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A Salt-Templating Protocol to Realize Few-Layered Ultrasmall MoS2 Nanosheets Inlayed into Carbon Frameworks for Superior Lithium-Ion Batteries Dayong Ren, Yanjie Hu, Hai Bo Jiang, Zongnan Deng, Petr Saha, Hao Jiang, and Chunzhong Li ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.5b01218 • Publication Date (Web): 07 Jan 2016 Downloaded from http://pubs.acs.org on January 13, 2016

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ACS Sustainable Chemistry & Engineering

A Salt-Templating Protocol to Realize Few-Layered Ultrasmall MoS2 Nanosheets Inlayed into Carbon Frameworks for Superior Lithium-Ion Batteries Dayong Ren,† Yanjie Hu,† Haibo Jiang,† Zongnan Deng,† Saha Petr,‡ Hao Jiang*† and Chunzhong Li*† †

Key Laboratory for Ultraﬁne Materials of Ministry of Education, School of Materials

Science and Engineering, East China University of Science and Technology, Shanghai 200237, China ‡

Centre of Polymer Systems, University Institute, Tomas Bata University in Zlin, Trida T.

Bati 5678, 760 01 Zlin, Czech Republic Corresponding author: Tel.: +86-21-64250949, Fax: +86-21-64250624 E-mail: [email protected] (Prof. H. Jiang) and [email protected] (Prof. C. Z. Li)

ACS Paragon Plus Environment


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ABSTRACT The preparation of few-layered ultrasmall MoS2 nanosheets inlayed into carbon frameworks is challenging to date. Herein, we realize the synthesis of such meaningful nanohybrids (labelled as MoS2/CFs hybrids) by a simple salt-templating protocol, where NaCl particles are chosen as a sacrificial template to grow MoS2 crystals on the surface during the glucose carbonization, which meanwhile effectively inhibits their growth and stacking. In regard to electrochemical energy storage and conversion, the resulting MoS2/CFs hybrids are beneficial for providing substantial and accessible electroactive sites as well as rapid electrons/ions transfer. The present hybrids, when applied as lithium-ion batteries anode materials, exhibit a remarkably enhanced reversible specific capacity as high as 1083.5 mAh g-1 at 200 mA g-1 with fast charge/discharge capability (465.4 mAh g-1 at 6400 mA g-1), which is much higher than the exfoliated MoS2 nanosheets (only 97.6 mAh g-1 at 6400 mA g-1) and the commercial graphite. More impressively, our MoS2/CFs hybrids simultaneously possess a superior cycle life with negligible capacity loss after 400 cycles at 1600 mA g-1. In addition to the excellent lithium ion storage, our MoS2/CFs hybrids may concurrently exhibit some intriguing properties for applications in other energy-related fields. KEYWORD Few-layered MoS2, carbon frameworks, nanohybrids, salt-templating, lithium-ion battery


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INTRODUCTION To speed up the lithium-ion batteries (LIBs) applications in electric vehicles and hybrid electric vehicles, a key lies in exploiting novel electrode materials with high energy/power densities and long cycle life to replace the commercial graphite anode (theoretical value: 372 mAh g-1).1-5 Two dimensional transition metal dichalcogenides (TMDs) attract tremendous interests in recent years due to their fascinating physical and chemical properties caused by their graphene-like structure.6-10 As a representative of TMDs, molybdenum disulfide (MoS2) has been extensively applied as functional materials in energy-related fields. It is well-known that MoS2 consists of a hexagonally packed layer of Mo atoms sandwiched between two layers of S atoms and the triple layers are stacked and held together by van der Waals interactions.11 The weak van der Waals interactions could provide a convenient environment between the adjacent interlayers for reversibly inserting and extracting abundant lithium ions.6 Meanwhile, MoS2 can also be converted into the metal Mo and Li2S with additional Lithium storage capacity. Therefore, the design and preparation around MoS2 are now hotspot today for achieving satisfying electrochemical performance. However, the single-layered and/or few-layered MoS2 nanosheets are very easy to stack and restack even in a dry process,12,13 plus their inherent poor electrical conductivity,14 greatly inhibiting their potential for application in LIBs. To get over the aforementioned obstacles, we should find a way to hybridize few-layered MoS2 nanosheets with high conductive carbon, which requires the few-layered MoS2 is well-maintained and its conductivity is also remarkably improved. Thus far, two protocols have been developed to obtain such hybrids. One is to grow few-layered MoS2 on the surface of carbonaceous materials,15-17 e.g. carbon nanotubes,18,19 graphene.20,21



