Journal of Alloys and Compounds 698 (2017) 828e834

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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

Effects of binders on electrochemical properties of the SnS2

nanostructured anode of the lithium-ion batteries
Lixiong Yin a, *, Simin Chai a, Jianzhong Ma b, Jianfeng Huang a, Xingang Kong a,
Peijie Bai a, Yao Liu a
a
School of Materials Science and Engineering, Shaanxi University of Science & Technology, Xi'an, Shaanxi, 710021, China
b
College of Resources and Environment, Shaanxi University of Science and Technology, Xi'an, Shaanxi, 710021, China

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

Article history: Binders play a significant role in enhancing the electrochemical performance of tin disulfide (SnS2) as the
Received 18 July 2016 anode for lithium-ion batteries (LIBs) because of their excellent dispersion and cohesion in the elec-
Received in revised form trodes. In the present work, flake-like SnS2 nanoparticles with a hexagonal structure were synthesized by
5 December 2016
a facile one-step hydrothermal method with a mean grain size of 7.7 nm. When sodium alginate (SA),
Accepted 16 December 2016
Available online 22 December 2016
carboxymethyl cellulose (CMC), poly acrylic acid (PAA), and CMC-PAA (1:1, wt%) are applied as binders
for the SnS2 anode electrode (the obtained electrodes are denoted as SnS2-S, SnS2-C, SnS2-CP, and SnS2-P,
respectively) in LIBs, the electrodes exhibited high reversible lithium-ion storage capacities of
Keywords:
Binder effect
762.00 mA h g
1, 891.65 mA h g
1, 913.94 mA h g
1, and 930.36 mA h g
1 at the current densities of
SnS2 100 mA g
1, respectively. Importantly, the SnS2-P electrode exhibited excellent rate capacity and cycling
Nanostructures performance. The eCOOH of PAA attached to SnS2 can increase the amount of free radicals, which can
Lithium ion battery prevent the detachment of SnS2 from the current collector, and the carboxyl group can effectively inhibit
the volume expansion and pulverization of particles of the electrode. Undoubtedly, PAA binder signifi-
cantly improves the cycling and rate performances of SnS2 anode material for LIBs.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Lithium-ion batteries (LIBs) with higher energy density and
longer cycle life are highly desirable for the practical applications in
electric vehicles and hybrid electric vehicles [1,2]. Such applications
are best achieved by enhancing the performances of anode mate-
rials in LIBs [3,4], and the specific capacities of anode materials
should surpass the value (372 mA h g
1) for the graphite anode. For
lithium storage, Sn (or Sb, Mo) oxides [5,6] and sulfides [7] have
been extensively investigated due to their potentially high capacity.
Generally, MeS bonds in metal sulfides are weaker than MeO
bonds in metal oxides, making them kinetically favourable for
conversion reactions [8], and thus sulfides exhibit better electro-
chemical performances than oxides for LIBs.
A typical transition metal sulfide SnS2 has a high theoretical
capacity of 645 mA h g
1 (4.4 Liþ/Sn), which is attributed to its
layered structure [9,10]. The specific capacity can reach up to
* Corresponding author.
E-mail address: ylx@sust.edu.cn (L. Yin).
1231 mA h g
1 (8.4 Liþ/Sn) if the first step alloying reaction
(LiSnS2 þ 2xLiþ þ 2xe
/ xLi2 S þ Sn) is also reversible.
Although the wide interlayer spacing of layered SnS2 can facilitate
the insertion/extraction of lithium-ions and electrons, the un-
avoidable large volume change of SnS2 during the cycling may lead
to its pulverization and severe capacity decay [11]. In addition, the
poor rate capability of the SnS2 anode is another arduous challenge
as a result of its intrinsically low electrical conductivity [12].
Recently, enormous efforts have been devoted to optimizing the
performance of binders. Binders can not only conglutinate active
materials and conductive additives but also maintain the structural
stability of anode materials. Meanwhile, the appropriate binders
can alleviate the volumetric expansion of anode material. The
electrochemical performances of SnS2 can be further improved due
to the excellent dispersion and cohesion of binders during the
process of lithiation/delithiation [13].
As a traditional binder, polyvinylidene fluoride (PVDF) cannot
provide satisfactory cycling stability, because the F atoms on the
binder's linear chain structure can easily react with lithium metal to
form LiF [14,15]. Chang et al. fabricated a layered SnS2 electrode
using PVDF as a binder, and the discharge capacity of the electrode

