific capacity, limited cycle
Received in revised form life and low initial coulombic efficiency, which limit its commercial applications. In order to solve these
21 November 2019
issues, SnS2/ZnS heterostructure nanosheets are synthesized on a reduced graphene oxide (expressed as
Accepted 22 November 2019
Available online xxx
SnS2/ZnS-rGO) derived from ZnSn(OH)6 through the solution sulfidation method. This composite has the
features of two-dimensional ultrathin nanosheets and heterostructure, which can shorten Liþ diffusion
distance, and provide additional charge transfer driving force. The three-dimensional (3D) SnS2/ZnS-rGO
Keywords:
SnS2/ZnS nanosheets
electrode represents high specific capacity (1458.3 mA h g1 at 0.2 A g1) and outstanding cycle stability
Heterostructures of 4000 cycles (432.4 mA h g1 at 10 A g1). This unique lithium storage mechanism has been studied by
Graphene in-situ and ex-situ XRD techniques in detail. This work not only provides a feasible method for the
Lithium-ion batteries preparation of bimetallic sulfides, but also gives a novel application prospect for the new self-built high
Storage mechanism energy density anode.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction mentioned defects of SnS2 to improve electrochemical perfor-

During the past few decades, lithium-ion batteries (LIBs) have
been made successfully in commercialization, such as mobile de-
vices, transportation vehicles and other storage devices [1e4].
However, the development of anode materials restricts the appli-
cation of high-power energy storage devices with high specific
capacity and excellent rate performance. Hence, it is urgent to
develop lithium storage anode materials with higher power and
capacity characteristics [5e8].
Among various anode materials, SnS2 with a large interlayer
micro-spacing is a promising anode material due to its high theo-
retical capacity, low toxicity and affluent elemental content [9e11].
Actually, SnS2 undergoes bad electron conductivity, huge volume
changes, and heavy aggregation during cycling process, which
causes unsatisfactory electrochemical performance. Up to now,
kinds of strategies have been proposed to conquer the above-
* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: canpei@mail.ustc.edu.cn (C. Wang), dongok0306@163.com
(Y. Dong), Danli@zzu.edu.cn (D. Li), zhjm@zzu.edu.cn (J. Zhang).
mance. One of effective method is to reduce its particle size or
combine with carbonaceous materials, which can improve poor
conductivity and relief the volume variations during cycling
[12e14]. Another significant strategy is constructing hetero-
structures for improving battery cycling performance and rate
capability [15e17]. For instant, Lin et al. invented a novel method to
prepare SnS2/MoS2 on carbon fiber by using hydrothermal method
[18]. Cao et al. synthesized ZnS/SnS2@N/S dual-doped carbon
nanoboxes derived from ZnSn(OH)6@PPy nanoboxes by one-step
sulfidation process, which exhibit high specific capacitance for
sodium storage [19]. Yang et al. obtained (SnCo)S2/SG nanocubes
through a simple vapor deposition method with a good sodium-ion
storage performance [20]. Although they all improve the electro-
chemical performance of the battery to a certain extent, these
strategies could not always meet the requirements of capacity, long
life-span, and power characteristics.
Herein, we report a novel method for preparing ultrathin SnS2/
ZnS heterostructure nanosheets with graphene network (SnS2/ZnS-
rGO) by a simple hydrothermal method using thioacetamide (TAA)
and ZnSn(OH)6 cubes in a graphene oxide solution, as illustrated in
Fig. 1. Briefly, we can get the nanosheet intercalation hollow SnS2/
ZnS cubes without adding GO. SnS2/ZnS cube will become

https://doi.org/10.1016/j.jallcom.2019.153147
0925-8388/© 2019 Elsevier B.V. All rights reserved.

