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Recyclable cobalt-molybdenum bimetallic carbide modified separator boosts the polysulfide adsorption-catalysis of lithium sulfur battery

钴-钼双金属碳化物修饰隔膜**化锂硫电池中多 硫化锂的吸附和催化转化

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Abstract

The polysulfide shuttling and sluggish redox kinetics, due to the notorious adsorption-catalysis underperformance, are the ultimate obstacles of the practical application of lithium-sulfur (Li-S) batteries. Conventional carbon-based and transition metal compound-based material solutions generally suffer from poor catalysis and adsorption, respectively, despite the performance gain in terms of the other. Herein, we have enhanced polysulfide adsorption-catalytic capability and protected the Li anode using a complementary bimetallic carbide electrocatalyst, Co3Mo3C, modified commercial separator. With this demonstration, the potentials of bimetal compounds, which have been well recognized in other environmental catalysis, are also extended to Li-S batteries. Coupled with this modified separator, a simple cathode (S/Super P composite) can deliver high sulfur utilization, high rate performance, and excellent cycle stability with a low capacity decay rate of ∼0.034% per cycle at 1 C up to 1000 cycles. Even at a high S-loading of 8.0 mg cm−2 with electrolyte/sulfur ratio=6 mL g−1, the cathode still exhibits high areal capacity of ∼6.8 mA h cm−2. The experimental analysis and the first principles calculations proved that the bimetallic carbide Co3Mo3C provides more binding sites for adsorbing polysulfides and catalyzing the multiphase conversion of sulfur/polysulfide/sulfide than monometallic carbide Mo2C. Moreover, the modified separator can be reutilized with comparable electrochemical performance. We also showed other bimetallic carbides with similar catalytic effects on Li S batteries and this material family has great promise in different energy electrocatalytic systems.

摘要

本文报道了一种钴-钼双金属碳化物(Co3Mo3C)催化材料用于修饰锂硫电池隔膜, **化多硫化锂的化学吸附和催化转化. 所组 装的电池表现出优异的电化学性能, 即使在8.0 mg cm−2的硫面积负载量条件下, 面积比容量仍高达6.8 mA h cm−2. 理论计算结果表明, 相比于单一金属碳化物Mo2C, 双金属碳化物Co3Mo3C具有更多的活性位点, 更利于化学固定多硫化锂, 并催化多硫化锂间相互转化; 同时, Ni3Mo3C和Fe3Mo3C亦表现出类似的高催化活性. 本研究对高性能锂硫电池关键催化材料的设计具有一定的指导意义.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21863006, 51662029, 61974082 and 61704096), Youth Science Foundation of Jiangxi Province (20192BAB216001), and Key Laboratory of Jiangxi Province for Environment and Energy Catalysis (20181BCD40004).

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Authors and Affiliations

  1. School of Chemistry, Nanchang University, Nanchang, 330031, China

    Ze Zhang  (张泽), A.-Hu Shao  (邵啊虎), Dong-Gen **ong  (熊冬根), Ji Yu  (吁霁) & Zhen-Yu Yang  (杨震宇)

  2. Department of Materials Science and Metalliclurgy, University of Cambridge, Cambridge, CB3 0FS, UK

    Jia-Nan Wang  (王嘉楠), Cheng-Yen Lao  (劳成琰), Kai **  (郗凯) & R. Vasant Kumar

  3. Department of Environmental Science and Engineering, Department of Applied Chemistry, School of Science, Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter (Ministry of Education), State Key Laboratory for Electrical Insulation and Power Equipment, **’an Jiaotong Univrsity, **’an, 710049, China

    Jia-Nan Wang  (王嘉楠) & Jian-Wei Liu  (刘建伟)

  4. Department of Engineering, University of Cambridge, CB3 0FA, Cambridge, UK

    Kai **  (郗凯) & Qiu Jiang  (江秋)

  5. Department of Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, China

    Shi-Yao Lu  (芦世瑶)

  6. Department of Precision Instrument, Tsinghua University, Bei**g, 10084, China

    Huang-Long Li  (**黄龙)

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  1. Ze Zhang  (张泽)
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  2. Jia-Nan Wang  (王嘉楠)
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  3. A.-Hu Shao  (邵啊虎)
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  4. Dong-Gen **ong  (熊冬根)
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  5. Jian-Wei Liu  (刘建伟)
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  6. Cheng-Yen Lao  (劳成琰)
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  7. Kai **  (郗凯)
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  8. Shi-Yao Lu  (芦世瑶)
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  9. Qiu Jiang  (江秋)
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  10. Ji Yu  (吁霁)
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  11. Huang-Long Li  (**黄龙)
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  12. Zhen-Yu Yang  (杨震宇)
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  13. R. Vasant Kumar
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Contributions

Author contributions Zhang Z, Yang ZY and ** K conceived the idea; Zhang Z prepared the materials, conducted the electrochemical experiments; Shao AH and **ong DG conducted the characterization of materials; Li HL performed the DFT calculations; Wang JN, Liu JW, Lao CY, Lu SY, Jiang Q, Yu J, Li HL and Kumar RV contributed to the correction of the manuscript; ** K and Yang ZY revised the manuscript written by Zhang Z. All the authors commented on the manuscript.

Corresponding authors

Correspondence to Kai **  (郗凯), Huang-Long Li  (**黄龙) or Zhen-Yu Yang  (杨震宇).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Ze Zhang is a lecturer at the College of Chemistry, Nanchang University. He received his BSc degree in 2012 from the College of Chemistry, and PhD degree in 2017 from the School of Materials Science and Engineering, Nankai University, China. His main research interest is in the area of advanced functional materials for rechargeable batteries with a focus on the exploration of high-energy Li-S batteries.

Kai ** is a research associate at the Cambridge Graphene Centre. He obtained his PhD degree in the Department of Materials Science and Metallurgy, University of Cambridge. His research focuses on materials engineering and physical chemistry for renewable energy conversion and storage, in particular lithium-sulphur (Li-S) batteries, lithium-ion batteries and solar cells. He was awarded the grand prize of the Dow Sustainability Innovation Student Challenge Award. His CamBattery team was awarded Technology Start Up of the Year by Cambridge University Entrepreneurs in 2012.

Huang-Long Li is an associate professor at the Department of Precision Instrument, Tsinghua University. His research interests include nanoelectronics, neuromorphic engineering, ab initio calculations, electronic materials and energy materials. He received his PhD degree in electrical engineering from the University of Cambridge (2014), and the BSc degree in physics from Peking University (2010).

Zhen-Yu Yang is a professor at the School of Chemistry, Nanchang University, China. He received his PhD degree at the Technical Institute of Physics and Chemistry, Chinese Academy of Sciences in 2005. He used to work as a visiting research fellow at Rensselaer Polytechnic Institute in USA from 2012 to 2013 and at Nanyang Technological University in Singapore in 2019, respectively. Currently, his main research focuses on energy storage materials for power sources, including Li-ion batteries, Li-S batteries, and supercapacitors.

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Recyclable cobalt-molybdenum bimetallic carbide modified separator boosts the polysulfide adsorption-catalysis of lithium sulfur battery

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Zhang, Z., Wang, JN., Shao, AH. et al. Recyclable cobalt-molybdenum bimetallic carbide modified separator boosts the polysulfide adsorption-catalysis of lithium sulfur battery. Sci. China Mater. 63, 2443–2455 (2020). https://doi.org/10.1007/s40843-020-1425-2

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