http://dx.doi.org/10.1016/j.jallcom.2016.12.215
0925-8388/© 2016 Elsevier B.V. All rights reserved.
 L. Yin et al. / Journal of Alloys and Compounds 698 (2017) 828e834
fell to 163 mA h g
1 from 462 mA h g
1 after 50 cycles at
100 mA g
1 with a low capacity retention rate of 35.3% [3]. Liu et al.
reported that pure SnS2 particles experienced a fast capacity decay
(the discharge capacity is less than 10 mA h g
1 after 20 cycles) at
1000 mA g
1 [16]. Besides, organic solvent N-methyl pyrrolidone
(NMP) is required as a dispersant to form slurry, which gives the
drawbacks of high cost and environmental problems [17]. Conse-
quently, an eco-friendly and cost-effective binder aimed to further
enhance the electrochemical performance of the SnS2 anode is
urgently desired. Some scholars have proposed that water-based
binders may substitute for PVDF to solve the problems in batte-
ries [15,18,19].
In this paper, SnS2 samples are successfully fabricated by a facile
hydrothermal method. The electrochemical performances of SnS2
have been comparatively investigated by using sodium alginate
(SA), carboxymethyl cellulose (CMC), poly acrylic acid (PAA), and
CMC-PAA (1:1, wt%) as binders. The obtained electrodes, which are
respectively denoted as SnS2-S, SnS2-C, SnS2-CP, and SnS2-P,
demonstrate remarkably dissimilar electrochemical performances.
The results indicate that the SnS2-P electrode possesses excellent
electrochemical activity, lower internal resistance and higher sur-
face conductivity.
2. Experimental section
2.1. Synthesis of SnS2 nanostructure
First, 4 mol L
1 Na2S$9H2O solution was added to 2 mol L
1
SnCl4$5H2O solution, and the pH value of the obtained tawny so-
lution was adjusted to pH ¼ 7 with NH3$H2O (Wt% ¼ 10%) solution.
Then, the mixed solution was subjected to mechanical stirring for
10 min and then ultrasonic dispersion for 10 min. Subsequently, the
obtained brown suspension was placed in a Teflon-lined autoclave
and heated at 150  C for 16 h with stirring. Finally, the precipitates
were centrifuged and washed with deionized water and anhydrous
ethanol for several times. The SnS2 sample was obtained after the
final drying in a vacuum freeze drier for 12 h.
2.2. Structural and physical characterizations
The phase-structural composition of the product was charac-
terized using powder X-ray diffraction (XRD, Rigaku, D/max-
2200PC, Cu Ka1 radiation, l ¼ 1.5406 Å, at 40 kV and 40 mA). The
details of the morphology were further characterized by trans-
mission electron microscopy (TEM, FEI Tecnai, G2 F20 S-TWIN,
Acceleration voltage: 200 kV).
2.3. Cell assembly and electrochemical testing
The electrochemical performances of the SnS2 electrodes were
evaluated by employing CR2032 coin-type cells. The acetylene car-
bon black, binders (SA, CMC, CMC-PAA, PAA), and the synthesized
SnS2 were mixed together (8:1:1, wt%) in 1e1.5 mL of deionized
water to form a homogenous slurry. The resultant flowing slurry was
coated on the copper foil using a doctor blade and dried in a vacuum
oven at 70  C for 12 h. The copper foil was cut into circles with a
diameter of 16 mm, on which the electrode area was about 2 cm2,
and the mass of SnS2 material was 2.0 mg cm
2 with a thickness of
0.15mm. The coin cells were assembled in an argon-filled glove-box
(Braun Insert gas-System GmbH) with lithium metal as the counter
electrode and reference electrode. 1 M LiPF6 (EC: DMC: EMC ¼ 1:1:1
by volume) was used as an electrolyte, and a porous polypropylene
film (Celgard 2400) was used as a separator.
The electrical surface resistivity (Res) and the surface conduc-
tivity (Cs) of SnS2-S, SnS2-C, SnS2-CP, and SnS2-P electrodes were
829
investigated by a four-probe instrument (RST-8). Galvanostatic
charge and discharge measurements of the assembled cells were
carried out at different current densities in the voltage range of
0.005e3.0 V versus Liþ/Li by using a computer-controlled Neware
Battery Testing System. Cyclic voltammetry (CV) was executed by
using a CHI 660E electrochemical workstation at a scan rate of
0.1 mV s
1 between 0.005 and 3.0 V (vs. Liþ/Li) at room tempera-
ture. Electrochemical impedance spectroscopy (EIS) was carried out
in the frequency range of 100 kHz to 0.01 Hz.
3. Results and discussions
3.1. Morphology and structure characterization
The XRD patterns of the as-synthesized SnS2 samples are shown
in Fig. 1a. All diffraction peaks can be indexed well to PDF No. 23-
0677, indicating that the SnS2 precursors were successfully pre-
pared via the one-step hydrothermal method. It is worth noting
that the average grain size of the SnS2 products is calculated as
7.72 nm using the (001) diffraction peak according to the Debye-
Scherrer formula (Eq. (1)):
D ¼ k $ l = b$cosq (1)
where K is the Scherrer constant, l is the wavelength of X-rays for
Cu Ka1 radiation, b is the full width at half height of the diffraction
peak, and q is the diffraction angle.
The morphology of SnS2 samples is characterized by TEM
(Fig. 1bed). The flake-like SnS2 exist together with nanoparticles, as
shown in Fig. 1b at low magnification. SnS2 nanoparticles stack on
the top of each other and constitute porous pores. Such an open
structure is favourable for the diffusion and transport of electrolyte
during rapid charge/discharge [20], and more exposed surfaces are
available for the reactions of lithium-ions with SnS2. It is clear that
the size distribution of SnS2 nanoparticles is in the range of
5e10 nm (Fig. 1c), which is consistent with the result calculated by
the Debye-Scherrer formula. SnS2 nanoflakes are stacked in layers
along the (100) direction, and the interplanar distance in the
nanoflakes is about 0.31 nm. The lattice spacing of the (001) plane is
0.59 nm (Fig. 1d), which is consistent with the XRD result.
3.2. Electrical properties of the electrodes
The Res and Cs values of SnS2-S, SnS2-C, SnS2-CP, and SnS2-P
electrodes are displayed in Fig. 2. The Res value of SnS2-P is
0.1 mU cm, as shown in Fig. 2a, and the Res value of the SnS2-CP
electrode shows no significant change when the weight proportion
of CMC to PAA is 1:1 in the mixed binder. Nevertheless, the Res
values of SnS2-C and SnS2-S electrodes are significantly increased to
extreme values when CMC and SA are used separately as binders in
the SnS2 electrode. The Cs values of the SnS2-P and SnS2-CP elec-
trodes are both 104 s cm
1 (Fig. 2b), which is consistent with their
surface resistivity characterized in Fig. 2a. Correspondingly, the Cs
value of SnS2-C is about half of that for the SnS2-CP electrode when
the binder is pure CMC, and the Cs value of the SnS2-S electrode
drops significantly to 1111 s cm
1. The SnS2-P electrode possesses
relatively low Res and high Cs values, which indicates that the PAA
binder has chemical inertia in electrodes. The excellent electrical
conductivity of PAA binder is more beneficial to the conduction of
ions and electrons in electrodes.
SA can provide reaction sites for incorporating additional func-
tional groups or modifying the existing functionality. The
cementability of binders can be tremendously affected by their own
molecular functional groups. SA is a linear copolymer with blocks of
1e4 linked b-D-mannuronic acid (M) and a-L-guluronic acid (G)
830 L. Yin et al. / Journal of Alloys and Compounds 698 (2017) 828e834

