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Advanced Materials Research Vol. 531 (2012) pp 471-477 Online available since 2012/Jun/04 at www.scientific.

net (2012) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.531.471

Synthesis of MoS2/C Submicrosphere by PVP-Assisted Hydrothermal Method for Lithium Ion Battery Hao Luo *1, a, Lingzhi Zhang *1,b and Lu Yue 1,c
1

GuangZhou Institute of Energy Conversion, Chinese Academy of Sciences, GuangZhou 510640, PR China luohao@ms.giec.ac.cn, b lzzhang@ms.giec.ac.cn, c yuelu@ms.giec.ac.cn

Keywords: Molybdenum disulfide; submicrosphere; anode; lithium ion battery

Abstract. Molybdenum disulfide/carbon (MoS2/C) submicrosphere was synthesized through a PVP-assisted hydrothermal reaction of sodium molybdate and thiourea (CS(NH2)2), The structure and morphology of MoS2 composites were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM). The lithium intercalation/de-intercalation behavior of as-prepared MoS2 submicrosphere electrode was also investigated. It was found that the MoS2 submicrosphere electrode exhibited the best electrochemical performance, retaining a specific capacity of 575mAh/g after 100 cycles, with higher first charge capacity (1037 mAh/g), which was better than those of the MoS2 prepared without PVP. Introduction Molybdenum disulfide (MoS2) is semiconductor material which exhibits a layered structure consisting of covalently bound SMoS trilayers, separated by a relatively large van der Waals gap. The electronic structure is such that band-edge excitation corresponds largely to a metal centered dd transition [1, 2]. Due to these features, the MoS2 compounds show numerous properties, such as catalysis, electrocatalysis, solid lubrication, electrochemical intercalation etc. The weak interlayer interaction allows foreign ions or molecules to be introduced between the layers through intercalation. Thus, MoS2 could be developed as an intercalation host to form a promising electrode material in high energy density batteries [38]. The electrochemical performance of transition metal disulfides, including MoS2, for Li-ion batteries has been investigated, and the results showed that the particle size and morphology of materials have a great influence on their electrochemical properties [3, 4, 9, 10]. Since lithium ions can intercalate into small holes/channels, it may be imagined that MoS2 nanostructured materials with plenty of defects can deliver even higher lithium intercalation capacity. There are many kinds of MoS2 micro/nano materials with various morphologies, such as inorganic fullerene-like nanopaticles [11], single-layer [12,13], nanotubes [14], nanorods[15], nanowries [16], nano/microflowers [17, 18], nano/microribbons [19], nano/micrometer spheres [20], porous spheres [21], nano/micrometer hollow spheres [22, 23], fiber [24], hollow-cage fullerenelike nanoparticles [25], fibrous floccus [25], spherical nanovesicles [25], nanoflakes [9, 10, 26, 27],etc. Among these morphologies above, bulk MoS2 electrodes exhibited decreased charge capacity from 800 to 226 mAh/g after 50 cycles [13]. On the other hand, restacked MoS2, prepared from commercially available MoS2, showed the first charge (Li+ extraction) capacity of 800 mAh/g and maintained a capacity of 750 mAh/g after 20 cycles at the current density of 50 mA/g. Feng et al. reported that MoS2 nanoflakes can reversibly store lithium with first capacity of 1175 mAh/g [9], and capacity remains 840 mAh/g after 20 cycles. Li et al. reported that 3D flowerlike MoS2 was fabricated by hydrothermal synthesis assisted with ionic liquid (IL, [BMIM] [BF4]) [18], their electrochemical lithiation/delithiation reversible capacity and cycling durability greatly decreased. Recently, there have been some reports on MoS2 about improving the capacity via structure modification. For instance, Wang and Li reported that MoS2 layers supported on coaxial carbon nanotubes led to a reversible capacity approaching 400 mAh/g is approximately twice that of bare
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carbon nanotubes under the same condition [28]. Ding et al. reported that MoS2 nanosheets (NSs) on the CNT backbone (CNT@MoS2NSs), prepared by glucose-assisted hydrothermal method, led to a reversible capacity as high as 698 mAh/g can still be retained after 60 discharge/charge cycles [27]. In contrast, the pure MoS2 flakes can only deliver a much lower capacity of 300 mAh/g. Xiao et al. and Chang et al. reported that nanocomposites formed by inserting the lithium ion coordination properties of polyethylene oxide (PEO) into the interlayer spacing of MoS2, led to a reversible capacity of >900 mAh/g at a rate of 50 mA/g [29]. Chen et al. reported that MoS2/C nanocomposites were synthesized by a facile hydrothermal route, which reversible maximal capacity was 1065 mAh/g and the capacity of 1011 mAh/g was retained after 120 cycles [30-32]. Jaephil Cho and co-workers reported that MoS2 nanoplates, interlayer distance of 0.69 nm, which is much larger than its bulk counterpart (0.62 nm), were synthesized by solvent hydrothermal route using Mo(CO)6 , S and xylene in an autoclave. This disordered graphene-like morphology led to a reversible capacity of 700 mAh/g. even at a 50C (53.1 A/g) rate [33]. In this work, we report a simple synthesis method to synthesize submicrosphere MoS2/C composites. The samples prepared can store lithium with a first charge capacity of 1037 mAh/g, and capacity remains 575 mAh/g after 100 cycles, at a rate of 50 mA/g in the voltage range of 0.013.0 V vs. Li/Li+. In addition, the MoS2/C electrode exhibits Columbic efficiency of only 65.38% at the 1st cycle. Moreover, the MoS2/C exhibits good cycling performance as an electrode material. Results and discussion Structural characterization

