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Article
ALD TiO2 coated flower-like MoS2 nanosheets on carbon cloth as sodium
ion battery anode with enhanced cycling stability and rate capability
Weina Ren, Weiwei Zhou, Haifeng Zhang, and Chuanwei Cheng
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b13179 • Publication Date (Web): 14 Dec 2016
Downloaded from http://pubs.acs.org on December 16, 2016

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4 ALD TiO2 coated flower-like MoS2 nanosheets on carbon cloth
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6 as sodium ion battery anode with enhanced cycling stability and
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9 rate capability
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11 Weina Rena, Weiwei Zhoub, Haifeng Zhanga, Chuanwei Chenga*
12 a
13 Shanghai Key Laboratory of Special Artificial Microstructure Materials and Technology, School
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15 of Physics Science and Engineering, Tongji University, Shanghai 200092, P.R. China
16 b
17 School of Materials Science and Engineering, Harbin Institue of Technology at Weihai, Weihai，
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264209, P. R. China
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20 Email: cwcheng@tongji.edu.cn
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Abstract
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27 In this paper, we report the fabrication of 3D flower-like MoS2 nanosheets arrays on
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29 carbon cloth as a binder-free anode for sodium ion battery. Ultrathin and conformal
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31 TiO2 layer are used to modify the surface of MoS2 by atomic layer deposition. The
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33 electrochemical performance measurements demonstrate that the ALD TiO2 layer can
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35 improve the cycling stability and rate capability of MoS2. The MoS2 nanosheets with
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37 0.5 nm TiO2 coating electrode shows the highest initial discharge capacity of 1392
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39 mA h g-1 at 200 mA g-1, which is increased by 53% compared with that of bare MoS2.
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After 150 cycles, the capacity retention rates of the TiO2 coated MoS2 achieves 75.8%
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42 of its second cycle’s capacity at 200 mA h g-1 in contrast to that of 59% of pure MoS2.
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44 Furthermore, the mechanism behind the experimental results are revealed by ex-situ
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46 scanning electron microscope (SEM), X-ray powder diffraction (XRD) and
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48 electrochemical impedance spectroscopy (EIS) characterizations, which confirm that
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50 the ultrathin TiO2 modifications can prevent the structural degradation and the
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52 formation of SEI film of MoS2 electrode.
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54 Keywords: Sodium ion battery; Anode; Atomic layer deposition; Flower-like MoS2
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56 nanosheets; TiO2;
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4 1. Introduction
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6 Na-ion batteries (NIBs) have received an increasing attention as promising
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8 alternatives to Li-ion batteries (LIB) due to the low cost, natural abundance and a
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10 similar redox potential to lithium of sodium element.1-3 However, the selection and
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12 exploring of suitable electrode materials for Na-ion batteries is still a great challenge
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due to that the Na+ has larger radius of (1.06 Å) than that of Li+ (0.76 Å) , leading to a
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15 higher volume expansion and lower energy densities.4 Currently, the investigated
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17 anode materials for sodium ion batteries include carbon based materials,5-7
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19 alloy-based materials,8-10 metal oxides11-13 and transition metal sulfides14-16. Among
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21 them, MoS2, as a member of layer transition metal dichalcogenides, is a promising
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23 candidate anode because of its graphite-like structure with large layer spacing of
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25 0.615 nm as well as high theoretical capacities (670 mA h g-1).17 However, the poor
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27 cycling stability and rates capability arising from the low electronic transmission rate
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and aggregation tendency plus the dissolution of reaction intermediates (Na2S) during
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charging/discharging remain the stumbling blocks on the road of development MoS2
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32 anode.18-20 To address these problems, one effective approach is preparation of
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34 ultra-thin and expanded spacing MoS221, 22
and combined with high conductivity
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36 materials like carbon14, 23-26
. Besides, deposition of a passivation layer at the
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38 electrode/electrolyte interface is another effective strategy to prevent the structure
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40 degradation and repeated formation of SEI films, which have been widely adopted in
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42 LIBs research27, 28 and also NIBs anodes29, 30. To this end, atomic layer deposition
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44 shows great potential for thin film deposition and electrode surface modification due
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to its advantages in excellent shape retention and thickness controllability.31-36
47 Herein, we report the preparation of ultrathin TiO2 modified 3D flower-like
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49 MoS2 nanosheets arrays on flexible carbon cloth by a hydrothermal method and a
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51 subsequent ALD process for the first time. As a binder-free anode for sodium ion
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53 battery, such an electrode design is favorable to improve the specific capacity, cycling
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55 stability and rates performance. First, the 3D flower-like nanosheets arrays directly
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57 supported on current collector with large surface area are facilitating the electron and
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3 ion diffusion and transportation (Scheme 1). Second, the TiO2 layer is stable enough
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5 during sodiation/desodiation cycles37, which can act as a satisfactory passivation and
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7 buffer layer of MoS2 to prevent the electrode corrosion and collapse. Moreover, the
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9 synergistic effect between the MoS2 and TiO2 is conducive to improve the electrode
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11 capacity and cycling stability. By testing them as NIBs anodes, enhanced capacity,
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13 cycling stability and rates capability are demonstrated by ALD TiO2 modification on
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15 MoS2 nanosheets surface.
