Journal Pre-proofs

MXene-decorated SnS2/Sn3S4 hybrid as anode material for high-rate lithium-ion

batteries

Junfeng Li, Lu Han, Yuquan Li, Jinliang Li, Guang Zhu, Xiaojie Zhang, Ting
Lu, Likun Pan

PII: S1385-8947(19)31993-X
DOI: https://doi.org/10.1016/j.cej.2019.122590
Reference: CEJ 122590

To appear in: Chemical Engineering Journal

Received Date: 11 June 2019

Revised Date: 17 August 2019
Accepted Date: 22 August 2019

Please cite this article as: J. Li, L. Han, Y. Li, J. Li, G. Zhu, X. Zhang, T. Lu, L. Pan, MXene-decorated SnS2/
Sn3S4 hybrid as anode material for high-rate lithium-ion batteries, Chemical Engineering Journal (2019), doi: https://
doi.org/10.1016/j.cej.2019.122590

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© 2019 Published by Elsevier B.V.

MXene-decorated SnS2/Sn3S4 hybrid as anode material for

high-rate lithium-ion batteries

Junfeng Li,a Lu Han,a Yuquan Li,a Jinliang Li,b* Guang Zhu,c Xiaojie Zhang,d Ting

Lu,a Likun Pana*

a Shanghai Key Laboratory of Magnetic Resonance, School of Physics and Materials,

East China Normal University, 3663 N. Zhongshan Rd., Shanghai 200062, China

b Siyuan Laboratory, Guangdong Provincial Engineering Technology Research Center

of Vacuum Coating Technologies and New Energy Materials, Department of Physics,

Jinan University, Guangzhou 510632, China

c Key Laboratory of Spin Electron and Nanomaterials of Anhui Higher Education

Institutes, Suzhou University, Suzhou 234000,China

d National & Local Joint Engineering Research Center for Mineral Salt Deep

Utilization, Huaiyin Institute of Technology, Huaian 223003, China

*Corresponding author: Tel: 86 21 62234132; Fax: 86 21 62234321;

E-mail: lkpan@phy.ecnu.edu.cn (Likun Pan); lijinliang@email.jnu.edu.cn (Jinliang

Li)

1
Abstract

The combination of transitional metal dichalcogenides with MXene is an

effective strategy to explore high-performance anode materials for lithium-ion

batteries (LIBs). In this work, SnS2/Sn3S4 hybrid decorated on Ti3C2 MXene (S-TC)

was prepared through a facile solvothermal and calcination process. The multi-layered

Ti3C2 matrix improves the electron transport capability, inhibits the aggregation and

accommodates the volume change of SnS2/Sn3S4 hybrid, while the SnS2/Sn3S4 hybrid

confined in the multilayer stacks serves as a spacer to decrease the tendency of layer

restacking and improves the limited capacities of Ti3C2. Besides, the nano-sized

SnS2/Sn3S4 hybrid with high specific surface area also enhances the contact between

electrolyte and electrode. When used as anode for LIBs, S-TC demonstrates a good

cycling stability (462.3 mAh g-1 at 100 mA g-1 after 100 cycles) and superior rate

performance (216.5 mAh g-1 at 5000 mA g-1). The strategy in this work should

provide a new insight into fabricating novel MXene-based anode material for

high-rate LIBs.

Keyword: MXene; SnS2; Sn3S4; lithium-ion batteries; electrochemical performance

2
1. Introduction

With the ever-increasing energy demand of electronic devices and power-driven

transportations, developing efficient energy storage technologies with high-rate

capability and good cycle stability has received wide concerns [1-7]. In a variety of

energy storage technologies, rechargeable lithium-ion batteries (LIBs) are regarded as

one of the most widely utilized power sources. Up to now, the commercial graphite as

anode material with a low theoretical specific capacity (372 mAh g-1) and poor

security severely blocks the wide application of LIBs [8-10]. Recently, transitional

metal dichalcogenides (TMDs) have been investigated as promising anode materials

for next-generation LIBs [11-16]. TMDs usually have lower activation energy

between sulfur and metal than that between oxygen and metal in oxides, which is

beneficial for conversion reaction [17, 18]. They also exhibit higher theoretical

capacities than commercial graphite. In particular, SnS2 and Sn3S4 possess superior

theoretical capacities and suitable redox potential when used as anode of LIBs [19].