Fig. 1. (a) XRD patterns, (b) TEM images and (c, d) HRTEM images of as-obtained SnS2 samples.

Fig. 2. (a) Electrical surface resistivity and (b) surface conductivity of as-obtained SnS2-S, SnS2-C, SnS2-CP and SnS2-P electrodes.

residues. It could be regarded as a block copolymer comprising
homopolymeric regions of M and G, where the alternating struc-
ture of MG is scattered. And, similarly to other binders, SA is
nonconductive [15], which is inimical to ion transport. Since the
carboxyl functional group exists in both CMC and PAA binders, the
ester bond structure can be formed by bonding of the carboxyl
group on the long chains with the hydroxyl group of active mate-
rials and the conductive particles [21]. It was reported that CMC
releases lithium-ions [13,17], which can increase the contents of
free lithium-ions in LIBs and shorten the diffusion pathway to the
anode particle surface. In comparison with CMC, the hydrogen
bonds are created due to the interactions of eCOOH groups of the
PAA binder, and the bonding can make the long-chain structures
cross-linked with each other to produce superior bonding network
[22]. The eCOOH attached to SnS2 can offer more free radicals,
resisting to the detachment of SnS2 from the current collector and
effectively inhibiting the volume expansion and pulverization of
the particles [23,24]. The excellent properties of the SnS2-P elec-
trode are reflected by the enhanced electrochemical performances
compared with the other three electrodes. The mechanism of PAA
for SnS2 anodes is illustrated in Fig. 3.
3.3. Electrochemical properties
The galvanostatic cycling performances of the obtained elec-
trodes between 0.005 and 3.0 V at 100 mA g
1 are shown in Fig. 4a.
 L. Yin et al. / Journal of Alloys and Compounds 698 (2017) 828e834 831

Fig. 3. Illustration of the charge/discharge processes of the SnS2-P anode.