Please cite this article as: C. Wang et al., Construction of uniform SnS2/ZnS heterostructure nanosheets embedded in graphene for advanced
lithium-ion batteries, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.153147
2 C. Wang et al. / Journal of Alloys and Compounds xxx (xxxx) xxx
Fig. 1. Schematic diagram of preparation of SnS2/ZnS and SnS2/ZnS-rGO.
monodisperse SnS2/ZnS heterostructure nanosheets under the
dispersion of graphene, and the SnS2/ZnS-rGO was obtained after
hydrothermal process. The total chemical reaction of this hydro-
thermal treatment can be expressed as
CH3CSNH2 þ 2H2O / H2S þ CH3COONH4
ZnSn(OH)6 þ 3H2S / ZnS þ SnS2 þ 6H2O
This method combines with the features of two-dimensional
ultrathin nanosheets and heterostructure, which can shorten Liþ
diffusion and provide additional charge transfer driving force
owing to the synergistic effect of this binary heterostructure
nanosheet composite. In addition, the introduced graphene
network can strengthen the stable of SnS2/ZnS-rGO composite,
enhance electrical transfer and cushion the volume expansion. In
particularly, the SnS2/ZnS heterojunction formed can provide an
additional charge transfer driving force for the built-in electric field
[16]. In addition, the nanosheet structure can be stabilized during
cycling owing to the synergistic effect of this binary system [9,15].
Thus, the synthesized SnS2/ZnS-rGO composite has excellent
lithium storage capability (1458.3 mA h g1 after 200th cycle at
0.2 A g1, and 432.4 mA h g1 after 4000th cycle at 10 A g1). When
compared with various high performance SnS2-based and ZnS-
based anode materials (Table S1) for LIBs, the SnS2/ZnS-rGO
anode exhibits outstanding electrochemical performance. This
method would provide a feasible method for the preparation of
bimetallic sulfides with new structure and outstanding electro-
chemical performance.
2. Experimental section
2.1. Materials and methods
2.1.1. Synthesis of ZnSn(OH)6 cubes
All reagents were purchased and used without further purifi-
cation. The ZnSn(OH)6 cubes were prepared according to the pre-
vious paper [21]. First, 10 mL of 0.2 M SnCl4 ethanol solution was
poured into 20 mL of 0.1 M ZnCl2, 0.1 M citric acid ethanol solutions.
Then, 50 mL of 0.41 M NaOH solution was cautiously dropwise
added to the mixture solution. After stirring for half-hours, the
ZnSn(OH)6 cubes was attained after washing three times using
deionized water and drying overnight.
2.1.2. Synthesis of SnS2/ZnS-rGO nanosheets
Graphite oxide (GO) was prepared by previous literature
[21e23]. The 0.0675 g of GO was dispersed in 45 mL of distilled
water by ultrasonic treatment for 3 h. Then, 1 mmol ZnSn(OH)6
cubes and 5 mmol thioacetamide (TAA) were added into GO
Please cite this article as: C. Wang et al., Construction of uniform SnS2/ZnS heterostructure nanosheets embedded in graphene for advanced
lithium-ion batteries, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.153147
suspension (40 mL) and stirred for 5 h. The resultant mixture was
transferred to a 50 mL autoclave and had a hydrothermally treated
at 180  C for 12 h. Finally, the SnS2/ZnS-rGO nanosheets was ob-
tained after freeze-drying. In contrast, the preparation of bare SnS2/
ZnS by the same method without GO.
2.2. Characterization
The structure of the as-made samples was characterized by X-
ray diffraction (XRD, Bruker D8 advance). Thermogravimetric
analysis (TGA) was implemented using a TA Instrument TGA-409
with the temperature ranging from 30 to 750  C in air atmo-
sphere. Raman analysis was performed on a LabRam HR spec-
trometer with 532 nm wavelength laser as a light source. The
Micromeritics ASAP 2420 nitrogen adsorption-desorption were
used to determine the specific porous structural features of SnS2/
ZnS-rGO nanosheets. The morphologies of the samples were con-
ducted on JEOL JSM-6700F field-emission scanning electron mi-
croscope. The transmission electron microscopy (TEM) images and
HR-TEM were performed by JEOL2100F transmission electron mi-
(1) croscope under 200 kV accelerating voltage. The valence state of
the SnS2/ZnS-rGO nanosheets was measured on an EscaLab 250Xi
(2) photoelectron spectrum with non-monochromatized Al-Ka
radiation.