The structure of Sn3S4 can also be considered as a superstructure of SnS2, which

means that they can be prepared at the same time. However, their relatively low

electron transport ability and unceasing volume change during cycling process restrict

the electrochemical kinetics and induce severe damage of the electrode structure,

resulting in their poor rate capability and rapid capacity fading during cycling process

[12, 20, 21].

In order to overcome the volume expansion and improve the rate performance of

TMDs-based anode, a wide variety of methods have been developed [21-23]. One

3
effective method is to prepare nano-sized hybrid materials. The nano-sized materials

could accommodate the mechanical stress during cycling process, enhance the

electrode/electrolyte contact and facilitate the lithium ion transfer, yielding a high-rate

performance, while the diverse hybrid structure can further buffer the mechanical

stress by serving as a volume-buffering reservoir for each other during the stepwise

lithium insertion and extraction [11, 19, 24-27]. It should be noted that nano-sized

materials are more resistant to fracture than conventional bulk materials, because for

smaller structures, the stress-relief volume accompanying crack growth is not

significant enough to overcome the surface energy penalty associated with the crack

growth [28, 29]. Another widely adopted method is to combine TMDs with

conductive materials to improve their charge transport capability during

charge/discharge process [30-32]. As an emerging kind of 2D layer transition metal

carbonitrides/carbides produced by selectively etching specific element from the

compound MAX phase, MXenes have received extensive attention because of their

favorable strength, high density and superior metallic conductivity [33, 34]. Therefore,

they should be also considered a promising matrix for nanostructured TMDs material.

On one hand, the introduction of metallic MXenes not only improves the electron

transport ability, alleviates the volume change but also averts the aggregation of

nanostructured TMDs material during lithium insertion and extraction process [35,

36]. On the other hand, the existence of TMDs also decreases the tendency of layer

restacking and improves the limited capacities caused by surface chemistry in MXene

[35, 37]. For example, Lai’s group synthesized Ti3C2 nanosheets anchored by SnS

4
nanoparticles through a ultrasound and annealing process, which delivered a

discharge capacity of 471 mAh g-1 even at a high current density of 2000 mA g-1 after

30 cycles [38]. Guo’s group also reported a 3D-nest MoS2 intercalated Ti3C2, which

was able to deliver a discharge capacity of 315 mAh g-1 at 500 mA g-1 after 50 cycles

[39].

To make full use of those inspiring structural strategies and synergetic effects,

multiple component hybrid combined with MXene should be highly desirable but

seldom explored by now. In this work, for the first time, we reported the synthesis of

SnS2/Sn3S4 hybrid decorated on Ti3C2 MXene (S-TC) and evaluated its application as

an anode material for LIBs. The multilayered Ti3C2 matrix improves the electron

transport ability, alleviates the volume change and averts the aggregation of

SnS2/Sn3S4 hybrid during lithium insertion and extraction, while the nano-sized

SnS2/Sn3S4 hybrid enhances the electrode/electrolyte contact, relieves the mechanical

stress and also decreases the tendency of layer restacking in Ti3C2. As a consequence,

S-TC demonstrates a high capacity of 462.3 mAh g-1 after 100 cycles at a current

density of 100 mA g-1 and an excellent rate capability of 216.5 mAh g-1 at a high

current density of 5000 mA g-1.

2. Experimental

2.1 Sample synthesis

Multilayered Ti3C2Tx (Tx represents –OH and –F species) was synthesized

according to the previous literature [2]. Typically, 0.4 g Ti3Al2C2 powder was

immersed in 40 mL 45% HF solution and stirred at 25˚C for 72 h. The products were

5
then washed with ultrapure water and ethanol for several times, and dried in a vacuum

at 60 ˚C for 12 h. The SnS2/Sn3S4-Ti3C2 hybrids were obtained via solvothermal and

calcination methods. Briefly, 0.2 g Ti3C2Tx MXene and 0.8 g cetyltrimethyl

ammonium bromide (CTAB) were added in 40 mL deionized water and stirred for 1 h.

