Understanding Electrochemical Reaction Mechanisms of Sulfur in All‐Solid‐State Batteries through Operando and Theoretical Studies **

Cao, Daxian; Sun, Xiao; Li, Fei; Bak, Seong‐Min; Ji, Tongtai; Geiwitz, Michael; Burch, Kenneth S.; Du, Yonghua; Yang, Guochun; Zhu, Hongli

doi:10.1002/ange.202302363

Title: Understanding Electrochemical Reaction Mechanisms of Sulfur in All‐Solid‐State Batteries through Operando and Theoretical Studies **

Journal Article · 13 April 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202302363 · OSTI ID:1969763

^[1]; Sun, Xiao ^[1]; Li, Fei ^[2]; Bak, Seong‐Min ^[3]; Ji, Tongtai ^[1]; Geiwitz, Michael ^[4]; Burch, Kenneth S. ^[4]; Du, Yonghua ^[3]; Yang, Guochun ^[2];

^[1]

Department of Mechanical and Industrial Engineering Northeastern University 360 Huntington Avenue Boston MA 02115 USA
State Key Laboratory of Metastable Materials Science &, Technology and Key Laboratory for Microstructural Material Physics of Hebei Province School of Science Yanshan University Qinhuangdao 066004 China
National Synchrotron Light Source II Brookhaven National Laboratory Upton NY 11973 USA
Department of Physics Boston College 140 Commonwealth Ave Chestnut Hill MA 02467-3804 USA

Abstract Due to its outstanding safety and high energy density, all‐solid‐state lithium‐sulfur batteries (ASLSBs) are considered as a potential future energy storage technology. The electrochemical reaction pathway in ASLSBs with inorganic solid‐state electrolytes is different from Li‐S batteries with liquid electrolytes, but the mechanism remains unclear. By combining operando Raman spectroscopy and ex situ X‐ray absorption spectroscopy, we investigated the reaction mechanism of sulfur (S ₈ ) in ASLSBs. Our results revealed that no Li ₂ S _8, Li ₂ S _6, and Li ₂ S ₄ were formed, yet Li ₂ S ₂ was detected. Furthermore, first‐principles structural calculations were employed to disclose the formation energy of solid state Li ₂ S _n (1≤ n ≤8), in which Li ₂ S ₂ was a metastable phase, consistent with experimental observations. Meanwhile, partial S ₈ and Li ₂ S ₂ remained at the full lithiation stage, suggesting incomplete reaction due to sluggish reaction kinetics in ASLSBs.

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Sponsoring Organization:: USDOE

OSTI ID:: 1969763

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 20 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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