MoS2 nanoplates assembled on electrospun polyacrylonitrile-metal organic framework-derived carbon fibers for lithium storage

doi:10.1016/j.nanoen.2019.04.045

Nano Energy

Volume 61, July 2019, Pages 104-110

https://doi.org/10.1016/j.nanoen.2019.04.045 Get rights and content

Highlights

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Ultrathin MoS₂ nanosheets are assembled on electrospun polyacrylonitrile-MOF-derived porous carbon nanofibers.
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Effects of structure and component on the electrochemical performances of PCNF@MoS₂ have been investigated.
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The PCNF@MoS₂ composites show enhanced lithium storage and cycling performance when applied as anode material for LIBs.

Abstract

Molybdenum disulfide (MoS₂) has been intensively investigated for its high theoretical capacity as an advanced anode material for lithium storage. However, the low electronic conductivity and frail layered structure give rise to its poor cycling stability and low rate performance. Herein, by taking advantages of the porous structure and the high N content of metal-organic frameworks (MOFs) derivatives, a facile and scalable method combining electrospinning and following a hydrothermal process was developed to fabricate MoS₂-based composite fibers, in which ultrathin MoS₂ nanoplates were vertically assembled on the polyacrylonitrile-MOF-derived N-doped porous carbon nanofibers (PCNF). As expected, benefiting from the hierarchical structure of PCNF and the synergies between MoS₂ and PCNF, the obtained PCNF@MoS₂ exhibited high capacity and cycling performance in a lithium battery.

Graphical abstract

Introduction

Lithium storage has attracted a great attention to circumvent the energy and environmental problems [[1], [2], [3], [4]]. Remarkably, the commercial graphite served as anode material in Lithium-ion batteries (LIBs) plays a significant role for decades because of its low-cost, easy preparation and favorable conductivity. However, the relative low special capacity (∼372 mA h g⁻¹), inferior rate performance and low initial Coulombic efficiency (CE) hamper its popularity in LIBs [[5], [6], [7]]. Thus, it's urgent to explore excellent anode materials with great capacity and stability. In recent years, two dimensional (2D) transition-metal sulfides, especially the layered MoS₂ with a sandwich structure, have gained extensive interest for its hierarchical nanostructure and physicochemical property [8,9]. Moreover, a great number of active sites are dispersed among the layered MoS₂, which endow the ultrathin layered MoS₂ with a high theoretical capacity (∼670 mA h g⁻¹) that is more promising than the commercial electrode materials of LIBs. Nevertheless, its inherently poor conductivity (relating to the electron and Li⁺ transfer) and frail sulfur electrochemistry lead to serious capacity fading and poor rate performance during the cycling process [[9], [10], [11]].

Many methods have been devoted to solve the above problems of MoS₂. It has been proved that a relatively wide distance between the atom layers is beneficial to the Li⁺ transfer to form Li₂S on MoS₂, which accelerates the lithiation/delithiation processes and reduces the destruction of MoS₂ nanostructure during the charge/discharge cycles [12]. Besides, it's a universal strategy to match MoS₂ with carbon-based materials, such as graphene [5,13], carbon nanotubes [[14], [15], [16], [17]] and carbon nanospheres [18], to enhance its conductivity and reversible capacity. Thus the rational design of MoS₂@carbon-based materials (crystal type, size and assembly) is likely to enhance the electrochemical performance. Polyacrylonitrile (PAN)-derived carbon is a frequently used carbon source, but it has relatively low capacity. Recently, owing to the uniform heteroatom decoration, high conductivity, and super high surface area and porous structure, the metal-organic frameworks (MOFs)-derived carbon materials for energy storage and transfer have become a hot research topic. However, it is easy to be sintered during the calcination process and resulting in reduced performance. The assembly of MOFs into hierarchical structure can well solve the above issues. In particular, the 1D nanofibers possess higher performance than 0D nanoparticles (NPs) because they are conducive to the electrons/mass transfer, and several works have reported the preparation of MOF-derived porous carbon nanofibers (PCNFs) by electrospinning, which exhibit excellent electrochemical performance when used as anode materials for LIBs [[19], [20], [21]].

The strategy of assembling MOFs in PAN electrospun fibers (PAN@MOF) and further synthesizing MoS₂ nanoplates on PAN@MOF-derived porous carbon nanofibers (denoted as PCNF@MoS₂) may be an effective way to further improve the performances of LIBs, which can give full play to their respective advantages. Herein, we report on the preparation of hierarchically structured PCNF@MoS₂ fibers via electrospinning and following a hydrothermal process, in which MoS₂ nanoplates were vertically assembled on the surfaces of PCNFs. Also, the electrochemical performance of the composites in LIBs was investigated. The synthesis process of PCNF@MoS₂ was schematically shown in Fig. 1. Firstly, PAN and N-rich ZIF-8 NPs (ZIFs) were electrospun to prepare nanofibers with high aspect ratios (ES-PAN@ZIFs). Secondly, ES-PAN@ZIFs fibers were annealed at a high temperature in the Ar atmosphere to obtain N-doped PCNFs. Finally, the ultrathin MoS₂ nanosheets were uniformly assembled on the surfaces of PCNFs by a hydrothermal process (PCNF@MoS₂). As expected, benefiting from the unique structure and components, the obtained PCNF@MoS₂ composite showed enhanced lithium storage and cycling performance when used as the anode material of LIBs, including a high reversible capacity of 1116.2 mA h g⁻¹ at 1000 mA g⁻¹ after 450 cycles, and 1304.3 mA h g⁻¹ at 500 mA g⁻¹ after 200 cycles.