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However, a serious structural collapse, aggregation, detachment of the MoS2 nanosheets will inevitably happen after a long repeated lithium insertion/extraction process. Another is to synthesize MoS2-C embedded structure, which has been deemed as an effective strategy. In this respect, several works are reported with enhanced electrochemical properties.22-24 Nevertheless, most of preparations are complex and expensive, sometimes involve sophisticated technique, which is hard to scale-up. Furthermore, if we can further reduce the size of the incorporated few-layered MoS2 nanosheets in carbon, a higher lithium storage capacity will be achieved. Herein, we demonstrate the few-layered ultrasmall MoS2 nanosheets inlayed into carbon frameworks (labelled as MoS2/CFs hybrids) by a simple and scalable salt-templating protocol, which can provide substantial and accessible electroactive sites as well as rapid electrons/ions transfer. When applied as lithium-ion batteries anode materials, the as-synthesized MoS2/CFs hybrids exhibit a remarkably enhanced reversible lithium storage capacity with fast charge/discharge capability and long cycle life. In addition, we believe that such an impressive structure will own huge potential for applications in other energy-related devices.

EXPERIMENTAL SECTION Synthesis of the MoS2/CFs hybrids: A typical synthesis of the MoS2/CFs hybrids is as followed. 0.7 g of ammonium thiomolybdate ((NH4)2MoS4) and 5 g of NaCl were ultrasonically dispersed in the glucose solution (0.125 g/40 mL deionized water). And then, the homogeneously solution was heated to 100 °C under intensively stirring until the complete evaporation of water. The as-obtained powder was annealed at 850 °C for 2h in flowing argon. After washing several times by deionized water, the resulting products are


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obtained by additional dry in a vacuum oven at 80 °C for 12 h. Synthesis of exfoliated MoS2 nanosheets: In a typical synthesis, 1.6 g of sodium oleate, 1.0 g of Na2MoO4 and 0.9 g of thiourea were dissolved in the mixed solution containing 15 mL of water, 15 mL of ethanol and 2 mL of oleic acid. And then, the pH of mixture was adjusted to ~ 1.0 by the use of 2.0 M HCl aqueous solution. The mixture was then put into a 50 mL Teflon-lined stainless steel autoclave. After sealed, the autoclave was transferred in an electronic oven at 180 °C for 24 h, and then naturally cooled down to room temperature. After that, the precipitates were collected by filtration, washed with distilled water and absolute ethanol for several times, and dried at 60 °C. The finally product is donated as the fresh exfoliated MoS2 nanosheets. The fresh exfoliated MoS2 nanosheets were annealed at 850 °C for 2 h in flowing argon. The resulting product is donated as the exfoliated MoS2 nanosheets. Characterization. The structure and morphology of as-prepared products were characterized with X-ray power diffract-meter (XRD, Rigaku D/Max2550, Cu Kα radiation) at a scan rate of 1° min-1, scanning electron microscopy (FESEM; Hitachi, S-4800), and transmission electron microscopy (TEM; JEOL, JEM-2100F) operated at 200 kV with an X-ray energy dispersive spectrometer (EDS). Thermogravimetric analysis (NETZSCH STA409PC) was carried out with a heating rate of 10 °C min–1 under flowing air. Electrochemical Measurements. Electrochemical measurements were performed using coin-type 2016 cells. The working electrode was prepared by mixing the as-obtained active materials, carbon black (Super-P-Li), and poly(vinyl difluoride) (PVDF) at a weight ratio of 80 : 10 : 10, and then pasted on pure Cu foil. Pure lithium foil was used as a counter electrode, and the separator was a polypropylene membrane (Celgard 2400). The electrolyte consists of