2.3. Electrochemical measurements
The mixture of the active material, polyvinylidene fluoride
(PVDF), and acetylene black with a weight ratio of 8:1:1 was
compressed onto a copper foil and the solvent is N-methyl-2-
pyrrolidinone (NMP), which was dried at 120  C for 12 h to fabri-
cate the working electrodes. An electrode mass of active materials
is about 0.65 ± 0.1 mg cm2. The coin cells were assembled by using
Li foil as negative electrode, and 1 M LiPF6 in ethylene carbonate/
diethyl carbonate (EC/DEC, 1:1 v/v) as electrolyte. The electro-
chemical workstation (CHI660E) and the Land multi-channel bat-
tery testing system (LAND CT2001A) were used to test the batteries
within a voltage range of 0.01e3.00 V.
3. Results and discussion
The microstructure of sample was obtained by electron micro-
scopy. In Fig. 2a and c, the SnS2/ZnS not only kept the cubic
morphology with its precursor of ZnSn(OH)6 (Figs. S1a and S1b),
but also has hollow structure with nanosheets on the shell. The
detailed morphology of SnS2/ZnS can be further observed in
Figs. S1c and S1d. Fig. 2b and Fig. S1e display homogeneous hex-
agonal SnS2/ZnS ultrathin nanosheets attached on rGO nanosheets.
The TEM image (Fig. S1f and Fig. 2d) further clarifies SnS2/ZnS
nanosheets ultrathin characteristics. The SAED pattern (inset in
Fig. 2d) also reveals a series of concentric rings, which demon-
strates that SnS2/ZnS maintains polycrystalline nature after the
hydrothermal synthesis process. The high-resolution TEM (HRTEM)
image (Fig. 2e) not only displays (101) and (100) planes of hexag-
onal SnS2, but also shows the (111) plane of cubic ZnS. And the rich
phase boundaries between SnS2 and ZnS are also clearly shown,
which clearly reveal the heterostructure of SnS2 and ZnS in hex-
agonal nanosheets. The phase interface is widely used in Ti-based
materials to enhance the energy storage performance of LIBs [24].
Furthermore, the mapping images of SnS2/ZnS-rGO present the
distribution of Sn, Zn, S and C element (Figs. S2aee), which con-
firms that SnS2eZnS are homogeneous distributed on the rGO
nanosheets.
The samples of this experiment were characterized by XRD as
shown in Fig. S3 and Fig. 2f. All characteristic peaks of the precursor
 C. Wang et al. / Journal of Alloys and Compounds xxx (xxxx) xxx 3

Fig. 2. SEM and TEM images of SnS2/ZnS (a and c) and SnS2/ZnS-rGO (b and d), the inset of (d) is the SAED pattern of SnS2/ZnS-rGO. (e) HRTEM image of SnS2/ZnS-rGO heter-
ostructures. (f) XRD patterns of SnS2/ZnS-rGO nanosheets and bare SnS2/ZnS.

can be assign to cubic phase ZnSn(OH)6 (JCPDS No. 73e2384) rGO composite. The existence of oxygen can be assigned to the
(Fig. S3). After vulcanization, all obtained samples exhibit high adsorbed oxygen or the surface oxidation of SnS2/ZnS-rGO in the air
purity and good crystallinity. This pattern clearly shows the hex- (Fig. 3d) [35,36]. The high-resolution Sn 3d spectrum (Fig. 3a)
agonal SnS2 (JCPDS 01e1010) and cubic ZnS phases (JCPDS
05e0566). For the SnS2/ZnS-rGO, the characteristic peak of rGO is
absent, which can be related to the weak diffracted intensity of the
graphene network [25e27]. TGA analysis was carried out to eval-
uate rGO content in the SnS2/ZnS-rGO composite under air condi-
tion (Fig. S4). The content of rGO can be calculated to be 9.31% in
SnS2/ZnS-rGO through comparing the weight changes of the pure
SnS2/ZnS and SnS2/ZnS-rGO samples. Raman spectroscopy is
recorded to characterize GO and SnS2/ZnS-rGO samples (Fig. S5).