Subsequently, different amount of K2SnO3 (0.3, 0.6 and 0.9 g) and thioacetamide (0.6,

1.2 and 1.8 g) were added into the above solutions, respectively, and transferred into

100 mL Teflon-lined autoclave which was heated at 180 ˚ C for 24 h. K2SnO3 and

thioacetamide were used as tin source and sulphur source, respectively. It should be

noted that unlike other tin sources, such as SnCl2 and SnCl4, K2SnO3 is soluble in

water without violent hydrolysis while thioacetamide in aqueous solution can be

easily decomposed to form hydrogen sulphide under solvothermal condition. The

molar ratio of K2SnO3 and thioacetamide is 1:8, which means that the thioacetamide

was excess in this work. In fact, the excess thioacetamide is helpful to make

sulphation reactions proceed efficiently [40, 41]. After cooling down, the

as-synthesized samples were washed with ultrapure water and ethanol and dried at 60

˚C for 12 h. After calcinating at 500 ˚C for 4 h in nitrogen flow, the products named

S-TC-1, S-TC-2 and S-TC-3 were obtained. Notably, the solvothermal process

provides suitable temperature and high pressure conditions. The suitable temperature

promotes the decomposition of thioacetamide to release hydrogen sulphide while the

elevated pressure applied offers a larger driving force for the sulphation reactions to

occur. Besides, the calcination method was further used to enhance the crystallization

of SnSx nanoparticles [42, 43]. For comparison, the product named S-2 was also

6
synthesized according to similar procedure without adding Ti3C2Tx MXene.

2.2 Characterizations

The phase structure and surface elemental state of the products were recorded by

X-ray diffractometer (XRD, PROPW3040/60) with Cu-Kα radiation and X-ray

photoelectron spectroscopy (XPS, ESCALAB 250XI) with Al-Kα radiation. The zeta

potential of the sample was determined using the Zetasizer Nano ZS90 equipment

(Malvern Instruments, Worcestershire, UK). The size, surface morphology and

interior structure of the products were investigated by JEOL field emission scanning

electron microscopy (FESEM) and JEOL transmission electron microscopy (TEM).

The elemental composition of the samples was analyzed by energy dispersive X-ray

spectroscopy (EDX, Bruker Quantax-400). V-Sorb-2800P analyzer with

Barrett-Joyner-Halenda mode was employed to determine the pore size distribution

and specific surface area profile of the products.

2.3 Electrochemical measurements

The working electrodes were prepared by mingling 70 wt% active material, 20 wt%

Super P and 10 wt% polyvinylidene fluoride in N-methyl-2-pyrrolidinone. The

resulting slurry was obtained after stirring for 0.5 h and then bladed on a Cu foil. The

Cu foil was dried at 110˚C for 10 h. Pure Li disc and glass membrane were used as

reference electrode and separator, respectively. The half coin cells (CR2032) were

prepared in a glovebox filled with inert Ar atmosphere. The electrolyte consisted of

LiPF6 (1 M), diethyl carbonate (1:1, w/w) and ethylene carbonate. The cyclic

voltammetry (CV), electrochemical impedance spectroscopy (EIS) and cycle tests

7
were performed on an electrochemical workstation and a LAND-2001A battery

testing system in a voltage range of 0.005-3.0 V at room temperature, respectively.

3. Results and discussion

Fig. 1 shows the typical synthesis procedure of S-TC. The multilayered Ti3C2Tx

with negative electrical charge due to the existence of –OH and –F was firstly

prepared by selectively etching Al layer from Ti3AlC2 phase. A typical positive

cationic surfactant, CTAB was dissociated into CTA+ and Br- in water and the CTA+

was introduced into the multi-layered Ti3C2Tx through the electrostatic interaction and

ion exchange [44, 45]. Meantime, the corresponding zeta potential value also

increased from -37 to +55 mV (Fig. S1), which is in accordance with the previous

report [46]. The negative [SnO3]2- ions could be easily moved into the space between

the multi-layered Ti3C2Tx and absorbed on its surface through electrostatic interaction

[46-48]. Subsequently, [SnO3]2- attached to the space between the multilayer and

surface of Ti3C2Tx was sulfurated and partially reduced during the solvothermal and

calcination process.