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17 2. Experimental Section
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19 2.1 Samples preparation
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21 Synthesis of 3D MoS2 nanosheets on carbon cloth: First, the carbon cloth was
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23 cleaned in acetone, ethanol and deionized water by ultrasonication for 20 minutes
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25 each, respectively, and then soaked in nitric acid with a concentration of 65% for 24
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27 hours to improve its surface hydrophilicity. Then the growth of MoS2 nanosheets on
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carbon cloth was accomplished by a hydrothermal method. In a typical process: 120
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mg sodium molybdate (NaMoO4.2H2O) and 190 mg of thiourea (CH4N2S) were
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32 dissolved in 30 ml of deionized water and stirred for 30 minutes until clear, and then
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34 the above solution was transferred to a 50 ml sealed Teflon-lined stainless steel
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36 autoclave with one piece of the treated carbon cloth placed inside. The temperature
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38 was kept at 200 °C by an electric oven and maintained for 20 h. After that, the sample
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40 was taken out and washed with deionized water repeatedly, then dried in an oven at
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42 80 °C.
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44 ALD of ultrathin TiO2 layer on MoS2 nanosheets: The ultrathin TiO2 layer coated
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on the MoS2 surface with different thickness was conducted by a Picosun R-200 ALD
47 system.38 During the deposition process, TiCl4 and H2O were used as the precursors
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49 of Ti and O, respectively. The TiO2 was deposited at 75 °C with the speed of ~ 0.8
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51 Å/cycle and the thickness of the TiO2 layer can be effectively controlled through
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53 different cycles’ settings: 7 cycles, 13 cycles and 25 cycles were used to deposit about
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55 0.5 nm, 1 nm and 2 nm, respectively.
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57 2.2 Material characterizations
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3 The microscopic structure and morphology of the as-synthesized MoS2 nanosheets
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5 and TiO2 coated MoS2 nanosheets were recorded by field-emission scanning electron
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7 microscope (FE-SEM, FEI Sirion200), high-resolution transmission electron
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9 microscope (HR-TEM, JEM-2010F) and selected area diffraction patterns. The crystal
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11 structure, composition and valence state of the samples were characterized by X-ray
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13 powder diffraction (XRD, Bruker D8-Advance) and X-ray photoelectron spectra
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15 (XPS, Kratos Axis Ultra DLD).
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17 2.3 Electrochemical Measurements
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Electrochemical measurements of all the active materials were carried out by using
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20 CR2032 coin-type cells. MoS2 and MoS2/TiO2 nanosheets on carbon cloth were
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22 directly used as binder-free anodes, and sodium foil (J&K Scientific) was used as the
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24 cathode for sodium ion battery. A microporous glass fiber membrane (Whatman) and
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26 1 M solution of NaClO4 in ethylene carbonate (EC) and dimethyl carbonate (DMC)
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28 (1:1 by weight) with 5 vol% fluoroethylene carbonate (FEC)were employed as the
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30 separator and electrolyte for the cells, respectively. The carbon’s density is 13.4 mg
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32 cm-2 and the average loading density of these active materials was about 3 mg cm-2.
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34 The galvanostatic charge–discharge cycles at different current densities and the rates
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performance were tested in a multi-channel battery tester (Neware Co., China) with a
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37 voltage of 0.01~2.5 V at room temperature. The cyclic voltammetry measurements
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39 were performed on a CHI760D electrochemical workstation.
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3. Results and Discussions
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44 3.1 Morphology and structure characterizations
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The morphology and structure of the as-obtained MoS2 nanosheets and TiO2 coated
47 ones were characterized by SEM and XRD. The low magnification SEM image in
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49 Figure 1a shows that spherical MoS2 structures with textured surfaces are almost
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51 uniformly wrapped around each carbon fiber. From a closer view in Figure 1b，it can
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53 be seen that the flower-like MoS2 structures are assembled of several thin nanosheets.
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55 The diameter of each flower is about 1 µm. After the ALD of 2 nm TiO2 coating, the
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57 morphology doesn’t change much, as shown in Figure 1c, which is attributed to the
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3 characteristics of ultrathin TiO2 layer and ultra-uniform deposition characteristics of
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5 ALD. The SEM images of MoS2 nanosheets coated with 0.5 nm and 1 nm TiO2 are
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7 also provided in Figure S1 in Supporting Information. The EDX elemental mapping
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9 (Figure S2 (b)-(e)) images obtained from the MoS2-2 nm TiO2 sample indicate the
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11 well distribution of the Mo, S, Ti and O elements. The phase purity and crystallinity
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13 of the as-prepared samples were further demonstrated by XRD. As displayed in
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15 Figure 1d, all the diffraction peaks are matched with the hexagonal phase of 2H-MoS2
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17 (JCPDS No. 37-1492).39, 40 The peaks at 14.2°, 33°, 40°, 44° and 58° are respectively
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indexed to (002), (100), (103), (006) and (110) planes of the single phase MoS2, and
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20 the peak at 26° comes from the carbon cloth substrate. Especially, the (002) peak at
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22 14.2° indicates the stacked layered structure of the MoS2 nanosheets.21 Noting that we
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24 haven’t observe the characteristic peaks of TiO2 in the TiO2 coated sample, which is
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26 due to the amorphous structure of TiO2 deposited at 75℃.
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28 In order to explore more detailed structural information of the MoS2 nanosheets
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30 and MoS2-TiO2 composites, TEM and HR-TEM observations were performed. As
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32 shown in Figure 2a, the ultrathin MoS2 nanosheets are interlaced with each other to
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34 form the flowers, which is consistent with the SEM observations. From the HR-TEM
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image of the pure MoS2 nanosheets in Figure 2b, we can easily observe the lamellar
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37 structure on the edge of MoS2 nanosheet with a thickness of about 9 nm, which is
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39 corresponding to 13~15 S-Mo-S layers with an interlayer spacing of about 0.635 nm.
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41 The thicknesses of MoS2 nanosheets are between 5~10 nm, which can be clearly
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43 observed from the TEM image in Figure S3. The corresponding SAED patterns in
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45 Figure 2c demonstrate that the MoS2 nanosheets are polycrystalline. The diffraction
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47 rings are accurately indexed to (110), (103), (100), and (002) planes of 2H-MoS2. The
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49 HR-TEM picture of the MoS2 with 2 nm TiO2 coating was shown in Figure 2d, which
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confirms that the amorphous TiO2 layer is uniformly coated the outside of the
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multilayer structure, and the thickness is precisely controlled at about 2 nm by ALD.