Fig. 4. (a) Charge-discharge cycling performances and CE; (b) charge/discharge profiles of SnS2-S, SnS2-C, SnS2-CP, and SnS2-P electrodes as anodes for LIBs at 100 mA g
1 in the
voltage window of 0.005e3 V; (c) rate performances; and (d) comparison of the initial discharge capacities of SnS2-S, SnS2-C, SnS2-CP, and SnS2-P electrodes at different current
densities.

The large irreversible capacity loss in the first discharge process
occurs for all four different electrodes and is attributed to the for-
mation of SEI layers resulting from the decomposition of the elec-
trolyte [25]. Although the second cycle discharge capacity of SnS2-P
electrode is 913.94 mA h g
1, corresponding to a capacity loss of
33.89%, the charge/discharge capacities of SnS2-P electrode are
decayed slowly before the 10th cycle and then tend to become
stable. The SnS2-P electrode displays a stable capacity of
547.56 mA h g
1 after 50 cycles with a capacity loss of 1.5% per
cycle. The results evidence the stability of the SnS2-P electrode
during the subsequent charge/discharge processes. Meanwhile, the
coulombic efficiency (CE) of the electrode quickly reaches 97% at
the second cycle, demonstrating an efficient lithium-ion interca-
lation/deintercalation process. In contrast, the charge/discharge
capacities of SnS2-CP, SnS2-C, and SnS2-S electrodes are descended
in sequence and are 438.77, 283.60, and 231.88 mA h g
1 after 50
cycles, respectively.
Fig. 4b displays the first and second charge/discharge voltage
behaviours of as-obtained anode electrodes. The first discharge
capacities of 1382.39, 1453.46, 1306.52, and 1261.53 mA h g
1 are
corresponding to the SnS2-P, SnS2-CP, SnS2-C, and SnS2-S elec-
trodes, respectively. Based on the charge/discharge voltage pla-
teaus of the electrodes, the processes of lithium-ions’ insertion/
deintercalation into SnS2 can be divided into three stages. In Stage І,
the plateau at higher voltage (around 1.3 V) is observed and is
attributed to the insertion of lithium-ions into SnS2 layers [1]. The
slopy plateaus at 0.2e0.4 V mainly originate from the conversion
reaction between LiSnS2 and lithium-ions, and SEI layers are
simultaneously formed on the surface of active materials (Stage ІІ)
[12]. The sloping plateau is observed at lower voltage, which is due
to the alloying reaction between Sn and lithium-ions (Stage ІІІ). The
side reactions between electrodes and electrolyte will be acceler-
ated because of the abundant active sites resulting from the high
specific surface areas of the SnS2 samples. A large number of
832 L. Yin et al. / Journal of Alloys and Compounds 698 (2017) 828e834

