- Chi, Xiaowei;
- Zhang, Ye;
- Hao, Fang;
- Kmiec, Steven;
- Dong, Hui;
- Xu, Rong;
- Zhao, Kejie;
- Ai, Qing;
- Terlier, Tanguy;
- Wang, Liang;
- Zhao, Lihong;
- Guo, Liqun;
- Lou, Jun;
- Xin, Huolin L;
- Martin, Steve W;
- Yao, Yan
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 (Na3PS4-xOx, 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 Na3PS4-xOx 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.