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54 The composition and chemical state of the TiO2 coated MoS2 sample was further
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56 investigated by XPS. The high-resolution XPS spectra in Figure 3 show a narrow
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58 range scans for the peaks of the four elements. The high-resolution Mo 3d XPS
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3 spectrum in Figure 3a show two peaks with binding energies of 232.8 and 229.6 eV,
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5 which are corresponding to the Mo4+ 3d3/2 and Mo4+ 3d5/2, respectively. The peak at
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7 236 eV is attributed to the Mo6+ 3d,24 which might be due to the oxidation of Mo4+ in
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9 the atmosphere. The S 2s peak is detected at 226.8 eV. The S2- 2p3/2 and S2- 2p1/2
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11 peaks in Figure 3b are centered at 162.3 eV and 163.5 eV, respectively.41, 42 As show
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13 in Figure 3c, there are two peaks at 464.7 and 458.9, which can be attributed to Ti
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15 2p1/2 and Ti 2p3/2, respectively.43 The O 1s XPS spectrum was shown in Figure 3d,
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17 besides the O 1s peaks at 530 eV attributed to the Ti–O–Ti bond, the peak at 532.0 eV
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could be assigned to the adsorbed water.44, 45
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20 3.2 Electrochemical Performance
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22 The electrochemical performance of as-synthesized MoS2 nanosheets and TiO2 coated
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24 ones with different thickness were evaluated by tested them as sodium ion battery
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26 anodes. First, we carried out the cyclic voltammetry measurements for each electrode
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28 at a scan rate of 0.2 mV s-1 between 0.001 V and 2.5 V. In the first cycle as shown in
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30 Figure 4a, the curves of all the electrodes show typical peaks of MoS2 in the reduction
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32 and oxidation reactions. The first reduction peak at~1.9 V attributed to the insertion of
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34 Na+ into MoS2, forming NaxMoS2 are observed in pure MoS2, 0.5 nm and 1nm TiO2
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coated MoS2 electrodes.25 Noting that this peak intensity decrease with the increase of
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37 TiO2 layer thickness until disappearing in the 2 nm TiO2 deposited MoS2 electrode,
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39 which might be due to that thick TiO2 layer would prevent the sodium ion to diffuse
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41 and react with the MoS2 in a timely manner. The following reduction peaks of all the
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43 electrodes at ~0.8 V and ~0.6 V are relevant to the further insertion of Na ions in
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45 MoS2.25, 46 The peak under 0.3 V in the deep cathodic process corresponds to the
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47 subsequent conversion reaction from NaxMoS2 to Mo. The corresponding oxidation
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49 peaks at about 0.4 V, 1.8 V and 2.3 V are also observed. In the second cycle in Figure
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4b of CV curves, the reduction peaks at ~0.8 V and ~0.6 V are reduced and change to
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higher potential of 0.7 V and 1.4 V, respectively. One peak at 1.4 V is attributed to the
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54 intercalation reaction of Na+ ions, and the other one at 0.7 V is assigned to the
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56 conversion reaction.21 The redox peaks tend to keep stable in the following four
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58 cycles as displayed in Figure S4, which indicates the stable and reversible process of
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3 sodiation/desodiation reactions.46-48 During the oxidation reduction process, the
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5 typical peaks of TiO2 are not observed, which may be due to the ultra-thin thickness
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7 of TiO2 layer.
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9 Figure 5a shows the charge-discharge voltage-capacity curves of all the samples
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11 for the first cycle at the current density of 200 mA g-1 and a potential window of 0.01
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13 V~2.5 V. The three voltage plateaus located at 0.8 V, 0.6 V and 0.2 V~0.01 V are
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15 observed in the four electrodes, which are consistent with the CV analysis in Figure
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17 4a. In order to prove the stable cycling performance of the TiO2 modified electrode,
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the galvanostatic charge-discharge test was continued until 150 cycles under the same
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20 condition, which was demonstrated in Figure 5b. According to the order of TiO2
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22 thickness from thin to thick, the initial discharge & charge capacities of each electrode
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24 are 1392.8 mA h g-1 & 957.4 mA h g-1 (0.5 nm), 1101 mA h g-1 & 751.7 mA h g-1 (1
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26 nm) and 1147.8 mA h g-1 & 745.8 mA h g-1 (2 nm), respectively. Compared with that
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28 of the pure MoS2 (910 mA h g-1 & 596.8 mA h g-1), the initial discharge capacity of
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30 the electrodes modified by TiO2 was significantly improved, and the initial coulombic
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32 efficiency (CE) has also been increased from 64 % to 69 %. After 150 cycles, the
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34 discharge specific capacity of MoS2 is 317.2 mA h g-1, which is only 59% of its
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second cycle’s capacity. Meanwhile, the capacity retention rate of the composite
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37 electrodes with 0.5 nm, 1 nm and 2 nm TiO2 coating are 75.8%, 74.1% and 64%,
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39 respectively. This performance improvement in TiO2 coated MoS2 might be attributed
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41 to the synergistic effect of the composite materials and the passivation nature of TiO2
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43 layer with functions of preventing pulverization of MoS2 caused by the volume
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45 change during charging/discharging process, as well as protecting the MoS2 from
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47 corrosion and preventing the formation of SEI film.