Fig. 1 XRD patterns of as-synthesized MoS2 samples synthesized by hydrothermal method: (a) sample 3; (b) sample 2; (c) sample 1; (d) sample 5; (e) sample 4 Fig.1 shows XRD patterns of as-synthesized MoS2 samples synthesized at different temperature from 180 to 200 for 24 h. All the reflections can be readily indexed to hexagonal 2H (two-layer hexagonal) MoS2 (JCPDS 37-1492). The XRD patterns of submicrosphere MoS2/PVP composites (Fig.1a-1c), MoS2 nanoflakes [27] (Fig.1e) and submicrosphere MoS2/C composites (Fig.1d) show a typical scan which is the characteristic of poorly crystalline layered disulfides and similar to the scan reported by Wildervanck and Jellinek for MoS2 produced by the decomposition of MoS3 [34, 35]. It exhibited a strong (002) maximum in low angle region and a broad envelope starting approximately at 2 = 30and lasting out to about 2 = 60. This envelope contains the (100), (101), (102), (103), (006), (105), (106), (110), and (008) reflections. Among these reflections, the well-defined maxima are at (100), (103), and (110) reflections. As can be seen from Fig. 1a to 1c, the intensity of the (002) and (004) plane diffraction peaks were increased while increasing the reaction temperature, which indicated the poor-stacked layered structure of MoS2/PVP composites. The weak diffraction peak at

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2 = 28.6 (Fig.1d), which is approximate to the value (2 = 26.3) reported by Chang et al. [32], can be attributed to the (002) plane of amorphous carbon, indicating that PVP was transformed into carbon. Its investigated that the particle size and morphology of materials have a great influence on their electrochemical properties. Well stacked layered structure of MoS2 exhibited good cycling performance [13]. Tian et al [23] have reported the synthesis of MoS2 nanotubes and nanorods by a hydrothermal method at a low temperature (180 ). According to their experimental results, reaction temperature played an important role in the morphology of the products. At 160 oC, only poor crystals were produced with almost no layer structure. Above 200 oC, the MoS2 layers became too thick to form tubes or rods difficultly.

Fig.2 SEM and TEM images of submicrosphere MoS2/PVP and MoS2/C composites: (a) SEM and (d) TEM images of sample 1; (b) SEM and (e) TEM images of sample 2; (c) SEM and (f) TEM images of sample 3; (g) SEM image of sample 5 (MoS2/C). The size and morphology of as-synthesized MoS2 samples prepared at different temperature were observed by SEM and TEM images (Fig.2). As shown in Fig.2, it can be seen that the as-synthesized MoS2 samples are uniform submicrosphere with diameters of 200~400 nm. The results gave the evidences that the surface of sample become rougher while increasing the reaction temperature. After annealing treatment, the surface of sample 5 becomes rougher than sample 3 with particles aggregation. As the anode materials of Li-ion battery, this three-dimensional architecture of MoS2/PVP composites with the rough surface can increase the interfacial areas between the electrolyte/electrode and thus improve lithium ions diffusion. Electrochemical characterization Fig.3 shows the differential curves of the MoS2 nanoplates at a scan rate of 0.5 mV s-1 in the voltage range of 03.0 V. As can be seen, the CV behavior is generally consistent with those reported previously [6, 28, 31, 32]. During the first cycle, two reduction (Li insertion) peaks were observed at 0.62 and 0.42 V, respectively, whereas one pronounced oxidation (Li extraction) peaks were observed at 2.36 V. The reduction peak at 0.62 Vis attributed to the intercalation of lithium ions into the MoS2 lattice which transforms the triangular prism (coordination of Mo by six S atoms) into an octahedral structure [6, 28,]. The second pronounced reduction peak can be ascribed to the reduction of LixMoS2 to Mo metal and Li2S via a conversion reaction. The oxidation peak at 2.32 V was attributed to the formation of MoS2. Fig.4 displays the charge-discharge voltage profiles of the MoS2/C electrode and cycling performances of raw MoS2, MoS2/ PVP composites and MoS2/C composites at a current density of 50 mA g-1. As shown in Fig.4A, in the first discharge process, MoS2/C electrode display two

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inconspicuous potential plateaus at 0.6 and 0.4V which is in accordance with CV behavior of MoS2/C electrode. The inconspicuous potential plateaus of the discharge of MoS2/C electrode was caused by low-dimensional crystallites, more disorder and dispersion in the amorphous carbon of MoS2.The first discharge and charge capacities are 1037 and 678mAh/g, respectively, corresponding to an 65.38% Coloumbic efficiency. As shown in Fig.4B, the charge capacity of MoS2/C electrode is 575mAh/g after 100 cycles, showing capacity retention of 55%. On the other hand, the MoS2/ PVP electrode shows an improved cycling performance compared with the raw MoS2 without PVP coating after 50 cycles. These demonstrate that PVP and C efficiently prevented the initial capacity loss too fast.