Two peaks located at 1343 and 1589 cm1 can be assigned to the D-
band and G-band, respectively [28e30]. The intensity ratio of the
disordered carbon (D-band) to graphitic carbon (G-band) of
SnS2/ZnS-rGO (1.21) is higher than that of GO (0.96), illustrating the
partial reduction of GO upon hydrothermal process [31e33]. The
Nitrogen adsorption-desorption isotherm curves display type IV
hysteresis loops (Fig. S6). The surface area of SnS2/ZnS-rGO is
~49.2 m2 g1 and the mainly mesoporous diameter is below 10 nm.
The low specific surface area reduces the contact between the
electrolyte and the anode materials, thereby shunning serious side
effects [34].
The chemical nature of SnS2/ZnS-rGO nanosheets was demon-
strated by X-ray photoelectron spectroscopy (XPS). Fig. S7 clearly
Fig. 3. XPS spectra of SnS2/ZnS-rGO nanosheets (a) Sn 3d, (b) Zn 2p, (c) S 2p and (d) C
indicates the Zn, Sn, S, C and O elements coexists in the SnS2/ZnS- 1s.

Please cite this article as: C. Wang et al., Construction of uniform SnS2/ZnS heterostructure nanosheets embedded in graphene for advanced
lithium-ion batteries, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.153147
4 C. Wang et al. / Journal of Alloys and Compounds xxx (xxxx) xxx

shows two peaks at 486.8 and 495.3 eV, which corresponding to Sn
3d5/2 and Sn 3d3/2, respectively, suggesting the existence of Sn4þ
ion [37]. Dual peaks in Zn 2p spectrum (Fig. 3b) at 1022.7 and
1045.6 eV are assigned to Zn2þ of the ZnS phase, respectively [38].
In the S 2p spectrum, the two peaks located at 163.0 and 161.8 eV
can be attributable to S 2p1/2 and S 2p3/2 of S2 (Fig. 3c), respectively
[37,39]. In Fig. 3d, the C 1s peaks located at 286.1 and 285.1 eV are
consistent with C¼O and CeO, respectively, and the other peak at
284.5 eV corresponds to C¼C [39,40].
The SnS2/ZnS and SnS2/ZnS-rGO electrodes were tested as an
anode for LIBs. Fig. 4a reveals the CV curves of SnS2/ZnS-rGO
electrodes. During the 1st cathodic sweep, the appearing reduction
peak at 1.20 V can be attributed to the transformation reaction and
the generation of a solid electrolyte interface (SEI), and the two
peaks centered at 1.77 V and 1.61 V can attribute to the intercalation
of Liþ into SnS2 layers [37,41]. The small reduction peak located at
0.41 V could be related to the conversion reaction of ZnS into Zn/
Li2S and the LieZn alloying reactions [38,42,43]. During the second
cathodic sweep, the peaks at 1.36 V and 0.86 V can be related to the
conversion reactions of SnS2 and ZnS to M (M ¼ Sn, Zn) and Li2S.
Two small peaks at 0.56 V and 0.45 V are the alloying process of
LieSn alloys. Additionally, these small reduction peaks occur below
0.3 V, which can correspond to the alloying of lithium zinc alloy
[9,38]. In the anodic process, the two obviously oxidation peaks
centered at 1.91 and 0.66 V could be assigned to the reversible
formation of SnS2 as well as the de-alloying of SneLi, respectively
[37,44]. The peaks at 0.57 and 1.37 V can be related to the de-
alloying reaction of LieZn alloys and the conversion reaction of
Zn/Li2S into ZnS, respectively [38,43]. It is worth noting that a pair
of redox peaks located at 1.63 V and 2.28 V can be observed in the
second cycle, which are consistent with the intercalation/de-
intercalation of lithium ion in the metal sulfide layer structure.