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49 Figure 5c exhibits the rates performance of the samples, the MoS2 nanosheets
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electrodes with ultrathin TiO2 modification show outstanding capacity retention at
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various current densities from 50 to 800 mA g-1. Even at a high rate of 800 mA g-1,
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54 their capacities retention could be still preserved at more than 42%, which
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56 corresponds to the capacities of 392 mA h g-1 for MoS2-0.5 nm TiO2, 369 mA h g-1 for
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58 MoS2-1 nm TiO2 and 329 mA h g-1 for MoS2-2 nm TiO2, respectively. When the
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3 current returns to 50 mA g-1, the TiO2 coated MoS2 electrodes showed the specific
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5 capacity of 801 mA h g-1, 754 mA h g-1 and 775 mA h g-1, respectively. Their capacity
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7 recovery rates are as high as 92% or more, while the pure MoS2 is only 71%. The
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9 capacity and cycling performance of the TiO2 coated MoS2 electrodes in our case are
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11 superior to most of the previous reported MoS2 based composite electrodes, as
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13 summarized in Table S1 in Supporting information.
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15 In order to verify the superiority of TiO2 coated MoS2 electrode, the long-term
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17 stability of the samples was further evaluated at a high current density of 500 mA g-1
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as shown in Figure 5d. After 200 cycles, the reversible capacity of MoS2-1 nm TiO2
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20 and MoS2-2 nm TiO2 electrodes could be still maintained at 182 and 157 mA h g-1,
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22 respectively, and the corresponding capacity retention were 60% and 69%. These
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24 capacities retention are far higher than that of bare and 0.5 nm TiO2 coated MoS2
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26 electrodes, which are only 40% and 33%. From the view of this, the cycle stability of
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28 MoS2-0.5 nm TiO2 electrode at high rate is not ideal. Such a similar poor cyclic
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30 performance with MoS2 might be due to that the 0.5 nm TiO2 layer is too thin to adapt
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32 to the rapid volume change during sodium ion intercalation/deintercalation, leading to
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34 severe structural damage and sulfur dissolution.49 Taking into account the capacity
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performance and the cycle stability, in can be concluded that the comprehensive
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37 performance of MoS2-1 nm TiO2 electrode is the best among the three electrodes with
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39 different thickness of TiO2.
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41 3.3 Mechanism Investigation
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43 The mechanism behind the high rate performance and exceptional cycling
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45 stability of the MoS2/TiO2 anode is also investigated. The morphology structure of
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47 electrode material after cycling can directly reflect its structural stability. Figure 6a-6d
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49 present the SEM images of MoS2 and MoS2 coated with 0.5 nm, 1 nm, and 2 nm TiO2
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electrodes after 150 cycles at 200 mA g-1. For the pure MoS2 sample, the flower-like
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structure is completely disappeared after several cycles due to the serious collapse and
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54 agglomeration problems. While for the TiO2 coated ones, the flower-like structures
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56 are kept well, demonstrating the protective effect of the TiO2 layer. The TEM images
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58 of bare MoS2 and TiO2 coated MoS2 samples after 5 charging-discharging cycles were
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3 also shown in Figure S5. No SEI films were observed in the TiO2 coated electrode in
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5 contrast to that of bare MoS2 one, indicating that the TiO2 layer modification can
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7 effectively prevent the formation of SEI films. Based on the above discussions, the
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9 high capacity retention characteristic of the ALD TiO2 coated MoS2 anodes might be
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11 attributed to the function of ultrathin TiO2 layer that can buffer the volume change of
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13 MoS2 during charging/discharging process and act as a protective barrier layer
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15 between the anode/electrolyte interface to prevent the formation of SEI film，as a
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17 result of keeping the structural integrity.
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Furthermore, the ex-situ XRD patterns of all the electrodes after 100 cycles at
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20 200 mA g-1 were measured to study the structure and phase change after sodium ion
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22 intercalation/de-intercalation process. As shown in Figure 7, from the bottom to up,
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24 the diffraction patterns correspond to the pure MoS2 (I), MoS2-0.5 nm TiO2 (II),
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26 MoS2-1 nm TiO2 (III), MoS2-2 nm TiO2 (IV), respectively. After several cycles, two
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28 new additional peaks at 9.46° and 19.2° are clearly observed in the TiO2 coated
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30 samples, which correspond to the estimated lattice spacings of 9.33 and 4.61 Å,
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32 respectively. The dual relationship between these two lattice spacings demonstrates
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34 that a new lamellar structure with an enlarged interlayer spacing was formed during
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the process of Na+ insertion and extraction.20 And the diffraction peaks of composite
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37 material at 32.3°, 43.4° and 56.8°indexed to the (100), (006) and (110) planes of
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39 MoS2 were also observed. These results suggest that the TiO2 layer can protect the
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41 crystal structure of MoS2 very well. However, the peak of corresponding (002) plane
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43 doesn’t appear in the pure MoS2 electrode, which indicates that the layered structure
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45 was severely damaged during the cycles without the protection of TiO2. The XRD
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47 results are consistent with the analyses of SEM in Figure 6.