lithium-ions will be irreversibly consumed [9], corresponding to

the second discharge curves in Fig. 4b. SnS2 þ Liþ þ e
/ LiSnS2 (2)
The rate capabilities of SnS2-S, SnS2-C, SnS2-CP, and SnS2-P
anode electrodes are demonstrated in Fig. 4c. It is obvious that the Liþ þ e
þ electrolyte / SEI ðLiÞ (3)
discharge capacities of SnS2-S and SnS2-C electrodes dropped
dramatically with the increased current densities, and these elec-
LiSnS2 þ 2xLiþ þ 2xe
/ xLi2 S þ Sn (4)
trodes could only retain capacities of 48.19 and 77.07 mA h g
1 at
800 mA g
1. By contrast, the rate capacity of the SnS2-CP electrode
is considerably improved at high current densities. Meanwhile, the Sn þ Liþ þ xe
4 Lix Sn ð0 ≪ x ≪ 4:4Þ (5)
SnS2-P electrode exhibits much better electrochemical perfor-
To further investigate the electrode kinetics and other charac-
mance compared with the other three electrodes. When the cur-
teristics of the as-prepared electrodes, EIS tests of the Sn-based
rent density reaches 800 mA g
1, the SnS2-P electrode can still
electrodes are employed. The Nyquist plots and corresponding
retain a discharge capacity of 478.25 mA h g
1. The differences in
equivalent circuit of the four different electrodes after one cycle are
the initial discharge capacities of SnS2-S, SnS2-C, SnS2-CP, and SnS2-
shown in Fig. 5b and c. The typical characteristics of the Nyquist
P anode electrodes are shown in Fig. 4d. It is clear that the capacity
plots consist of a semicircle and a sloping straight line in the high-
differences of the four electrodes become evident with the gradual
and low-frequency ranges, respectively. The intersection in the
increases of the current density, and the SnS2-P electrode displays
high-frequency range represents the electrolyte resistance (Re) at
excellent structural stability at high current densities. The results
the SnS2 interface. Besides, the semicircle is attributed to the con-
clearly demonstrate that the structure of the PAA binder plays an
stant phase element of SEI layer resistance (CPE1) and contact
important role in alleviating the volumetric expansion of the SnS2
resistance (Rs). Another part of the semicircle consists of the
anode material and is favourable for improving the electrochemical
charge-transfer resistance (Rct) and constant phase element of the
performances of SnS2 anode materials at high current density.
electrode/electrolyte interfaces (CPE2). The sloping line in the low-
To better understand the electrochemical features of Liþ storage
frequency range is assigned to Warburg impedance (Zw) corre-
in four different Sn-based anode electrodes, the CV measurements
sponding to the lithium-ions diffusion process [5]. The fitted
of the initial cycle for each electrode are performed in the range of
impedance parameters according to the Nyquist plots of as-
0.005e3.0 V at 0.1 mV s
1, as shown in Fig. 5a. The strong cathodic
prepared electrodes are listed in Table 1. The table shows that the
peak at around 1.23 V can be attributed to the formation of LixSnS2
Rct and Zw values of the SnS2-P electrode are, respectively, 25.45 and
(Reaction (2)), in which the lithium-ions are inserted into SnS2
14.71  10
3 U, and these values are significantly lower than those
layers, and no other phases are formed during the cycling [12,26].
of the other electrodes. The results confirm that the PAA binder not
The peak at 0.42 V is due to the irreversible formation of a solid SEI
only reduces the charge transfer resistance of the electrode but also
layer (Reaction (3)), which is formed because of decomposition of
significantly enhances the kinetic performance of the SnS2 anode
the electrolyte and the conversion of LiSnS2 into Sn (Reaction (4)),
during lithium insertion/extraction.
respectively [25]. In the alloying process, some lithium-ions are
To further confirm the effects of the binders on the kinetic
consumed, simultaneously leading to the occurrence of strain,
changes of the SnS2 materials during the alloying/dealloying, the
which can inhibit the volume expansion [27,28]. The other cathodic
Nyquist plots and morphologies of the four electrodes after 50
peak at around 0.08 V corresponds to the formation of LixSn by the
cycles are investigated by EIS and SEM tests, respectively. As shown
alloying between Sn and Li (Reaction (5)) [7]. During the anodic
in Fig. 6a, the semicircle diameters of the Nyquist plots after 50
oxidation, there are three corresponding oxidation peaks at 0.64,
cycles at high-frequency are both larger than those of the first cycle
1.24, and 2.01 V, respectively, which are attributed to the deli-
thiation process. The oxidation peak at 0.64 V indicates the
reversible dealloying processes of Sn and Li. The oxidation peak at Table 1
1.24 V correspond to the partially reversible reaction of LixS to form Impedance parameters are derived using equivalent circuit models of SnS2-S, SnS2-
LiSnS2. Conspicuously, the additional oxidation peak at 2.01 V can C, SnS2-CP, and SnS2-P electrodes.

be assigned to the lithium deintercalation from the SnS2 layers Electrode Re/U n1 Rs/U Zw/(  10
3) U n2 Rct/U
without phase decomposition. It is noted that the CV curves of four SnS2-S 2.52 0.71 53.59 28.86 0.62 41.56
different electrodes substantially overlap with each other, which SnS2-C 2.92 0.70 27.88 61.76 0.69 40.37
indicates that the binders in the electrodes are not involved into the SnS2-CP 2.05 0.71 67.14 23.47 0.64 58.12
lithiation/delithiation reactions of the lithium-ion storage. SnS2-P 2.14 0.80 31.50 14.71 0.60 25.45