The CV curves of SnS2/ZnS display similar shape of peaks during the
scans (Fig. S8).
The galvanostatic discharge/charge curves of SnS2/ZnS-rGO are
displayed at 0.2 A g1 in Fig. 4b. The long and flat discharge plateau
in the period of initial cycle, which can be assigned to the process of
lithiation and SEI formation. Especially, the discharge profiles with
two stable plateaus at 0.95 and 1.41 V can be in accordance with the
reduction peaks in CV in the second cycle. The cycling perfor-
mances of the two electrodes at 0.2 A g1 are shown in Fig. 4c. The
SnS2/ZnS-rGO displays a high initial capacity of 1901.5 mA h g1
and a retained capacity of 1458.3 mA h g1 after 200 cycles.
Although its 1st coulombic efficiency is only 67.5% (due to the
irreversible SEI formation), it is quickly up to 90.3% at the 2nd cycle.
Meanwhile, it keeps stably above 96% after 10 cycles. In contrast,
SnS2/ZnS reveals a low capacity of 283.3 mA h g1 after 200th cycle
and its retention rate is 33.9%, indicating the rGO layer greatly

Fig. 4. (a) Cyclic voltammetry (CV) for the initial 5 cycles at a scanning sweep rate of 0.1 mV s1. (b) Charge-discharge profiles for initial two cycles at 0.2 A g1. (c) Cycle per-
formance at a current density of 0.2 A g1. (d) Rate performance at different densities. (e) The comparison of specific capacity for SnS2/ZnS-rGO electrode with various recently
reportes. (f) Nyquist plots of SnS2/ZnS-rGO electrode before cycling, after 1st cycle and after 20th cycles at 0.2 A g1 (the inserted image is the fitted equivalent circuit). (g) Long
cycling performance of SnS2/ZnS-rGO at 5 A g1 and 10 A g1, respectively.

Please cite this article as: C. Wang et al., Construction of uniform SnS2/ZnS heterostructure nanosheets embedded in graphene for advanced
lithium-ion batteries, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.153147
 C. Wang et al. / Journal of Alloys and Compounds xxx (xxxx) xxx 5

improves the electrochemical properties of SnS2/ZnS-rGO com-

posites. The introduction of rGO can uniformly disperse the SnS2/
ZnS heterostructure nanosheets and increase the contact between
the active substrate and the electrolyte. This makes the SEI film
easier to form, resulting in additional pseudocapacitive capacity.
Furthermore, due to the presence of SnS2/ZnS heterostructure
nanosheets, the introduced rGO is more susceptible to exposure to
the electrolyte, particularly at the edges and defects of rGO, which
can provide more storage sites for lithium ions.
Fig. 4d displays the rate capacities of SnS2/ZnS and SnS2/ZnS-
rGO composites in the ranging from 0.1 to 10 A g1. The SnS2/ZnS-
rGO electrode exhibits excellent capacities of 1208.6, 1027.3, 941.9,
877.8, 818.8, 718.7 and 557.1 mA h g1 at 0.1, 0.2, 0.5, 1, 2, 5, and
10 A g1, respectively. When its current density is back to 0.1 A g1,
a reversible capacity of 1009.2 mA h g1 is reobtained, suggesting
the SnS2/ZnS-rGO electrode has a good structural stability. To
further investigate the cyclic stability of the SnS2/ZnS-rGO com-
posite at 5 A g1 and 10 A g1 (Fig. 4g). An initial 9-cycle pre-
condition (1st - 3rd cycle at 0.1 A g1, 4th - 6th cycle at 0.2 A g1,
Fig. 5. Electrochemical properties of the SnS2/ZnS-rGO electrode at 0.01e3.0 V (a) CV
and 7th - 9th cycle at 0.5 A g1) were performed before testing at curves of SnS2/ZnS-rGO at various sweep rates from 0.1 to 1.0 mV s1, (b) Cathode and
5 A g1 and 10 A g1. The SnS2/ZnS-rGO electrode provides a anode peak current changes with various scan rate, (c) CV response at 0.1 mV s1 and
discharge capacity of 625.9 mA h g1 after 3000 cycles when its (d) The proportion of the diffusion-controlled and capacitive charge at different sweep
current density is up to 5 A g1. The discharge capacity of the SnS2/ rates.