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49 To understand why the MoS2-0.5 nm TiO2 electrode and MoS2-1 nm TiO2
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electrode exhibit different long cycling stability at varied current density, impedance
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measurements of the two samples were carried out after 50 cycles at a constant
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54 current density of 200 mA g-1 and after 100 cycles at a constant current density of 500
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56 mA g-1. As show in Figure 8a and 8b, all the Nyquist plots were consisted of two
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58 semicircles at high and medium frequencies and straight sloping lines at low
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3 frequencies. It well known that the intercept of the Z’ axis in the high frequency
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5 corresponds to the bulk resistance of electrolyte, separator and electrodes, the high
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7 frequency semicircle corresponds to the resistance of SEI film, the medium frequency
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9 semicircle corresponds to the charge-transfer resistance, and the low frequency
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11 sloping line is associated with the diffusion of sodium ions in the active material.49-52
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13 The corresponding Nyquist plots was fitted by an equivalent circuit model as shown
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15 in Figure S6. As shown in Figure 8a, it can be seen that the semicircles at high and
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17 medium frequencies of MoS2-0.5 nm TiO2 electrode are smaller than that of the
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MoS2-1 nm TiO2 electrode, which reveals that the MoS2-0.5 nm TiO2 electrode
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20 possesses the lower interfacial resistance after 50 cycles at 200 mA g-1. Obviously,
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22 when the current density changes to 500 mA g-1 as shown in Figure 8b, the interface
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24 resistance of MoS2-0.5 nm TiO2 electrode is much larger than that of MoS2-1 nm TiO2
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26 electrode, which is arising from the collapse of structures and the absence of electrical
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28 contact. Figure 8c and 8d show the Z’-ω−1/2 (ω =2πf) curves in the low frequency
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30 region, and the low slope indicates good sodium ion kinetics in the electrode
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32 materials.14, 50, 51 They clearly show that the sodium ion kinetics of MoS2-0.5 nm TiO2
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34 was better than that of MoS2-1 nm TiO2 after cycles at 200 mA g-1 and worse than it
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after cycles at 500 mA g-1. This result is consistent with the phenomenon of the above
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37 long-term galvanostatic charge-discharge test, the lower interface resistance and better
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39 sodium ion kinetics are the main factors leading to the excellent cycling stability.
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4. Conclusions
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44 In conclusion, 3D flower-like MoS2 nanosheets arrays on carbon cloth have been
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fabricated by a facile and scalable hydrothermal route as binder-free anode for sodium
47 ion batteries. The cycling stability and rate capability of MoS2 nanosheets electrodes
48
49 were improved greatly by ALD deposited conformal TiO2 layer. After 150 cycles at
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51 200 mA g-1, a remarkable capacity retention characteristic (75.8% of second capacity)
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53 was demonstrated for the TiO2 coated electrode. Such an excellent electrochemical
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55 performance is ascribed to functional TiO2 layer that can keep the structure integrity
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57 of MoS2 nanosheets as well as prevent the SEI layer formation. The ex-situ SEM and
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3 XRD results revealed that the TiO2 layer is able to improve the crystallinity and 3D
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5 structure retention of MoS2 nanosheets during cycling process, and the EIS tests
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7 showed the relatively thick TiO2 layer can reduce the resistance of SEI film and the
8
9 electron-transfer, and promote the diffusion efficiency of the sodium ion at a higher
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11 current density. Our study provides a valuable reference for the electrode design and
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13 surface engineering towards high performance sodium ion batteries with long cycling
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15 life and high rate capability.
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17 Supporting Information
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19 SEM images of 3D MoS2 nanosheets coated with 0.5 nm and 1 nm TiO2 layer; EDX
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21 mapping of MoS2-2 nm TiO2; TEM images of 3D MoS2 nanosheets; CV curves of
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23 MoS2, MoS2-0.5 nm TiO2, MoS2-1 nm TiO2 and MoS2-2 nm TiO2 at a scanning rate
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25 of 0.2 mV s-1 in the first 5 cycles; TEM images of MoS2 nanosheets and MoS2-2 nm
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27 TiO2 after 5 cycles; The equivalent circuit diagram of the Nyquist plots; The table of
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comparison of electrochemical performance.
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31 Acknowledgements
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33 This work was financially supported by 973 Program (Grant no.2013CB632701) and
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35 the National Natural Science Foundation of China (Grant no. 51202163).
36
37 References
38
39 (1) Yabuuchi, N.; Kubota, K.; Dahbi, M.; Komaba, S., Research Development on Sodium-Ion
40 Batteries. Chem. Rev. 2014, 114, 11636-11682.
41 (2) Pan, H.; Hu, Y.-S.; Chen, L., Room-Temperature Stationary Sodium-Ion Batteries for Large-Scale
42
43 Electric Energy Storage. Energy Environ. Sci. 2013, 6, 2338-2360.
44 (3) Wang, L.; Lu, Y.; Liu, J.; Xu, M.; Cheng, J.; Zhang, D.; Goodenough, J. B., A Superior Low-Cost
45 Cathode for a Na-Ion Battery. Angew. Chem. Int. Ed. 2013, 52, 1964-1967.
46 (4) Dahbi, M.; Yabuuchi, N.; Kubota, K.; Tokiwa, K.; Komaba, S., Negative Electrodes for Na-Ion
47
48 Batteries. Phys. Chem. Chem. Phys. 2014, 16, 15007-15028.
49 (5) Wen, Y.; He, K.; Zhu, Y.; Han, F.; Xu, Y.; Matsuda, I.; Ishii, Y.; Cumings, J.; Wang, C., Expanded
50 Graphite as Superior Anode for Sodium-Ion Batteries. Nat. Commun. 2014, 5, 4033.
51
(6) Sun, J.; Lee, H.-W.; Pasta, M.; Yuan, H.; Zheng, G.; Sun, Y.; Li, Y.; Cui, Y., A
52
53 Phosphorene-Graphene Hybrid Material as a High-Capacity Anode for Sodium-Ion Batteries. Nature
54 Nanotech. 2015, 10, 980-985.
55 (7) Kong, D.; Cheng, C.; Wang, Y.; Liu, B.; Huang, Z.; Yang, H. Y., Seed-Assisted Growth of Α-Fe2O3
56
Nanorod Arrays on Reduced Graphene Oxide: A Superior Anode for High-Performance Li-Ion and
57
58 Na-Ion Batteries. J. Mater. Chem. A 2016, 4, 11800-11811.
59
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 ACS Applied Materials & Interfaces Page 12 of 25

1
2
3 (8) He, M.; Walter, M.; Kravchyk, K. V.; Erni, R.; Widmer, R.; Kovalenko, M. V., Monodisperse SnSb
4 Nanocrystals for Li-Ion and Na-Ion Battery Anodes: Synergy and Dissonance between Sn and Sb.
5
Nanoscale 2015, 7, 455-459.
