An electrochemically stable homogeneous glassy electrolyte formed at room temperature for all-solid-state sodium batteries

Xiaowei Chi; Ye Zhang; Fang Hao; Steven Kmiec; Hui Dong; Rong Xu; Kejie Zhao; Qing Ai; Tanguy Terlier; Liang Wang; Lihong Zhao; Liqun Guo; Jun Lou; Huolin L Xin; Steve W Martin; Yan Yao

doi:10.1038/s41467-022-30517-y

An electrochemically stable homogeneous glassy electrolyte formed at room temperature for all-solid-state sodium batteries

Nat Commun. 2022 May 23;13(1):2854. doi: 10.1038/s41467-022-30517-y.

Authors

Xiaowei Chi^#^{1

2}, Ye Zhang^#¹, Fang Hao^#¹, Steven Kmiec^#³, Hui Dong¹, Rong Xu⁴, Kejie Zhao⁴, Qing Ai⁵, Tanguy Terlier⁶, Liang Wang^{7

8}, Lihong Zhao¹, Liqun Guo¹, Jun Lou⁵, Huolin L Xin⁹, Steve W Martin¹⁰, Yan Yao¹¹

Affiliations

¹ Department of Electrical and Computer Engineering and Texas Center for Superconductivity at the University of Houston, University of Houston, Houston, TX, 77204, USA.
² Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China.
³ Department of Materials Science & Engineering, Iowa State University, Ames, IA, 50011, USA.
⁴ School of Mechanical Engineering, Purdue University, West Lafayette, IN, 47907, USA.
⁵ Department of Materials Science and NanoEngineering, Rice University, Houston, TX, 77005, USA.
⁶ Shared Equipment Authority, SIMS laboratory, Rice University, Houston, TX, 77005, USA.
⁷ Department of Physics, Northern Illinois University, Dekalb, IL, 60115, USA.
⁸ Institute of Advanced Structure Technology and School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China.
⁹ Department of Physics and Astronomy, University of California, Irvine, Irvine, CA, 92697, USA.
¹⁰ Department of Materials Science & Engineering, Iowa State University, Ames, IA, 50011, USA. swmartin@iastate.edu.
¹¹ Department of Electrical and Computer Engineering and Texas Center for Superconductivity at the University of Houston, University of Houston, Houston, TX, 77204, USA. yyao4@uh.edu.

^# Contributed equally.

Abstract

All-solid-state sodium batteries (ASSSBs) are promising candidates for grid-scale energy storage. However, there are no commercialized ASSSBs yet, in part due to the lack of a low-cost, simple-to-fabricate solid electrolyte (SE) with electrochemical stability towards Na metal. In this work, we report a family of oxysulfide glass SEs (Na₃PS_4-xO_x, where 0 < x ≤ 0.60) that not only exhibit the highest critical current density among all Na-ion conducting sulfide-based SEs, but also enable high-performance ambient-temperature sodium-sulfur batteries. By forming bridging oxygen units, the Na₃PS_4-xO_x SEs undergo pressure-induced sintering at room temperature, resulting in a fully homogeneous glass structure with robust mechanical properties. Furthermore, the self-passivating solid electrolyte interphase at the Na|SE interface is critical for interface stabilization and reversible Na plating and stripping. The new structural and compositional design strategies presented here provide a new paradigm in the development of safe, low-cost, energy-dense, and long-lifetime ASSSBs.