Section snippets

Materials

Zinc nitrate hexahydrate [Zn(NO₃)₂^.6H₂O], methanol, ethanol, N, N-dimethylformamide (DMF), thiourea (TTA), and hexa ammonium heptamolybdate tetrahydrate [(NH₄)₆Mo₇O₂₄^.4H₂O] were purchased from Sinopharm Chemical Reagent Co., Ltd (Shanghai, China), 2-methylimidazole (2-MIA) and polyacrylonitrile (PAN, M_w = 150000) were supplied by Sigma-Aldrich Chemistry (USA). All the materials were analytical grade and were applied directly without further purification.

Synthesis of ZIF-8 nanoparticles (ZIFs)

ZIFs were synthesized by a previously

Results and discussion

The ZIFs with a uniform diameter of ∼50 nm were synthesized (Fig. S1), and were densely assembled within the PAN fibers via electrospinning (ES-PAN@ZIFs). The fiber surfaces were rough due to the high content of NPs (Fig. S2). After calcination, the 1D structure of the electrospun fibers was retained well, and N-doped PCNFs with high porosity were obtained (Fig. S3). During the followed solvothermal process, by pinning on carbon or the strong interactions with carbon, MoS₂ nanoplates were

Conclusions

In summary, we report the synthesis of hierarchically structured PAN-MOF-derived PCNF@MoS₂ fibers by a multistep method. Ultrathin MoS₂ nanoplates were uniformly vertically assembled on the surfaces of PCNFs, in which almost no restacking of MoS₂ nanoplates was observed under proper precursor content, demonstrating the template effect of PCNFs. After the electrochemical characterization, PCNF@MoS₂ exhibited enhanced cycling and rate performance when applied as anode material in LIBs, revealing

Acknowledgements

We acknowledge funding support from the National Natural Science Foundation of China (Grant 21431006, 51403195), the Fundamental Research Funds for the Central Universities (Grants JZ2018HGTB0250, JZ2017HGTA0229), the Anhui Provincial Natural Science Foundation (1908085ME155), the open project of Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering (Grant No. 45000-411104/007), the Foundation for Innovative Research Groups of the National Natural Science

Chuan-Ling Zhang received her Ph.D. under the supervision of Prof. Shu-Hong Yu at the University of Science and Technology of China (USTC) in 2013. Then, she worked as a postdoctoral researcher with Prof. Shu-Hong Yu at USTC. Currently, she is an associate professor at HeFei University of Technology. Her current research focuses on designing novel functional composite materials by electrospinning-assisted assembly of nanoparticles and investigating their related properties.

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Zhi-Hao Jiang received his Bachelor at Hubei University of Science and Technology in 2016, and he will graduate from Hefei University of Technology in 2019. His main research field is electrospinning of MOFs to prepare doped carbon nanofibers for Li-ion battery.

Bing-Rong Lu received her Bachelor from HuaiNan Normal University in 2015, and the master degree from HeFei University of Technology in 2018 under the supervision of Prof. Chuan-Ling Zhang. Her current research focuses on electrospinning of MOF nanoparticles to prepare composite carbon nanofibers for ORR electrocatalyst and lithium ion battery.

Jiang-Tao Liu received his Bachelor from Huainan Normal University in 2016, and the Master degree will be obtained under the supervision of Prof. Chuan-Ling Zhang at the Hefei University of Technology in 2019. His current work is to design and synthesize one-dimensional MOF and MOF-derived porous carbon nanomaterials for ORR catalysts and Zinc-air batteries.

Fu-Hu Cao received his Ph.D. under the supervision of Prof. Yan-Mei Wang at the University of Science and Technology of China (USTC) in 2013. After two years as a postdoctoral fellow with Prof. Shu-Hong Yu at Hefei University of Technology (HFUT), he joined HFUT as a lecturer in 2015. His current research is mainly about the application of electrospun nanofibers in filtration and separation.

Hao Li received his Bachelor from Hefei University of Technology in 2017, and he is currently pursuing a Master Degree under the supervision of Prof. Chuan-Ling Zhang in Hefei University of Technology. His current research focuses on electrospinning of functional nanoparticles for responsive materials.

Zhi-Long Yu received his Bachelor at Northwestern Polytechnical University (NWPU), and Ph.D. degree in chemistry from the University of Science and Technology of China (USTC) under the guidance of Prof. Shu-Hong Yu. Now he is a postdoctoral researcher (National Postdoctoral Innovative Talents) in USTC. His current research interest is focused on the design and fabrication of novel polymeric materials, including composite aerogels, engineering materials and bio-inspired materials.

Shu-Hong Yu received his Ph.D. in Inorg. Chem. in 1998 from the University of Science and Technology of China (USTC). From 1999 to 2001, he joined in Tokyo Institute of Technology as a Postdoctoral Research Fellow. From 2001 to 2002, he was as an Alexander von Humboldt Research Fellow in the Max Planck Institute of Colloids and Interfaces, Germany. He was appointed as a full professor in 2002 and the Cheung Kong Professorship in 2006 by the Ministry of Education in USTC. His current research interests include bioinspired synthesis and self-assembly of nanostructured materials and nanocomposites, and their related properties.

¹: These authors contributed equally to this work.

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Full paperMoS2 nanoplates assembled on electrospun polyacrylonitrile-metal organic framework-derived carbon fibers for lithium storage

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Synthesis of ZIF-8 nanoparticles (ZIFs)

Results and discussion

Conclusions

Acknowledgements

Nanomater. Energy