6
7 (9) Darwiche, A.; Toiron, M.; Sougrati, M. T.; Fraisse, B.; Stievano, L.; Monconduit, L., Performance
8 and Mechanism of FeSb2 as Negative Electrode for Na-Ion Batteries. J. Power Sources 2015, 280,
9 588-592.
10
11 (10) Qian, J.; Wu, X.; Cao, Y.; Ai, X.; Yang, H., High Capacity and Rate Capability of Amorphous
12 Phosphorus for Sodium Ion Batteries. Angew.Chem. 2013, 125, 4731-4734.
13 (11) Zheng, Y.; Zhou, T.; Zhang, C.; Mao, J.; Liu, H.; Guo, Z., Boosted Charge Transfer in SnS/SnO2
14 Heterostructures: Toward High Rate Capability for Sodium-Ion Batteries. Angew. Chem. Int. Ed. 2016,
15
16 55, 3408-3413.
17 (12) Lu, Y.; Zhang, N.; Zhao, Q.; Liang, J.; Chen, J., Micro-Nanostructured CuO/C Spheres as
18 High-Performance Anode Materials for Na-Ion Batteries. Nanoscale 2015, 7, 2770-2776.
19 (13) Rahman, M. M.; Sultana, I.; Chen, Z.; Srikanth, M.; Li, L. H.; Dai, X. J.; Chen, Y., Ex Situ
20
21 Electrochemical Sodiation/Desodiation Observation of Co3O4 Anchored Carbon Nanotubes: A High
22 Performance Sodium-Ion Battery Anode Produced by Pulsed Plasma in a Liquid. Nanoscale 2015, 7,
23 13088-13095.
24 (14) Choi, S. H.; You, N. K.; Lee, J. K.; Kang, Y. C., 3D MoS2-Graphene Microspheres Consisting of
25
26 Multiple Nanospheres with Superior Sodium Ion Storage Properties. Adv. Funct. Mater. 2015, 25,
27 1780-1788.
28 (15) Hou, H.; Jing, M.; Huang, Z.; Yang, Y.; Zhang, Y.; Chen, J.; Wu, Z.; Ji, X., One-Dimensional
29
Rod-Like Sb2S3-Based Anode for High-Performance Sodium-Ion Batteries. ACS Appl. Mat. Interfaces
30
31 2015, 7, 19362-19369.
32 (16) Wang, J.; Liu, J.; Yang, H.; Chao, D.; Yan, J.; Savilov, S. V.; Lin, J.; Shen, Z. X., MoS2
33 Nanosheets Decorated Ni3S2@ MoS2 Coaxial Nanofibers: Constructing an Ideal Heterostructure for
34
Enhanced Na-Ion Storage. Nano Energy 2016, 20, 1-10.
35
36 (17) Su, D.; Dou, S.; Wang, G., Ultrathin MoS2 Nanosheets as Anode Materials for Sodium-Ion
37 Batteries with Superior Performance. Adv. Energy Mater. 2015, 5, 1401205.
38 (18) Choi, S. H.; Kang, Y. C., Synergetic Effect of Yolk-Shell Structure and Uniform Mixing of
39
SnS-MoS2 Nanocrystals for Improved Na-Ion Storage Capabilities. ACS Appl. Mat. Interfaces 2015, 7,
40
41 24694-24702.
42 (19) Wang, Y. X.; Chou, S. L.; Wexler, D.; Liu, H. K.; Dou, S. X., High-Performance Sodium-Ion
43 Batteries and Sodium-Ion Pseudocapacitors Based on MoS2/Graphene Composites. Chem. -Eur. J.
44
2014, 20, 9607-9612.
45
46 (20) Hu, Z.; Wang, L.; Zhang, K.; Wang, J.; Cheng, F.; Tao, Z.; Chen, J., MoS2 Nanoflowers with
47 Expanded Interlayers as High-Performance Anodes for Sodium-Ion Batteries. Angew.Chem. 2014, 126,
48 13008-13012.
49
(21) Zhang, S.; Yu, X.; Yu, H.; Chen, Y.; Gao, P.; Li, C.; Zhu, C., Growth of Ultrathin MoS2
50
51 Nanosheets with Expanded Spacing of (002) Plane on Carbon Nanotubes for High-Performance
52 Sodium-Ion Battery Anodes. ACS Appl. Mat. Interfaces 2014, 6, 21880-21885.
53 (22) Xie, X.; Makaryan, T.; Zhao, M.; Van Aken, K. L.; Gogotsi, Y.; Wang, G., MoS2 Nanosheets
54
Vertically Aligned on Carbon Paper: A Freestanding Electrode for Highly Reversible Sodium-Ion
55
56 Batteries. Adv. Energy Mater. 2015, 6, 1502161.
57 (23) Sahu, T. S.; Mitra, S., Exfoliated MoS2 Sheets and Reduced Graphene Oxide-An Excellent and
58
59
60
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Page 13 of 25 ACS Applied Materials & Interfaces

1
2
3 Fast Anode for Sodium-Ion Battery. Sci. Rep. 2015, 5, 12571.
4 (24) Wang, J.; Luo, C.; Gao, T.; Langrock, A.; Mignerey, A. C.; Wang, C., An Advanced MoS2/Carbon
5
Anode for High-Performance Sodium-Ion Batteries. Small 2015, 11, 473-481.