Fig. 5. (a) CV curves of cells assembled with four different binders at a scan rate of 0.1 mV s
1; (b) Nyquist plots (the insert diagram at the bottom right of Fig. 5b is the partial
amplification); and (c) equivalent circuit model of the studied systems in the frequency range of 100 kHz to 0.01 Hz.
 L. Yin et al. / Journal of Alloys and Compounds 698 (2017) 828e834
Fig. 6. Nyquist plots (a) after 50 cycles of the electrodes (the inset at the bottom right is the partial amplification); SEM images of (b) SnS2 products, (c) SnS2-S, (d) SnS2-C, (e) SnS2-
CP and (f) SnS2-P electrodes after 50 cycles.
(Fig. 5b). This phenomenon indicates the formation of a stable SEI
layer and shows changes after the activation process of SnS2 ma-
terials. Additionally, the oblique line of the SnS2-S electrode dis-
plays a large inclination compared with Fig. 5b, demonstrating the
volume expansion of SnS2 materials during the Liþ insertion/
deinsertion [12]. The semicircle diameter of the SnS2-P electrode is
enlarged, showing that the increasing Rct and Zw values exhibit an
inconspicuous change. The EIS results of the four electrodes after 50
cycles demonstrate that the PPA binder is more beneficial to the
lithium-ions and electrons transport, and the SnS2 materials may
maintain the stable structure in the SnS2-P electrode.
The SEM images of SnS2 products and SnS2-S, SnS2-C, SnS2-CP,
and SnS2-P electrodes after 50 cycles are shown in Fig. 6bef. It is
found that the regular spherical particles still exist. However, the
SnS2-S and SnS2-C electrodes show conspicuous aggregation of
particles. Although the SnS2-CP electrode maintains a uniform size
distribution and the pores assembled by particles are discernible, it
is apparent that the particle size is conspicuously increased.
Simultaneously, the SnS2-S, SnS2-C, and SnS2-CP electrodes exhibit
collapse and a variable pulverization. By contrast, the SnS2-P film
still tightly adheres to the copper foil, the SnS2 materials present
the flake-like morphology after 50 cycles, and the diameter of the
particles is around 10 nm. These results demonstrate the excep-
tional adhesion ability of PAA compared with the other three water-
soluble binders, which is consistent with the reported literature
date [29]. The -COOH groups of PAA can effectively inhibit the
volume expansion and pulverization of the SnS2 anode [18].
According to the above results, it can be concluded that the
enhanced electrochemical performances of SnS2-P electrode are
originated from: firstly, the high surface areas of the ultrathin flake-
like SnS2 nanoparticles can increase the contact of electrode and
electrolyte, which will increase the number of potentially active
sites for the lithium-ions transfer reaction [30]; then, the nano-
structural SnS2 growing along the c-axis orientation is favourable
for rapid lithium-ions diffusion [31]; moreover, the hydrogen
bonding between the carboxylic groups is highly beneficial for
reducing the volume expansion of SnS2 material. As a result, the
cycling stability of electrodes can be markedly enhanced during the
lithium-ions insertion/deinsertion [18,32].
833
4. Conclusions
Flake-like SnS2 nanoparticles have been successfully prepared
and the formed crystallites are in the range of around 7e8 nm. The
electrochemical performances of SnS2 have been comparatively
investigated by using SA, CMC, PAA, and CMC-PAA (1:1, wt%) as
binders, respectively. The SnS2-P electrode showed excellent elec-
trochemical activity, lower internal resistance, and higher surface
conductivity. The smaller particle size and greater number of active
sites of the active material can mitigate the volume change of SnS2.
Also, sufficient number of carboxyl groups of PAA with high tensile
strength assist in accommodation of lithium-ions and improve-
ment of the electric conductivity of the active materials during the
