Liquid-phase synthesis of Li2S and Li3PS4 with lithium-based organic solutions

doi:10.1088/1674-1056/ac7459

中国物理B ›› 2022, Vol. 31 ›› Issue (9): 98203-098203.doi: 10.1088/1674-1056/ac7459

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

收稿日期:2022-05-07 修回日期:2022-05-25 接受日期:2022-05-29 出版日期:2022-08-19 发布日期:2022-09-03
通讯作者: Fan Wu E-mail:fwu@iphy.ac.cn
基金资助:
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).

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

Received:2022-05-07 Revised:2022-05-25 Accepted:2022-05-29 Online:2022-08-19 Published:2022-09-03
Contact: Fan Wu E-mail:fwu@iphy.ac.cn
Supported by:
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).

摘要/Abstract

摘要： 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 ℃.

关键词: lithium sulfide, sulfide solid electrolyte, liquid phase synthesis, lithium-based organic solution

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 ℃.

Key words: lithium sulfide, sulfide solid electrolyte, liquid phase synthesis, lithium-based organic solution

中图分类号: (Lithium-ion batteries)

82.47.Aa

65.40.gk (Electrochemical properties) 82.45.Gj (Electrolytes)

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[J]. 中国物理B, 2022, 31(9): 98203-098203.

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Liquid-phase synthesis of Li₂S and Li₃PS₄ with lithium-based organic solutions

Liquid-phase synthesis of Li₂S and Li₃PS₄ with lithium-based organic solutions

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