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a solution of 1 M LiPF6 in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 in volume). The cells were assembled in an argon-filled glove box. The charge and discharge measurements were carried out on a LAND-CT2001C test system at different current densities. Cyclic voltammogram experiment was performed on an Autolab PGSTAT302N electrochemical workstation at scan rates of 0.2 mV s-1. RESULTS AND DISCUSSION

Scheme 1. Schematic illustration for the fabrication of the MoS2/CFs hybrids using NaCl crystals as a template

Scheme 1 illustrated the representative fabrication process of the MoS2/CFs hybrids. Here, the NaCl crystals, as a sacrifice template, first mix with (NH4)2MoS4-C6H12O6 aqueous solution, which is heated to 100 °C with a vigorous stirring till the moisture is completely evaporated. Then NaCl crystals are formed, decorating with (NH4)2MoS4-C6H12O6 precursor. Upon annealing at 850 °C for 2h in Ar, MoS2 crystals grow on the surface of NaCl crystals with the glucose carbonization. After the subsequent rinsing, the as-designed MoS2/CFs hybrids are obtained, which show a typical laminated structure with a smooth surface, as shown in Figure 1a.


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Figure 1. (a) SEM image, (b) high-magnification and (c) high-resolution TEM images, and (d) TEM-EDS mapping of the as-synthesized MoS2/CFs hybrids

The microstructure of the MoS2/CFs hybrids has been further investigated by high-magnification and high-resolution TEM. Considering that the MoS2 crystals and carbon frameworks are simultaneously formed when annealed the (NH4)2MoS4-C6H12O6 matrix in inert atmosphere, the growth and stacking of MoS2 crystals are effectively inhibited. Therefore, we can observe that the few-layered ultrasmall MoS2 nanosheets are well-dispersed and well-inlayed into glucose-calcinated carbon frameworks with a size of ~ 4 nm, as shown in Figure 1b. Moreover, we can also find that some of MoS2 nanosheets are lying flat on the surface of carbon frameworks (yellow circles in Figure 1c), giving a lattice spacing of 0.27 nm, i.e. the MoS2 (101) plane. The elemental distribution of a MoS2/CFs hybrid is further investigated by TEM-EDS mapping, as shown in Figure 1d and Figure S1, showing a uniform distribution of all the Mo, S and C elements in the observed scope. This



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result further examines the formation of the as-synthesized MoS2/CFs hybrids.

Figure 2. XRD pattern and Raman spectra of the MoS2/CFs hybrids.

Figure 2a shows the X-ray diffraction (XRD) pattern of the as-obtained MoS2/CFs hybrids. All the peaks can be attributed to the hexagonal MoS2 crystal faces (JCPDS No.: 37-1492). It is noted that the (002) peak of MoS2 crystals usually centered at 14° disappears, directly indicating the formation of few-layered MoS2 nanosheets for the as-synthesized MoS2/CFs hybrids,25 which is in good agreement with the aforementioned TEM results. It is well-accepted that Raman spectroscopy can identify the number of layers in few-layer MoS2 crystals based on the value of frequency difference (∆k).26 Therefore, we provide the Raman spectroscopy information of both MoS2 and carbon related part. The ∆k is about 24.8 cm-1, indicating the MoS2 crystals in our hybrids are composed of less than four-layered nanosheets. As for the carbon-related part in Figure 2b, the disordered carbon peak (D band) and the ordered graphitic carbon peak (G band) are observed at 1359 and 1587 cm-1 with ID/IG intensity ratio of ~ 0.93, implying a relatively high graphitization, which will boost the electrical conductivity. Furthermore, the MoS2/CFs also show a relatively high BET surface


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area of 60.8 m2 g-1 with pore volume of 0.27 cm3 g-1 compared to the exfoliated MoS2 nanosheets (17 m2 g-1), as shown in Figure S2. Such few-layered ultrasmall MoS2 nanosheets are beneficial for providing sufficient and accessible electroactive sites, and meanwhile shortening the diffusion paths of ions, resulting in high energy/power densities in combination with the high-quality carbon frameworks.