6
7 (25) Xiong, X.; Luo, W.; Hu, X.; Chen, C.; Qie, L.; Hou, D.; Huang, Y., Flexible Membranes of
8 MoS2/C Nanofibers by Electrospinning as Binder-Free Anodes for High-Performance Sodium-Ion
9 Batteries. Sci. Rep. 2015, 5, 9254.
10
11 (26) Chen, C.; Xu, H.; Zhou, T.; Guo, Z.; Chen, L.; Yan, M.; Mai, L.; Hu, P.; Cheng, S.; Huang, Y.,
12 Integrated Intercalation-Based and Interfacial Sodium Storage in Graphene-Wrapped Porous Li4Ti5O12
13 Nanofibers Composite Aerogel. Adv. Energy Mater. 2016, 6, 1600322.
14 (27) Wang, K. X.; Li, X. H.; Chen, J. S., Surface and Interface Engineering of Electrode Materials for
15
16 Lithium-Ion Batteries. Adv. Mater. 2015, 27, 527-545.
17 (28) Wang, L.; Wang, D.; Dong, Z.; Zhang, F.; Jin, J., Interface Chemistry Engineering for Stable
18 Cycling of Reduced GO/SnO2 Nanocomposites for Lithium Ion Battery. Nano Lett. 2013, 13,
19 1711-1716.
20
21 (29) Lahiri, A.; Olschewski, M.; Gustus, R.; Borisenko, N.; Endres, F., Surface Modification of
22 Battery Electrodes Via Electroless Deposition with Improved Performance for Na-Ion Batteries. Phys.
23 Chem. Chem. Phys. 2016, 18, 14782-14786.
24 (30) Liu, Y.; Fang, X.; Ge, M.; Rong, J.; Shen, C.; Zhang, A.; Enaya, H. A.; Zhou, C., SnO2 Coated
25
26 Carbon Cloth with Surface Modification as Na-Ion Battery Anode. Nano Energy 2015, 16, 399-407.
27 (31) Li, C.; Zhang, H.; Cheng, C., CdS/CdSe Co-Sensitized 3D SnO2/TiO2 Sea Urchin-Like Nanotube
28 Arrays as an Efficient Photoanode for Photoelectrochemical Hydrogen Generation. RSC Adv. 2016, 6,
29
37407-37411.
30
31 (32) Zhang, H.; Zhang, D.; Qin, X.; Cheng, C., Three-Dimensional CdS-Sensitized Sea Urchin Like
32 TiO2-Ordered Arrays as Efficient Photoelectrochemical Anodes. J. Phys. Chem. C 2015, 119,
33 27875-27881.
34
(33) Li, C.; Zhu, X.; Zhang, H.; Zhu, Z.; Liu, B.; Cheng, C., 3D ZnO/Au/CdS Sandwich Structured
35
36 Inverse Opal as Photoelectrochemical Anode with Improved Performance. Adv. Mater. Interfaces 2015,
37 2, 1500428.
38 (34) Ren, W.; Zhang, H.; Kong, D.; Liu, B.; Yang, Y.; Cheng, C., A Three-Dimensional Hierarchical
39
TiO2 Urchin as a Photoelectrochemical Anode with Omnidirectional Anti-Reflectance Properties. Phys.
40
41 Chem. Chem. Phys. 2014, 16, 22953-22957.
42 (35) Guan, C.; Wang, J., Recent Development of Advanced Electrode Materials by Atomic Layer
43 Deposition for Electrochemical Energy Storage. Adv. Sci. 2016, 3, 1500405.
44
(36) Guan, C.; Qian, X.; Wang, X.; Cao, Y.; Zhang, Q.; Li, A.; Wang, J., Atomic Layer Deposition of
45
46 Co3O4 on Carbon Nanotubes/Carbon Cloth for High-Capacitance and Ultrastable Supercapacitor
47 Electrode. Nanotechnology 2015, 26, 094001.
48 (37) Chen, C.; Wen, Y.; Hu, X.; Ji, X.; Yan, M.; Mai, L.; Hu, P.; Shan, B.; Huang, Y., Na+ Intercalation
49
Pseudocapacitance in Graphene-Coupled Titanium Oxide Enabling Ultra-Fast Sodium Storage and
50
51 Long-Term Cycling. Nat. Commun. 2015, 6, 6929.
52 (38) Zhang, H.; Ren, W.; Cheng, C., Three-Dimensional SnO2@ TiO2 Double-Shell Nanotubes on
53 Carbon Cloth as a Flexible Anode for Lithium-Ion Batteries. Nanotechnology 2015, 26, 274002.
54
(39) Huang, G.; Chen, T.; Chen, W.; Wang, Z.; Chang, K.; Ma, L.; Huang, F.; Chen, D.; Lee, J. Y.,
55
56 Graphene-Like MoS2/Graphene Composites: Cationic Surfactant-Assisted Hydrothermal Synthesis and
57 Electrochemical Reversible Storage of Lithium. Small 2013, 9, 3693-3703.
58
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3 (40) Yang, T.; Chen, Y.; Qu, B.; Mei, L.; Lei, D.; Zhang, H.; Li, Q.; Wang, T., Construction of 3D
4 Flower-Like MoS2 Spheres with Nanosheets as Anode Materials for High-Performance Lithium Ion
5
Batteries. Electrochim. Acta 2014, 115, 165-169.