cycling. Therefore, the use of PAA as a binder is favourable for the
SnS2 material allowing to achieve stable anode performance at high
current densities.
Acknowledgements
We are grateful for the financial support provided by the Na-
tional Natural Science Foundation of China (No. 51541204), the
China Postdoctoral Science Foundation (No. 2016M592737), the
National Key Laboratory of Silicate Building Materials (No.
SYSJJ2015-18), the Science and Technology Department Foundation
of Shaanxi Province (No. 2016GY-199), and the Innovation and
Entrepreneurship Training Program of College Students (No.
201510708154).
References
[1] J.T. Zai, K.X. Wang, Y.Z. Su, X.F. Qian, J.S. Chen, High stability and superior rate
capability of three-dimensional hierarchical SnS2 microspheres as anode
material in lithium ion batteries, J. Power Sources 196 (2011) 3650e3654.
[2] C.F. Lin, X.Y. Fan, Y.L. Xin, F.Q. Cheng, M.O. Lai, H.H. Zhou, L. Lu, Li4Ti5O12-based
anode materials with low working potentials, high rate capabilities and high
cyclability for high-power lithium-ion batteries: a synergistic effect of doping,
incorporating a conductive phase and reducing the particle size, J. Mater.
Chem. A 2 (2014) 9982e9993.
[3] K. Chang, Z. Wang, G.C. Huang, H. Li, W.X. Chen, J.Y. Lee, Few-layer SnS2/
graphene hybrid with exceptional electrochemical performance as lithium-
ion battery anode, J. Power Sources 201 (2012) 259e266.
[4] M. Armand, J.M. Tarascon, Building better batteries, Natrue 451 (2008)
834 L. Yin et al. / Journal of Alloys and Compounds 698 (2017) 828e834
652e657.
[5] S.M. Hwang, Y.G. Lim, J.G. Kim, Y.U. Heo, J.H. Lim, Y. Yamauchi, M.S. Park,
Y.J. Kim, S.X. Dou, J.H. Kim, A case study on fibrous porous SnO2 anode for
robust, high-capacity lithium-ion batteries, Nano Energy 10 (2014) 53e62.
[6] C.Y. Zhang, P.G. Zhang, J. Dai, H. Zhang, A.J. Xie, Y.H. Shen, Facile synthesis and
electrochemical properties of MoO2/reduced graphene oxide hybrid for effi-
cient anode of lithium-ion battery, Ceram. Int. 42 (2016) 3618e3624.
[7] H.Y. Sun, M. Ahmad, J. Luo, Y.Y. Shi, W.C. Shen, J. Zhu, SnS2 nanoflakes deco-
rated multiwalled carbon nanotubes as high performance anode materials for
lithium-ion batteries, Mater. Res. Bull. 49 (2014) 319e324.
[8] L. Wu, H.Y. Lu, L.F. Xiao, X.P. Ai, H.X. Yang, Y.L. Cao, Improved sodium-storage
performance of stannous sulfide@reduced graphene oxide composite as high
capacity anodes for sodium-ion batteries, J. Power Sources 293 (2015)
784e789.
[9] X. Jiang, X.L. Yang, Y.H. Zhu, J.H. Shen, K.C. Fan, C.Z. Li, In situ assembly of
graphene sheets-supported SnS2 nanoplates into 3D macroporous aerogels for
high-performance lithium ion batteries, J. Power Sources 237 (2013)
178e186.
[10] K.Y. Li, S.C. Yan, L.Y. Zhou, M. Yang, Y. Shi, Y.Q. Wang, J.C. Xie, Facile sol-
vothermal synthesis of flowerlike SnS2 nanosheets for enhanced lithium ion
storage property, J. Nanosci. Nanotechnol. 16 (2016) 5761e5769.
[11] X.Q. Xie, D.W. Su, S.Q. Chen, J.Q. Zhang, S.X. Dou, G.X. Wang, SnS2 nano-
platelet@graphene nanocomposites as high-capacity anode materials for
sodium-ion batteries, Chem. Asian J. 9 (2014) 1611e1617.
[12] W.N. Deng, X.H. Chen, Z. Liu, A.P. Hu, Q.L. Tang, Z. Li, Y.N. Xiong, Three-
dimensional structure-based tin disulfide/vertically aligned carbon nanotube
arrays composites as high-performance anode materials for lithium ion bat-
teries, J. Power Sources 277 (2015) 131e138.
[13] L. Qiu, Z.Q. Shao, D.X. Wang, W.J. Wang, F.J. Wang, J.Q. Wang, Enhanced
electrochemical properties of LiFePO4 (LFP) cathode using the carboxymethyl
cellulose lithium (CMC-Li) as novel binder in lithium-ion battery, Carbohydr.
Polym. 111 (2014) 588e591.
[14] C. Chen, S.H. Lee, M. Cho, J. Kim, Y.K. Lee, Cross-linked chitosan as an efficient
binder for Si anode of Li-ion batteries, ACS Appl. Mater. Interfaces 8 (2016)
2658e2665.