Figure 3. (a) CV curves at a scan rate of 0.2 mV s-1 and (b) charge/discharge curves at a current density of 200 mA g-1 for the initial 3 cycles of the MoS2/CFs hybrids, (c) rate capabilities of the MoS2/CFs hybrids and exfoliated MoS2, (d) cycling behavior and Columbic efficiency of the MoS2/CFs hybrids and exfoliated MoS2 at a current density of 1600 mA g-1.

Normally, it is indispensable to optimize the as-synthesized MoS2/CFs hybrids structure for maximizing their lithium ion storage. Herein, we find that it is very convenient to control



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MoS2 content just by changing the added glucose quantity. An appropriate MoS2 content should be given. This is because too high a content of MoS2 will lead to the formation of larger MoS2 nanosheets and the stacking to some extent (Figure S3). We further evaluate their electrochemical performances of the as-synthesized MoS2/CFs hybrids with different MoS2 content by assembling them into popular coin-type 2016 half-cells, respectively. The specific results are shown in Figure S4, showing that the MoS2/CFs hybrids with 74% MoS2 content possess a highest charge/discharge capacity at different current densities. In the subsequent discussion, we choose the optimized MoS2/CFs hybrids to further evaluate their electrochemical performance. The first three cyclic voltammetry (CV) curves of the MoS2/CFs hybrids at 0.2 mV s-1 over a voltage range of 0.01 and 3.0 V are shown in Figure 3a. In the first cathodic scan, two obviously reduction peaks at ca. 1.04 and 0.44 V can be observed, corresponding to the reversible phase transitions of partially lithiated LixMoS2 and conversion reaction process: LixMoS2 + (4-x)Li+ + (4-x)e- → Mo + 2Li2S.27 The weak peak at 1.49 V can be attributed to the reduction reaction of the oxygen-containing functional groups from carbon frameworks.28 In the reverse anodic scan, a weak peak at 1.72 V can be attributed to the incomplete oxidation of Mo metal. The broad peak at 2.30 V is assigned to the delithiation of Li2S (Li2S → S + 2Li+ + 2e-). In the subsequent cathodic scan, three new reduction peaks at around 1.92, 1.10, and 0.40 V emerged. Accordingly, the reduction peak at 1.92 V is indicative of the formation of Li2S.29 The other two reduction peaks at 1.10 V and 0.40 V are attributed to the association of association of Li with Mo.30 Figure 3b shows the initial three charge and discharge curves of the MoS2/CFs hybrids measured at a current density of 200 mAg-1 between 0.01 and 3.0 V. The MoS2/CFs hybrids show a first discharge


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capacity of 1496.2 mAh g-1 and charge capacity of 1130.7 mAh g-1, with a high initial Columbic efficiency of 75.5%. In the next discharge and charge processes, the discharge and charge capacity maintained 1153.8 mAh g-1 and 1090.0 mAh g-1, with a Columbic efficiency of over 94.5%.

Figure 4. Electrochemical impedance spectra of the MoS2/CFs hybrids before and after cycles, and the exfoliated MoS2 before cycle.