8
 Fig. 1 Schematic illustration on the synthesis procedure of S-TC.

The crystal phases of the samples were characterized by XRD. The XRD pattern of

Ti3AlC2 (Fig. S2) is in accordance with the standard XRD pattern (JCPDS 52-0875),

indicating its high purity. After selectively etching Al layer using HF, the (002)

diffraction peak in Ti3C2Tx is widened but (104) peak disappears, as observed from

the XRD pattern of Ti3C2Tx in Fig. 2a, which has also been reported in previous

literature [3]. Besides, three diffraction peaks at 2θ = 8.96 ˚ , 18.53 ˚ and 27.96 ˚

correspond to the (002), (006) and (008) planes of Ti3C2 [49, 50]. And the other two

diffraction peaks at 2θ =14˚ and 23.89 ˚ are related to AlO(OH) resulting from the

residual Al3+ in the interior of Ti3C2Tx and fluorinated Ti3C2F2 [45, 51]. The XRD

pattern of S-TC-2 is also shown in Fig. 2a, where the peaks at 2θ = 31.94°, 21.50° and

16.10° correspond to Sn3S4 (JCPDS 27-0900), while the other extra peaks at 2θ =

15.03°, 32.12° and 49.96° are ascribed to SnS2 (JCPDS 23-0677). Besides, the peaks

at 25.28°, 37.80° and 48.05° assigned to anatase TiO2 (JCPDS 21-1272) can be

9
observed, due to the surface oxidation of Ti3C2Tx during the solvothermal process. It

should be noted that those anatase TiO2 located on the surface of Ti3C2Tx is also

electrochemically active and can provide extra lithium-ion storage. In order to

confirm the partial oxidation of Ti3C2Tx, pure Ti3C2Tx was also treated through

similar solvothermal process as S-TC without adding K2SnO3 and thioacetamide, and

served as control (named as Ti3C2-TiO2). The XRD result (Fig. S3a) shows the

existence of (002) peak of Ti3C2Tx and characteristic peaks of anatase TiO2,

indicating the partial oxidation of Ti3C2Tx, which is in accordance with previous

report [52]. Besides, the high deconvolution of C 1s and Ti 2p in S-TC (See details in

Fig. 3b, S5c and S6) also show the co-existence of Ti3C2Tx and TiO2 [1]. Notably, in

the XRD pattern of S-TC-2 the disappearance of (002) peak of Ti3C2Tx should be due

to the inhibited restacking of Ti3C2Tx sheets caused by the existence of SnSx

nanoparticles, which has also been reported previously [53, 54]. The XRD pattern of

the CTAB modified Ti3C2Tx sample is also shown in Fig. S3b. It can be observed that

the (002) diffraction peak of Ti3C2Tx (Fig. S2) shifts from 8.96˚ to 8.39˚ after CTAB

modification, indicating that the interlayer spacing of Ti3C2Tx in S-TC-2 (also

modified by CTAB) increases slightly due to the intercalation of carbon atoms in the

alky chain [44, 45], which is beneficial to the lithium insertion. The XRD patterns of

S-TC-1 and STC-3 are similar to that of S-TC-2, as displayed in Fig. S4. The pore

size distribution and specific surface area profiles of the samples were investigated by

nitrogen adsorption-desorption isotherms. As shown in Fig. 2b, the nitrogen

adsorption-desorption isotherms of Ti3C2Tx, S-TC-1, S-TC-2 and S-TC-3 display IV

10
type curves. The distinct hysteresis loop at the P/P0 of about 0.4-1.0 indicates the

existence of abundant mesopores. As shown in Table S1, the larger specific surface

areas of S-TC-1 and S-TC-2 than Ti3C2Tx should be due to the existence of

nanoparticles with huge specific surface area. The lower specific surface area of

S-TC-3 should be ascribed to the aggregation of excessive nanoparticles. Besides, an

appropriate amount of nanoparticles embedded in the multilayered sheets of Ti3C2

should also lead to the formation of mesopores in S-TC-1 and S-TC-2. The relatively

abundant mesopores can offer more pathways for lithium ion transport, which is

beneficial to lithium-ion storage performance.

Fig. 2 (a) XRD patterns of Ti3C2Tx and S-TC-2. (b) Nitrogen

adsorption-desorption isotherms of Ti3C2Tx, S-TC-1, S-TC-2 and S-TC-3.

