Title: Chemistry Design Towards a Stable Sulfide-Based Superionic Conductor Li₄Cu₈Ge ₃S₁₂

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 Li₄Cu₈Ge ₃S₁₂ 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^-4 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.

Authors:

Wang, Yingqi ^[1]; Lü, Xujie  ^[1];

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Zheng, Chong ^[2]; Liu, Xiang ^[3]; Chen, Zonghai ^[4]; Yang, Wenge ^[1]; Lin, Jianhua ^[5]; Huang, Fuqiang ^[6]

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+ Show Author Affiliations

1. Center for High Pressure Science & Technology Advanced Research, Shanghai (China)
2. Northern Illinois Univ., DeKalb, IL (United States)
3. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont IL 60439 USA
4. Argonne National Lab. (ANL), Argonne, IL (United States)
5. Peking Univ., Beijing (China). State Key Lab. of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering
6. Peking Univ., Beijing (China). State Key Lab. of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering; Chinese Academy of Sciences (CAS), Shanghai (China). CAS Key Lab. of Materials for Energy Conversion, Shanghai Inst. of Ceramics

Publication Date:

Tue Apr 02 00:00:00 EDT 2019

Research Org.:

Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Org.:

National Natural Science Foundation of China (NSFC); China Scholarship Council; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

OSTI Identifier:

1515841

Alternate Identifier(s):

OSTI ID: 1509750

Grant/Contract Number:  

AC02-06CH11357; U1530402; Y93GJ11101

Resource Type:

Accepted Manuscript

Journal Name:

Angewandte Chemie (International Edition)

Additional Journal Information:

Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 23; Journal ID: ISSN 1433-7851

Publisher:

Wiley

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chalcogenide framework; crystal engineering; enhanced stability; solid electrolyte; superionic conductor; chalcogenide open framework