ZnS-rGO electrode remains relatively stable after 850 cycles at
10 A g1, and even shows high discharge specific capacity of
the CV curve indicates the contribution of the surface capacitance
432.4 mA h g1 after 4000 cycles. When compared with various
with a ratio of 44.4% using the current separation method devel-
high performance SnS2-based and ZnS-based anode materials
oped by Dan et al. (Fig. 5c) [50]. At other scan rates of 0.2, 0.4, 0.6,
(Fig. 4e [45e47]; Table S1) for LIBs, the SnS2/ZnS-rGO anode reveals
0.8, and 1 mV s1, the capacitive contributions of SnS2/ZnS-rGO
high specific capacity, superior rate capacities, and prominent long
(Fig. 5d) are 47.7, 56.3, 64.8, 68.9 and 71.9%, respectively. It shows
cycle life. As a result, the SnS2/ZnS-rGO anode shows great advan-
that the pseudocapacitor charge storage has a significant advantage
tage for practical business applications with high specific capacity
and advantageous cycle stability. From the SEM images (Fig. S9), it
can be observed that the 3D conductive networks structure still
maintained, which may assist in improving electrical continuity
and even enhancing kinetics of the SnS2/ZnS-rGO electrode.
To further investigate the reason of the outstanding electro-
chemical performance of SnS2/ZnS-rGO, the electrochemical
impedance spectroscopy (EIS) technologies were conducted to
study the kinetics of the SnS2/ZnS-rGO and SnS2/ZnS electrodes.
Fig. S10 shows the Nyquist plots of SnS2/ZnS-rGO and SnS2/ZnS
electrodes tested before cycling. The charge transfer impedance of
SnS2/ZnS-rGO electrode is less than that of SnS2/ZnS electrode,
which may be related to the better electrical conductivity of rGO in
SnS2/ZnS-rGO electrode. The Nyquist plots of SnS2/ZnS-rGO and
SnS2/ZnS electrodes before cycling, after 1st and 20th cycle at
200 mA g1, respectively (Fig. 4f and Fig. S11). The Nyquist plots
was fitted with an equivalent circuit (the inserted image in Fig. 4f).
In the fitted equivalent circuit, Rs represents the internal ohmic
resistance, meanwhile, R1, CPE and W1 represent the charge
transfer resistance, the constant phase angle element and the
diffusion impedance, respectively [32,48,49]. Table S2 shows the
detailed fitted values of every elements (SI). It is inferred that the
conductivity of the composite increases during the cycling process,
which can further confirm the integrity of the conductive networks
of the electrode material and the stability of the surface SEI film.
The EIS analysis is also consistent with the sluggish rise in specific
capacity of SnS2/ZnS-rGO electrode.
To explore the possible reasons for the improvement of SnS2/
ZnS-rGO electrode during rate and cycle processes, the kinetic Fig. 6. (a) Discharge and charge curves of the 1st cycle. (b) Ex-situ XRD patterns of the
performances of SnS2/ZnS-rGO electrode were researched by CV above marked states and the (111) plane profile of standard ZnS (JCPDS: 05e0566). (c)
tests at different scan rates (Fig. 5a). By plotting log(i) and log(v), Two-dimensional (2D) color diffraction pattern of in-situ XRD patterns and (d) corre-
the value of b is decided by the slope, and a pair of redox peaks are sponding 3D waterfall patterns during the discharge/charge processes for SnS2/ZnS-
rGO composite in the 2q of 27.5e29.0 . (e) Schematic illustration of lithium storage
calculated to be 0.85 and 0.78, respectively (Fig. 5b). It is shown that mechanism of SnS2, depicting conversion reaction combined with alloying reaction.
the peak current is almost uniformly controlled by the capacitance (For interpretation of the references to color in this figure legend, the reader is referred
control and diffusion control processes. The orange shadow area in to the Web version of this article.)