The surface elemental composition and chemical state of the samples were

clarified by using XPS measurements. The XPS survey spectra (Fig. 3a) confirm the

existence of C, Ti, O, F in Ti3C2Tx and C, Ti, O, F, Sn, S in S-TC-2. The decrease of

F in S-TC-2 should be due to the decomposition of F-containing group during

calcination process [13]. The C 1s and Ti 2p spectra of Ti3C2Tx are shown in Fig. S5a

11
and b, respectively, and the detailed descriptions can be referred to Supporting

Information. As shown in the C 1s spectrum of S-TC-2 (Fig. 3b), the fitted peaks at

284.5 and 285.9 eV correspond to C-C and C-O, and the other fitted peaks at 288.7

and 293.1 eV are ascribed to C=O and O-C=O, respectively [55, 56]. As shown in the

Sn 3d spectrum of STC-2 (Fig. 3c), two fitted peaks at 486.7 and 495.2 eV are

attributed to 3d5/2 and 3d3/2 states of Sn4+, while the smaller peaks at binding energies

of 485.4 and 493.8 eV are ascribed to 3d5/2 and 3d3/2 states of Sn2+, respectively [38,

57]. As shown in the S 2p spectrum of S-TC-2 (Fig. 3d), the fitted peaks at 161.7 and

162.9 eV are ascribed to 2p2/3 and 2p1/2 states of S2- which is combined with Sn2+ and

Sn4+, respectively, and the other fitted peak at binding energy of 169.0 eV is due to

the bond of –SOx- configuration [58, 59]. As shown in the Ti 2p spectrum of S-TC-2

(Fig. S5c), the fitted peaks at 459.1 and 464.8 eV are in accordance with 2p2/3 and

2p1/2 states of Ti-O bond, indicating the existence of TiO2, while the other fitted peaks

at 455.9 and 464.8 eV are ascribed to Ti-C/Ti(II) and Ti-F [60, 61]. The

deconvolutions of C 1s, Sn 3d, S 2p and Ti 3d spectra of S-TC-1 and S-TC-3 are

similar to those of S-TC-2, as shown in Fig. S6.

12
 Fig. 3 (a) XPS survey spectra of Ti3C2Tx and S-TC-2. XPS (b) C 1s, (c) Sn 3d

and (d) S 2p spectra of S-TC-2.

The morphologies and structures of the samples were further characterized by

FESEM and TEM measurements. The Ti3AlC2 shows a typical 2D structure with

compact multilayer accumulation (Fig. 4a). The Al layer of Ti3AlC2 precursor can be

selectively etched by HF, resulting in a more open multilayered Ti3C2Tx, as shown in

Fig. 4b. The multilayered Ti3C2Tx enhances the contact between electrode and

electrolyte, and also improves the electron transfer due to the exposed Ti-C layers,

which is beneficial to electrochemical energy storage. The SnS2/Sn3S4 hybrid was

decorated on the multilayered Ti3C2Tx after solvothermal and calcination process (Fig.

4c and S7). Interestingly, it can be found that plenty of SnS2/Sn3S4 nanoparticles were

embedded in the open channel of multilayered Ti3C2Tx. The multilayered Ti3C2Tx can

13
serve as a volume-buffering matrix and electron transport channel for SnS2/Sn3S4

hybrid. Besides, the uniform elemental distribution of Ti, C, Sn and S can also be

observed form the EDX mapping of S-TC-2 (Fig. 4d). The surface morphologies of

S-TC-1 and S-TC-3 are displayed in Fig. S8. The elemental compositions of S-TC-1,

S-TC-2 and S-TC-3 determined by EDX measurement are also summarized in Table

S2. The internal fine structure of S-TC-2 was also investigated by high-resolution

TEM. The lattice distances of 3.52 Å and 3.16 Å in Fig. 4f correspond to the (101)

plane of anatase TiO2 and (100) plane of SnS2, respectively, while the lattice distance

of 3.74 Å should belong to the crystal plane of Sn3S4, which are in conformity to the

XRD results.

Fig. 4 FESEM images of (a) Ti3AlC2, (b) Ti3C2Tx and (c) S-TC-2. (d) EDX

mapping of S-TC-2. (e-g) TEM and high-resolution TEM images of S-TC-2.

The lithium-ion storage performances of the as-prepared electrodes were

evaluated in lithium half-cell. The initial CV curves of Ti3C2Tx and S-CT-2 electrodes

14
performed in the potential window of 0.005-3 V at a scan rate of 0.2 mV s-1 are shown

in Fig. 5a and b. For Ti3C2Tx, the irreversible peaks located at 0.82 and 0.60 V in the

first cathodic scan should be attributed to the formation of stable solid electrolyte

interphase (SEI) film on the surface of Ti3C2Tx and some side reactions [2]. The broad

peak at 1.0 V should be attributed to the reversible reactions of lithium with the

multilayered Ti3C2 [36]. For S-TC-2, the extra broad peak at 1.19 V during the first

cathodic scan should be due to the stepped decomposition of SnSx [19, 22, 38]. As

reported by previous literatures [19, 62], the decomposition reactions of SnSx

gradually disappeared in subsequently cycles, which should be responsible for the

initial capacity loss. The other cathodic peak at 0.19 V should be attributed to the

alloying reaction of LixSn (0 < X ≤ 4.4) [19, 63, 64]. The subsequent anodic peaks at

