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Chin. Phys. B, 2022, Vol. 31(9): 098203    DOI: 10.1088/1674-1056/ac7459
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Liquid-phase synthesis of Li2S and Li3PS4 with lithium-based organic solutions

Jieru Xu(许洁茹)1,2,3,4, Qiuchen Wang(王秋辰)1,2, Wenlin Yan(闫汶琳)1,2,3,4, Liquan Chen(陈立泉)1,2,3,4, Hong Li(李泓)1,2,3,4, and Fan Wu(吴凡)1,2,3,4,5,†
1 Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China;
2 University of Chinese Academy of Sciences, Beijing 100049, China;
3 Tianmu Lake Institute of Advanced Energy Storage Technologies, Liyang 213300, China;
4 Yangtze River Delta Physics Research Center, Liyang 213300, China;
5 Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, China
Abstract  Sulfide solid electrolytes are widely regarded as one of the most promising technical routes to realize all-solid-state batteries (ASSBs) due to their high ionic conductivity and favorable deformability. However, the relatively high price of the crucial starting material, Li2S, results in high costs of sulfide solid electrolytes, limiting their practical application in ASSBs. To solve this problem, we develop a new synthesis route of Li2S via liquid-phase synthesis method, employing lithium and biphenyl in 1, 2-dimethoxyethane (DME) ether solvent to form a lithium solution as the lithium precursor. Because of the comparatively strong reducibility of the lithium solution, its reaction with sulfur proceeds effectively even at room temperature. This new synthesis route of Li2S starts with cheap precursors of lithium, sulfur, biphenyl and DME solvent, and the only remaining byproduct (DME solution of biphenyl) after the collection of Li2S product can be recycled and reused. Besides, the reaction can proceed effectively at room temperature with mild condition, reducing energy cost to a great extent. The as-synthesized Li2S owns uniform and extremely small particle size, proved to be feasible in synthesizing sulfide solid electrolytes (such as the solid-state synthesis of Li6PS5Cl). Spontaneously, this lithium solution can be directly employed in the synthesis of Li3PS4 solid electrolytes via liquid-phase synthesis method, in which the centrifugation and heat treatment processes of Li2S are not necessary, providing simplified production process. The as-synthesized Li3PS4 exhibits typical Li+ conductivity of 1.85×10-4 S·cm-1 at 30 ℃.
Keywords:  lithium sulfide      sulfide solid electrolyte      liquid phase synthesis      lithium-based organic solution  
Received:  07 May 2022      Revised:  25 May 2022      Accepted manuscript online:  29 May 2022
PACS:  82.47.Aa (Lithium-ion batteries)  
  65.40.gk (Electrochemical properties)  
  82.45.Gj (Electrolytes)  
Fund: This work is supported by Key R&D Project funded by Department of Science and Technology of Jiangsu Province (Grant No. BE2020003), Key Program-Automobile Joint Fund of National Natural Science Foundation of China (Grant No. U1964205), General Program of National Natural Science Foundation of China (Grant No. 51972334), General Program of National Natural Science Foundation of Beijing (Grant No. 2202058), Cultivation Project of Leading Innovative Experts in Changzhou City (Grant No. CQ20210003), National Overseas High-level Expert Recruitment Program (Grant No. E1JF021E11), Talent Program of Chinese Academy of Sciences, "Scientist Studio Program Funding" from Yangtze River Delta Physics Research Center and Tianmu Lake Institute of Advanced Energy Storage Technologies (Grant No. TIES-SS0001), and Science and Technology Research Institute of China Three Gorges Corporation (Grant No. 202103402).
Corresponding Authors:  Fan Wu     E-mail:  fwu@iphy.ac.cn

Cite this article: 

Jieru Xu(许洁茹), Qiuchen Wang(王秋辰), Wenlin Yan(闫汶琳), Liquan Chen(陈立泉), Hong Li(李泓), and Fan Wu(吴凡) Liquid-phase synthesis of Li2S and Li3PS4 with lithium-based organic solutions 2022 Chin. Phys. B 31 098203

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