Figure 3c shows the rate capabilities of the MoS2/CFs hybrids. As a control, the exfoliated MoS2 nanosheets are also prepared and evaluated (Figure S5). It can be seen that our hybrids exhibit prominent rate capability, delivering an average discharge capacity of 1083.5 mAh g-1 at a current density of 200 mA g-1, which is higher than the exfoliated MoS2 nanosheets (887.6 mAh g-1). Even at a rate as high as 6400 mA g-1, a capacity of around 465.5 mAh g-1 is still maintained, remarkably higher than the exfoliated MoS2 nanosheets (only 97.6 mAh g-1 at 6400 mA g-1). After rate testing for 5 cycles at 6400 mA g-1, the discharge capacity of 957.3 mAh g-1 can be regained when the test current back to 200 mA g-1. Such high lithium storage capacity of our MoS2/CFs hybrids is also superior to most of the reported MoS2/C



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hybrids32-36 (Table S1), such as MoS2/polyaniline nanowire,35 MoS2 coated on graphene networks,19 and hierarchical MoSx/CNT.36 More importantly, our hybrids also possess an impressive cycling stability. As shown in Figure 4d. The reversible capacity can remain ~ 630 mAh g-1 at 1600 mA g-1 after 10 cycles, and keep no obvious fading even after 400 cycles. As for the exfoliated MoS2 nanosheets, they exhibit sharp capacity decay at the same testing condition (51.8% retention after 100 cycles). These favorable electrochemical properties are mainly due to the unique hierarchical nanostructure. (1) The carbon frameworks sever as the spatial isolation matrix which not only can effectively avoid the restacking of MoS2 nanosheets, but also can accelerate the ions/electrons transport. (2) Few-layered ultrasmall MoS2 nanosheets provide substantial and accessible electrochemical active sites, contributing a higher specific capacity. (3) The MoS2 nanosheets are well-dispersed and well-inlayed into amorphous carbon frameworks, alleviating the change of structural stress during the repeated charge/discharge process. Hence, a satisfied cycle life is achieved. These advantages can be verified by the electrochemical impedance spectra (EIS) analysis. As shown in Figure 4, the MoS2/CFs hybrids demonstrate a much lower resistance (74.3 Ω) than exfoliated MoS2 nanosheets (127.8 Ω). The Nyquist plots of MoS2/CFs hybrids after 400 cycles are also measured, which are almost overlapped with those before cycles, suggesting a high structural integrity. CONCLUSIONS In conclusion, we demonstrate the synthesis of few-layered ultrasmall MoS2 nanosheets inlayed into carbon frameworks hybrids by a simple salt-templating protocol. In such protocol, NaCl particles are chosen as sacrificial template and growth surface for growing MoS2


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crystals during the glucose carbonization, and hence effectively inhibiting their growth and stacking. The resulting MoS2/CFs hybrids provide substantial and accessible electroactive sites as well as rapid electrons/ions transfer. As lithium-ion batteries anode materials, they exhibit a remarkably enhanced reversible specific capacity as high as 1083.5 mAh g-1 at 200 mA g-1, fast charge/discharge capability (465.4 mAh g-1 at 6400 mA g-1) and a long cycle life with negligible capacity loss after 400 cycles at 1600 mA g-1. The present work is meaningful not only for the adopted simple synthesis protocol, but also the realization of few-layered ultrasmall MoS2 nanosheets inlayed into carbon frameworks. Except the high lithium storage capacity, we believe that the impressive MoS2/CFs hybrids may have some other intriguing properties for applications in supercapacitor, hydrogen production, and so forth. ASSOCIATED CONTENT Supporting Information. Figure S1-S5. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (Prof. H. Jiang) [email protected] (Prof. C. Z. Li), Tel: +86-21-64250949, Fax: +86-21-64250624. Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS



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This work was supported by the National Natural Science Foundation of China (21236003, 21522602), the Shanghai Rising-Star Program (15QA1401200), the International Science and Technology Cooperation Program of China (2015DFA51220), the 111 Project (B14018), and the Fundamental Research Funds for the Central Universities.

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Nanosheets Inlayed into Carbon Frameworks - ACS Publications

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