0.51 and 0.65 V should be ascribed to a stepped de-alloying reaction of LixSn [19, 63,

65]. The other irreversible anodic peaks at 1.23 and 1.73 V should be due to the

oxygenation of metallic tin at higher potentials [64, 65]. It should be noted that the

cathodic peak at 1.19 V disappears while a cathodic peak at 0.75 V appears in the

second cycle, which should be due to the electrochemical activation process during

the first lithiation process [66, 67]. The CV curves overlaps well after the third cycles,

suggesting the excellent electrochemical reversibility. The charge/discharge curves of

Ti3C2Tx and S-TC-2 electrodes in the potential window of 0.005-3 V at 100 mA g-1

are also shown in Fig. 5c and d, respectively. It can be observed that Ti3C2Tx delivers

a first charge (discharge) capacity of 264 mAh g-1 (708 mAh g-1) with a coulombic

efficiency of 37.3 %, while S-TC-2 delivers a first charge (discharge) capacity of 707

15
mAh g-1 (1348 mAh g-1) with a coulombic efficiency of 37.2%. The much higher

capacity of S-TC-2 than Ti3C2Tx should be attributed to the synergetic effects between

Ti3C2 and SnS2/Sn3S4 hybrid. Furthermore, both of them exhibit low coulombic

efficiencies in the first cycle, which should be related to the formation of SEI layer

due to the decomposition of electrolyte and some irreversible reactions. The

coulombic efficiencies of Ti3C2Tx and S-TC-2 quickly reach over 90% in the second

cycle, indicating their high electrochemical reversibility.

Fig. 5 CV curves of (a) Ti3C2Tx and (b) S-TC-2 electrodes at a scan rate of 0.2

mV s-1. Charge/discharge curves of (c) Ti3C2Tx and (d) S-TC-2 electrodes at a

current density of 100 mA g-1 between 0.005 and 3 V.

The cycling performances of the as-prepared electrodes at 100 mA g-1 are shown

in Fig. 6a. The S-TC-1, S-TC-2 and S-TC-3 electrodes maintain reversible capacities

16
of 402.5, 462.3 and 434 mAh g-1, while the Ti3C2Tx and S-2 electrodes only deliver

low reversible capacities of 114.3 and 54 mAh g-1 after 100 cycles, respectively. The

moderate lithium-ion storage ability for Ti3C2Tx is due to the limited cation

intercalation ability of multilayered sheets and the rapid lithium-ion storage

degradation for S-2 is caused by severe pulverization of the structure during lithium

insertion/extraction process. The S-TC-1, S-TC-2 and S-TC-3 electrodes show high

and stable capacities due to the synergetic effect between multilayered Ti3C2 and

SnS2/Sn3S4 hybrid. Firstly, the multilayered Ti3C2 with high metallic conductivity can

not only improve the electron transport capability, but also inhibit the aggregation and

accommodate the volume change of SnS2/Sn3S4 hybrid during charge and discharge

process. Secondly, the confinement of SnS2/Sn3S4 nanoparticles in the multilayer

stacks can decrease the tendency of layer restacking and improve the limited

capacities of Ti3C2. Besides, the nano-sized SnS2/Sn3S4 with high specific surface

area can enhance the contact between electrolyte and electrode, which is beneficial for

lithium-ion storage performance. It should be noted that S-TC-2 demonstrates a

highest reversible capacity. Compared with S-TC-2, the lower capacity for S-TC-1

should result from relatively low content of SnSx nanoparticles, while for S-TC-3, the

excess content of SnSx nanoparticles will lead to aggregation of active materials and

result in capacity fading. In order to further investigate the electric and ionic

conductivity of S-TC, EIS measurements were conducted at an open circuit voltage.