[15] M. Ling, J. Qiu, S. Li, C. Yan, M.J. Kiefel, G. Liu, S. Zhang, Multifunctional SA-
PProDOT binder for lithium ion batteries, Nano Lett. 15 (2015) 4440e4447.
[16] Y. Liu, C. Wang, H. Yang, Z.J. Shi, F.Q. Huang, Uniform-loaded SnS2/single-
walled carbon nanotubes hybrid with improved electrochemical performance
for lithium ion battery, Mater. Lett. 159 (2015) 329e332.
[17] L. Qiu, Z.Q. Shao, M.L. Liu, J.Q. Wang, P.F. Li, M. Zhao, Synthesis and electro-
spinning carboxymethyl cellulose lithium (CMC-Li) modified 9, 10-anthra-
quinone (AQ) high-rate lithium-ion battery, Carbohydr. Polym. 102 (2014)
986e9892.
[18] Y. Bie, J. Yang, X. Liu, J. Wang, Y.N. Nuli, W. Lu, Polydopamine wrapping silicon
cross-linked with polyacrylic acid as high-performance anode for lithium-ion
batteries, ACS Appl. Mater. Interfaces 8 (2016) 2899e2904.
[19] N. Petkov, J. Xu, M.A. Morris, J.D. Holmes, Confined growth and crystallog-
raphy of one-dimensional Bi2S3, CdS, and SnSx nanostructures within chan-
neled substrates, J. Phys. Chem. 112 (2008) 7345e7355.
[20] X.Q. Xie, S.Q. Chen, B. Sun, C.Y. Wang, G.X. Wang, 3D networked tin oxide/
graphene aerogel with a hierarchically porous architecture for high-rate
performance sodium-ion batteries, ChemSusChem 8 (2015) 2948e2955.
[21] Z.P. Cai, Y. Liang, W.S. Li, L.D. Xing, Y.H. Liao, Preparation and performances of
LiFePO4 cathode in aqueous solvent with polyacrylic acid as a binder, J. Power
Sources 189 (2009) 547e551.
[22] S. Komaba, K. Shimomura, N. Yabuuchi, T. Ozeki, H. Yui, K. Konno, Study on
polymer binders for high-capacity SiO negative electrode of Li-Ion batteries,
J. Phys. Chem. C 115 (2011) 13487e13495.
[23] P. Daraei, S.S. Madaeni, N. Ghaemi, H. Ahmadi Monfared, M.A. Khadivi,
Fabrication of PES nanofiltration membrane by simultaneous use of multi-
walled carbon nanotube and surface graft polymerization method: compari-
son of MWCNT and PAA modified MWCNT, Sep. Purif. Technol. 104 (2013)
32e44.
[24] F. Zhang, W.B. Zhang, Y. Yu, B. Deng, J.Y. Li, J. Jin, Solegel preparation of PAA-
g-PVDF/TiO2 nanocomposite hollow fiber membranes with extremely high
water flux and improved antifouling property, J. Membr. Sci. 432 (2013)
25e32.
[25] J. Wang, C. Luo, J.F. Mao, Y.J. Zhu, X.L. Fan, T. Gao, A.C. Mignerey, C.S. Wang,
Solid-state fabrication of SnS2/C nanospheres for high-performance sodium
ion battery anode, ACS Appl. Mater. Interfaces 7 (2015) 11476e11481.
[26] K.Y. Li, S.C. Yan, Z.X. Lin, X.B. Dai, P. Qu, Preparation and lithium ion batteries
properties of SnS2 nanoparticle/reduced graphene oxide nanosheet nano-
composites using supercritical carbon dioxide, Synth. Met. 217 (2016)
138e143.
[27] J. Lin, Z.W. Peng, C.S. Xiang, G.D. Ruan, Z. Yan, D. Natelson, J.M. Tour, Graphene
nanoribbon and nanostructured SnO2 composite anodes for lithium ion bat-
teries, ACS Nano 7 (2013) 6001e6006.
[28] S.C. Yan, K.Y. Li, Z.X. Lin, H.Z. Song, T. Jiang, J.S. Wu, Y. Shi, Fabrication of a
reversible SnS2/RGO nanocomposite for high performance lithium storage,
RSC Adv. 6 (2016) 32414e32421.
[29] Y. Yui, M. Hayashi, K. Hayashi, J. Nakamura, Electrochemical properties of Sn-
Co electrode with various kinds of binder materials for sodium ion batteries,
SSIon 288 (2016) 219e223.
[30] D.N. Lei, M. Zhang, B.H. Qu, J.M. Ma, Q.H. Li, L.B. Chen, B.G. Lu, T.H. Wang,
Hierarchical tin-based microspheres: solvothermal synthesis, chemical con-
version, mechanism and application in lithium ion batteries, Electrochim. Acta
106 (2013) 386e391.
[31] S.Y. Liu, X. Lu, J. Xie, G.S. Cao, T.J. Zhu, X.B. Zhao, Preferential c-axis orientation
of ultrathin SnS2 nanoplates on graphene as high-performance anode for Li-
ion batteries, ACS Appl. Mater. Interfaces 5 (2013) 1588e1595.
[32] T.F. Zhou, W.K. Pang, C.F. Zhang, J.P. Yang, Z.X. Chen, H.K. Liu, Z.P. Guo, Per-
formance by structural phase transition from two-dimensional hexagonal-
SnS2 to orthorhombic-SnS, ACS Nano (2014) 8323e8333.