Please cite this article as: C. Wang et al., Construction of uniform SnS2/ZnS heterostructure nanosheets embedded in graphene for advanced
lithium-ion batteries, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.153147
6 C. Wang et al. / Journal of Alloys and Compounds xxx (xxxx) xxx
in the entire capacity at higher scan rates.
In order to determine the unique alloying/dealloying and
transformation mechanism of the synthetic SnS2/ZnS-rGO, a series
of structural characterizations were performed. Fig. 6a shows a
series of marked points during the discharge/charge processes. The
ex situ XRD was tested in the 2q range of 20e36 (Fig. 6b), the peak
at around 28.6 gradually disappeared during the discharge process
(I-Ⅳ), which can be assign to the (111) plane of the ZnS (JCPDS
05e0566). When the electrode is charged to 1.38 and 3.0 V (Ⅴ and
Ⅵ), the peak at around 28.6 appeared again. The above phenom-
ena can correspond to the following conversion reaction:
ZnS þ 2Liþ þ 2e # Zn þ Li2S
The in-situ XRD was measured to study the Li storage mecha-
nism of SnS2/ZnS-rGO electrode (Fig. 6c and d). It is obvious that the
peak at approximately 28.6 arises periodically, which is consistent
with the result of the ex-situ XRD. Additionally, the diffraction peak
at about 28.2 can correspond to the (100) crystal plane of the SnS2
of the initial state. And this peak arises periodically during
discharge process, which may be related to the alloy reaction to
form LixSn according to some relevant literature [9,37,38]. The
relevant reaction mechanism can be depicted as:
Conversion reaction: SnS2 þ 4Liþ þ 4e # Sn þ 2Li2S
Alloying/dealloying reaction: Sn þ xLiþ þ xe # LixSn
The corresponding schematic diagram of lithium storage
mechanism is shown in Fig. 6e, which describes the conversion
reaction and alloying reaction during the charge-discharge process
of SnS2. Meanwhile, the lithium reaction mechanism of ZnS is the
same as that of SnS2.
4. Conclusions
In summary, we report a hydrothermally method for preparing
SnS2/ZnS-rGO nanosheets using thioacetamide and ZnSn(OH)6
cubes in a graphene oxide solution. The prepared SnS2/ZnS-rGO
composite shows the structural advantage of the synergistic effect
among the SnS2/ZnS heterostructure nanosheets with rGO. When
SnS2/ZnS-rGO used as the anode material of LIBs, this composite
exhibits prominent electrochemical performance according to the
high specific capacity (1458.3 mA h g1 after 200th cycle at
0.2 A g1), outstanding rate performance (average specific capacity
of 557.1 mA h g1 at 10 A g1) and long cycle stability
(432.4 mA h g1 after 4000th cycle at 10 A g1). This paper provides
a feasible method for the preparation of bimetallic sulfides, and we
convince this synthetic strategy can be applied to the next gener-
ation of other advanced electrode materials.
Author contribution
The contribution of this work is decreasing in the order of the
authors in this article, and the communication author of this article
provides financial assistance.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Please cite this article as: C. Wang et al., Construction of uniform SnS2/ZnS heterostructure nanosheets embedded in graphene for advanced
lithium-ion batteries, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.153147
Acknowledgements
This financial was supported by the Natural Science Foundation
of Henan Province (No. 182300410278), the National Natural Sci-
ence Foundation of China (Grant No. 21701144 and 21373189), the
China Postdoctoral Science Foundation (Grant No. 2016M592303
and 2017T100536).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jallcom.2019.153147.
(3)
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