Fig. S9 shows the typical EIS spectra of S-TC-2, S-TC-2, S-TC-3 electrodes after 100

cycles at a current density of 100 mA g-1. The Nyquist plots are fitted based on the

17
equivalent electric circuit, as shown in the inset of Fig. S9. The fitted Rct values of

S-TC-1, S-TC-2 and S-TC-3 are 328, 109 and 257 Ω, respectively. The lowest Rct

value of S-TC-2 indicates its faster electrochemical reaction kinetic at the

electrode/electrolyte interface, which should be beneficial for the enhancement of

lithium-ion storage capacity. Galvanostatic intermittence titration technique (GITT)

was also carried out to investigate the ion diffusion and conductivity properties of

S-TC. The GITT curves and corresponding Li+ diffusion coefficients of S-TC are

shown in Fig. S10. The cells were relaxed for 2 h after charge/discharge for 30 min at

the current density of 50 mA g-1 during the GITT tests and the calculating process of

diffusion coefficient is shown in Supporting Information. As presented in Fig. S10,

the GITT curves of S-TC-1, S-TC-2 and S-TC-3 show similar features and the Li+

diffusion coefficient varies in the course of discharge/charge. Notably, the Li+

diffusion coefficients of S-TC-1, S-TC-2 and S-TC-3 are close to each other,

indicating their similar ion diffusion and conductance abilities during the initial cycle.

The rate performance of S-TC-2 was further tested at 100, 200, 500, 1000, 2000 and

5000 mA g-1 (Fig. 6b). The S-TC-2 electrode delivers reversible specific capacities of

601.3, 540.4, 479.4, 423.9, 352.2, 216.5 mAh g-1 at 100, 200, 500, 1000, 2000 and

5000 mA g-1, respectively. When the current density returns to 100 mA g-1, the

reversible specific capacity of S-TC-2 could recover to 542.8 mAh g-1, indicating its

stable rate performance and structural ability. The comparison of the electrochemical

performance of S-TC-2 anode with other reported SnS2-based anodes in the literatures

is shown in Table S3. It can be seen that the S-TC-2 anode demonstrates better rate

18
capability than most of other SnS2-based anode for LIBs. Fig. 6c shows the long

cycling life of S-TC-2 electrode at a high current density of 5000 mA g-1 after rate

testing. The S-TC-2 electrode still maintains a reversible capacity of 101.4 mAh g-1

after 500 cycles, showing its excellent long-term cycling performance. The XRD

pattern of the cycled S-TC-2 electrode material is shown in Fig. S12. The main

diffraction peaks corresponding to TiO2, Sn3S4 and SnS2 can be clearly observed,

indicating the structural stability of S-TC-2 [68].

Fig. 6 (a) Cycling performances of Ti3C2Tx, S-TC-1, S-TC-2, S-TC-3 and S-2

electrodes at 100 mA g-1. (b) Rate performance of S-TC-2 electrode. (c) Long cycling

performance of S-TC-2 electrode at 5000 mA g-1.

In order to further understand the lithium-ion storage mechanism of S-TC-2, i.e.

diffusion and pseudocapacitive controlled contributions, the CV curves were tested at

different scan rates from 0.2 to 1.0 mV s-1 and displayed in Fig. 7a. The diffusion

19
controlled process is contributed by the interaction of the electrode and the

pseudocapacitive process is related to the surface reaction of the electrode [69].

Furthermore, the diffusion and pseudocapacitive controlled contributions can be

described by the following equation [70]:

𝑖 = a𝑣𝑏 (1)

where a and b are regolabile values, i and v represent the actual current and

corresponding rate, respectively. When the b value is closed to 1, the lithium-ion

storage is dominated by pseudocapacitive process, and when b value approaches 0.5,

indicating that the lithium-ion storage is controlled by diffusion controlled process

[71]. As shown in Fig. 7b, the b value can be calculated from the slope of log (v)-log

(i) linear relationship. The b values are 0.968, 0.558, 0.595, 0.928, 0.847, 0.775, 0.80,

and 0.84 at different voltages of 0.01, 0.3, 0.6, 0.9, 1.2, 1.5, 1.8 and 2.1 V, as shown

in Fig. 7c, indicating that the lithium-ion storage is affected by both of

pseudocapacitive and diffusion controlled processes. The ratios of pseudocapacitive

and diffusion controlled contributions to the total capacity can be obtained according

to the equation [72]:

12
i = 𝑘1𝑣 + 𝑘2𝑣 (2)

where k1v and k2v1/2 are the currents contributed by pseudocapacitive and diffusion

controlled processes at a certain voltage, respectively. As shown in Fig. 7d, the

pseudocapacitive contributions are 30.1%, 37.9%, 42.7%, 46.3% and 49.1% at scan

rates of 0.2, 0.4, 0.6, 0.8 and 1.0 mV s-1, respectively. It should be noted that the

partial pseudocapacitive contribution in S-TC-2 electrode is beneficial for its excellent

20
rate performance, due to the improved lithium-ion diffusion and rapid electron

transfer in pseudocapacitive process compared with diffusion controlled process.