Fig.3 Cyclic voltammograms of MoS2/C electrodes at a scan rate of 0.5 mV s-1 in the voltage range of 03.0 V

Fig.4 (A) The charge-discharge curves of MoS2/C composites; (B) Cycling behaviors of raw MoS2, MoS2/ PVP composites and MoS2/C composites. Experimental Materials and equipment The sodium molybdate (Na2MoO42H2O), polyvinyl pyrrolidone (PVP, K30) and thiourea (CS(NH2)2) are analytical pure regents (AR) and purchased and used without further treatments. The electrolyte of 1 M ethylene carbonate (EC, 99.9%)/ diethylene carbonate (DEC, 99.9%) (v/v = 1/1, water content10 ppm) was purchased from Zhangjiagang Guotai-Huarong New Chemical Mterials Co.(China).

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The XRD patterns were recorded by a Holland Philips X'Pert PW3040/60 using Cu (K) radiation (=0.15418 nm) operating at 40 kV and 40 mA with 2 ranging from 10 to 70. The SEM images were taken with Japan Hitachi S-4800 field-emission scanning electron microscope. The TEM images were taken with a JEOL-2010 transmission electron microscope at an accelerating voltage of 200 kV. The coin cells were then galvanostatically charged and discharged using a multi-channel battery test system (Neware BTS-610, China). Cyclic voltammetry (CV) were obtained with a Zennium/IM6 electrochemical workstation (Zahner, Germany). Synthesis of MoS2/C composites In a typical synthesis, 0.36 g (1.5 mmol) of Na2MoO42H2O and 0.69 g (9 mmol) of thiourea were dissolved in 30 ml de-ionized water. After stirring a few minutes, 0.6 g of PVP were added to the above clear solution. Then 12 mol/L HCl was dropped into the solution while being stirred to adjust the pH value to less than 1. The transparent mixture was put into 100 ml Teflon-lined stainless steel autoclave and sealed tightly. The autoclave was maintained at 180, 190, and 200 for 24 h, respectively (MoS2/PVP, sample 1 to 3). After reaction, the autoclave was cooled to room temperature naturally. The black precipitates were collected through centrifugal method, washed with distilled water several times to remove the residue of the reactants, and finally dried at 60 in a vacuum oven for 10 h. As contrast, MoS2 sample (sample 4) was also synthesized according to the above process without any PVP at 200 for 24 h. The MoS2/C composites (sample 5) was prepared by an annealing treatment utilizing as-synthesized MoS2 samples (MoS2/PVP, sample 3) in tube furnace at 700 for 3 h in a stream of argon gas. Characterization of electrochemical properties The coin cells (CR2025) were assembled to test the electrochemical performance of the as-synthesized MoS2 samples (MoS2/C composites, Sample 5), lithium metal served as counter and reference electrodes, a polypropylene film was used as separator, and electrolyte was 1.0M LiPF6 solution in a mixture of EC/DEC (1:1 in volume). The working electrodes were prepared by coating a slurry of active material, carbon black and a polyvinylidene fluoride (PVDF) in a weight ratio of 70:20:10 on a copper foil current collector. After dried at 110 in a vacuum oven for 24 h, the resulting electrodes with an active material were transferred to an Ar-filled glove box to assemble testing cells. The cells were then galvanostatically charged and discharged at a constant current density of 50 mA g-1 in a voltage range of 0.01 and 3.0V (vs. Li/Li+) using a multi-channel battery test system (Neware BTS-610) at 25 . The Capacity of the composites were calculated based on the whole composite as active mass. Cyclic voltammetry (CV) were conducted in the potential range of 0.03.0V versus Li/Li+ at a scan rate of 0.5mVs1 on an electrochemical workstation at 25 . Conclusion MoS2/PVP and MoS2/C submicrosphere have been synthesized through a facile hydrothermal method at low temperature utilizing the raw materials of sodium molybdate, polyvinyl pyrrolidone (PVP) and thiourea (CS(NH2)2), and the structure and morphology of products were characterized by means of XRD, SEM and TEM. The lithium intercalation/de-intercalation behavior of as-prepared MoS2 submicrosphere electrode was also investigated. It was found that the MoS2/C submicrosphere electrode exhibits good cycling performance as an electrode material. The first discharge capacity is 1037mAh/g, and capacity retention after 100 cycles was 55% which was better than those of the MoS2 prepared without PVP (197mAh/g after 100 cycles). Moreover, the MoS2/C exhibited Acknowledgements This work was supported by the National Science Foundation of China (50973112), the Hundred Talents Program of the Chinese Academy of Science (CAS), CAS-Guangdong Collaboration Program (2009B091300025), and Science & Technology Project of Guangzhou (China).

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Synthesis of MoS2/C Submicrosphere by PVP-Assisted Hydrothermal Method for Lithium Ion Battery 10.4028/www.scientific.net/AMR.531.471