6
7 (41) Zhou, J.; Qin, J.; Zhang, X.; Shi, C.; Liu, E.; Li, J.; Zhao, N.; He, C., 2D Space-Confined
8 Synthesis of Few-Layer MoS2 Anchored on Carbon Nanosheet for Lithium-Ion Battery Anode. ACS
9 Nano 2015, 9, 3837-3848.
10
11 (42) Zhang, J.; Yu, H.; Chen, W.; Tian, X.; Liu, D.; Cheng, M.; Xie, G.; Yang, W.; Yang, R.; Bai, X.,
12 Scalable Growth of High-Quality Polycrystalline MoS2 Monolayers on SiO2 with Tunable Grain Sizes.
13 ACS Nano 2014, 8, 6024-6030.
14 (43) Yuan, Y.-J.; Ye, Z.-J.; Lu, H.-W.; Hu, B.; Li, Y.-H.; Chen, D.-Q.; Zhong, J.-S.; Yu, Z.-T.; Zou,
15
16 Z.-G., Constructing Anatase TiO2 Nanosheets with Exposed (001) Facets/Layered MoS2
17 Two-Dimensional Nanojunctions for Enhanced Solar Hydrogen Generation. ACS Catal. 2015, 6,
18 532-541.
19 (44) Ho, W.; Yu, J. C.; Lin, J.; Yu, J.; Li, P., Preparation and Photocatalytic Behavior of MoS2 and
20
21 WS2 Nanocluster Sensitized TiO2. Langmuir 2004, 20, 5865-5869.
22 (45) Liu, C.; Wang, L.; Tang, Y.; Luo, S.; Liu, Y.; Zhang, S.; Zeng, Y.; Xu, Y., Vertical Single or
23 Few-Layer MoS2 Nanosheets Rooting into TiO2 Nanofibers for Highly Efficient Photocatalytic
24
Hydrogen Evolution. Appl. Catal. B-Environ. 2015, 164, 1-9.
25
26 (46) David, L.; Bhandavat, R.; Singh, G., MoS2/Graphene Composite Paper for Sodium-Ion Battery
27 Electrodes. ACS Nano 2014, 8, 1759-1770.
28 (47) Park, J.; Kim, J.-S.; Park, J.-W.; Nam, T.-H.; Kim, K.-W.; Ahn, J.-H.; Wang, G.; Ahn, H.-J.,
29
Discharge Mechanism of MoS2 for Sodium Ion Battery: Electrochemical Measurements and
30
31 Characterization. Electrochim. Acta 2013, 92, 427-432.
32 (48) Liao, J.-Y.; De Luna, B.; Manthiram, A., TiO2-B Nanowire Arrays Coated with Layered MoS2
33 Nanosheets for Lithium and Sodium Storage. J. Mater. Chem. A 2016, 4, 801-806.
34
(49) Ahmed, B.; Anjum, D. H.; Hedhili, M. N.; Alshareef, H. N., Mechanistic Insight into the Stability
35
36 of HfO2-Coated MoS2 Nanosheet Anodes for Sodium Ion Batteries. Small 2015, 11, 4341-4350.
37 (50) Zhu, Y.; Xu, Y.; Liu, Y.; Luo, C.; Wang, C., Comparison of Electrochemical Performances of
38 Olivine NaFePO4 in Sodium-Ion Batteries and Olivine LiFePO4 in Lithium-Ion Batteries. Nanoscale
39
2013, 5, 780-787.
40
41 (51) Ko, Y. N.; Park, S. B.; Jung, K. Y.; Kang, Y. C., One-Pot Facile Synthesis of Ant-Cave-Structured
42 Metal Oxide-Carbon Microballs by Continuous Process for Use as Anode Materials in Li-Ion Batteries.
43 Nano Lett. 2013, 13, 5462-5466.
44
(52) Zhang, S.; Xu, K.; Jow, T., Electrochemical Impedance Study on the Low Temperature of Li-Ion
45
46 Batteries. Electrochim. Acta 2004, 49, 1057-1061.
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6 Scheme 1 Schematic diagram for the description of Na+ insertion and e- diffusion processes.
7 Figure 1 SEM images of (a, b) 3D MoS2 nanosheets; (c) MoS2 nanosheets coated with 2 nm TiO2 ;
8 (d) XRD patterns of MoS2 and TiO2 coated MoS2 nanosheets.
9 Figure 2 (a) TEM image, (b) HRTEM image and (c) SAED patterns of MoS2 nanosheets; (d)
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11 HRTEM images of MoS2-2 nm TiO2.
12 Figure 3 High-resolution XPS spectra of the (a) Mo 3d peak, (b) S 2p peak, (c) Ti 2p peak and (d)
13 O 1s peak, respectively.
14 Figure 4 (a) the first cycle and (b) the second cycle of CV curves of MoS2, MoS2-0.5 nm TiO2,
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16 MoS2-1 nm TiO2 and MoS2-2 nm TiO2 electrodes measured at a scanning rate of 0.2 mV s-1.
17 Figure 5 (a) Charge–discharge profiles of initial cycles at 200 mA g-1; (b) Cycling performances
18 at 200 mA g-1; (c) The rate of electrode at various current densities of 50, 100, 200, 400 and 800
19 mA g-1, respectively; (d) Cycling performances at 500 mA g-1 for the electrodes of MoS2,
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21 MoS2-0.5 nm TiO2, MoS2-1 nm TiO2 and MoS2-2 nm TiO2.
22 Figure 6 SEM images of (a) 3D MoS2 nanosheets; (b) coated with 0.5 nm TiO2; (c) coated with 1
23 nm TiO2; (d) coated with 2 nm TiO2; after 150 cycles at a current density of 200 mA g-1.
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Figure 7 XRD patterns of MoS2 nanosheets (I) and coated with 0.5 nm (II), 1 nm (III) and 2 nm
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26 (IV) TiO2 after 150 cycles at a current density of 200 mA g-1.
27 Figure 8 Nyquist plots of MoS2-0.5 nm TiO2 and MoS2-1 nm TiO2 electrodes: (a) after 50 cycles
28 at 200 mA g-1 and (b) after 100 cycles at 500 mA g-1. ) Linear fits in low frequency region of the
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Scheme 1 Schematic diagram for the description of Na+ insertion and e- diffusion
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