The superior lithium-ion storage ability of S-TC-2 can be ascribed to the

following reasons. Firstly, the multilayered Ti3C2 with high metallic conductivity can

not only improve the electron transport ability, but also inhibit the aggregation and

accommodate the volume change of SnS2/Sn3S4 nanoparticles during charge and

discharge process. Secondly, the confinement of SnS2/Sn3S4 nanoparticles in the

multilayer stacks can decrease the tendency of layer restacking and improve the

limited capacities of Ti3C2. Thirdly, the SnS2/Sn3S4 nanoparticles with high specific

surface area decorated on Ti3C2 can enhance the contact between electrolyte and

electrode, resulting in lithium-ion diffusion. Besides, the partial pseudocapacitive

contribution in S-TC electrode at high current density can further improve the

lithium-ion diffusion as well as provide extra capacity, resulting in excellent

lithium-ion storage performance.

21
 Fig. 7 (a) CV curves of S-TC-2 electrode at different scan rates. (b) Linear

relationship between log (i) and log (v) at different voltages. (c) b values of S-TC-2 at

different voltages. (d) The ratios of pseudocapacitive and diffusion controlled

contributions at different scan rates.

4. Conclusions

In summary, S-TC has been prepared through a facile solvothermal and

calcination process. When evaluated as anode material for LIBs, S-TC exhibits

superior high-rate capability (216.5 mAh g-1 at 5000 mA g-1, respectively) and stable

cycling performance (426.3 mAh g-1 at 100 mA g-1 after 100 cycles) due to the

synergetic effects between the multi-layered Ti3C2 and SnS2/Sn3S4 hybrid

nanoparticles. The S-TC should be a promising high-rate anode for LIBs.

Acknowledgements

This work was supported by National Natural Science Foundation of China

22
(51702056), China Postdoctoral Science Foundation (No.2017M622902), Important

Project of Anhui Provincial Education Department (KJ2018A0446).

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Figure captions

Fig. 1 Schematic illustration on the synthesis procedure of S-TC.

Fig. 2 (a) XRD patterns of Ti3C2Tx and S-TC-2. (b) Nitrogen adsorption-desorption

isotherms of Ti3C2Tx, S-TC-1, S-TC-2 and S-TC-3.

Fig. 3 (a) XPS survey spectra of Ti3C2Tx and S-TC-2. XPS (b) C 1s, (c) Sn 3d and (d)

S 2p spectra of S-TC-2.

Fig. 4 FESEM images of (a) Ti3AlC2, (b) Ti3C2Tx and (c) S-TC-2. (d) EDX mapping

of S-TC-2. (e-g) TEM and high-resolution TEM images of S-TC-2.

Fig. 5 CV curves of (a) Ti3C2Tx and (b) S-TC-2 electrodes at a scan rate of 0.2 mV s-1.

Charge/discharge curves of (c) Ti3C2Tx and (d) S-TC-2 electrodes at a current density

of 100 mA g-1 between 0.005 and 3 V.

Fig. 6 (a) Cycling performances of Ti3C2Tx, S-TC-1, S-TC-2, S-TC-3 and S-2

electrodes at 100 mA g-1. (b) Rate performance of S-TC-2 electrode. (c) Long cycling

performance of S-TC-2 electrode at 5000 mA g-1.

Fig. 7 (a) CV curves of S-TC-2 electrode at different scan rates. (b) Linear

relationship between log (i) and log (v) at different voltages. (c) b values of S-TC-2 at

different voltages. (d) The ratios of pseudocapacitive and diffusion controlled

contributions at different scan rates.

Graphical Contents Entry

35
Research Highlights

 The unique SnS2/Sn3S4-Ti3C2 composites were studied as anode material of LIBs.

 The SnS2/Sn3S4 hybrid and Ti3C2 MXene display high synergetic effects.

 The SnS2/Sn3S4-Ti3C2 composites demonstrate superior rate performance.

36