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面向稳定的硫化物基超离子导体LiCuGeS的化学设计

Chemistry Design Towards a Stable Sulfide-Based Superionic Conductor Li Cu Ge S.

作者信息

Wang Yingqi, Lü Xujie, Zheng Chong, Liu Xiang, Chen Zonghai, Yang Wenge, Lin Jianhua, Huang Fuqiang

机构信息

Center for High Pressure Science & Technology Advanced Research, Shanghai, 206203, P. R. China.

Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL, 60115, USA.

出版信息

Angew Chem Int Ed Engl. 2019 Jun 3;58(23):7673-7677. doi: 10.1002/anie.201901739. Epub 2019 Apr 29.

Abstract

Sulfide-based superionic conductors with high ionic conductivity have been explored as candidates for solid-state Li batteries. However, moisture hypersensitivity has made their manufacture complicated and costly and also impeded applications in batteries. Now, a sulfide-based superionic conductor Li Cu Ge S with superior stability was developed based on the hard/soft acid-base theory. The compound is stable in both moist air and aqueous LiOH aqueous solution. The electrochemical stability window was up to 1.5 V. An ionic conductivity of 0.9×10  S cm with low activation energy of 0.33 eV was achieved without any optimization. The material features a rigid Cu-Ge-S open framework that increases its stability. Meanwhile, the weak bonding between Li and the framework promotes ionic conductivity. This work provides a structural configuration in which weak Li bonding in the rigid framework promotes an environment for highly conductive and stable solid-state electrolytes.

摘要

具有高离子电导率的硫化物基超离子导体已被探索用作固态锂电池的候选材料。然而,对水分的高敏感性使得它们的制造复杂且成本高昂,也阻碍了其在电池中的应用。现在,基于硬/软酸碱理论开发了一种具有卓越稳定性的硫化物基超离子导体LiCuGeS。该化合物在潮湿空气中和LiOH水溶液中均稳定。其电化学稳定窗口高达1.5 V。未经任何优化就实现了0.9×10  S cm的离子电导率以及0.33 eV的低活化能。该材料具有刚性的Cu-Ge-S开放框架,这提高了其稳定性。同时,Li与框架之间的弱键促进了离子电导率。这项工作提供了一种结构构型,其中刚性框架中弱的Li键促进了高导电性和稳定的固态电解质的环境。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bdf1/6850061/8e8a4b4e674e/ANIE-58-7673-g001.jpg

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