Air‐stable Li3.12P0.94Bi0.06S3.91I0.18 solid‐state electrolyte with high ionic conductivity and lithium anode compatibility toward high‐performance all‐solid‐state lithium metal batteries
Daokuan Jin,
Haodong Shi,
Yuxin Ma,
Yangyang Liu,
Yang Wang,
Yanfeng Dong,
Mingbo Wu,
Zhong‐Shuai Wu
Affiliations
Daokuan Jin
State Key Laboratory of Heavy Oil Processing Institute of New Energy College of Chemistry and Chemical Engineering China University of Petroleum (East China) Qingdao China
Haodong Shi
State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian China
Yuxin Ma
State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian China
Yangyang Liu
State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian China
Yang Wang
State Key Laboratory of Heavy Oil Processing Institute of New Energy College of Chemistry and Chemical Engineering China University of Petroleum (East China) Qingdao China
Yanfeng Dong
Department of Chemistry College of Sciences Northeastern University Shenyang China
Mingbo Wu
State Key Laboratory of Heavy Oil Processing Institute of New Energy College of Chemistry and Chemical Engineering China University of Petroleum (East China) Qingdao China
Zhong‐Shuai Wu
State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian China
Abstract Sulfide solid‐state electrolytes (SSEs) with superior ionic conductivity and processability are highly promising candidates for constructing all‐solid‐state lithium metal batteries (ASSLMBs). However, their practical applications are limited by their intrinsic air instability and serious interfacial incompatibility. Herein, a novel glass‐ceramic electrolyte Li3.12P0.94Bi0.06S3.91I0.18 was synthesized by co‐doping Li3PS4 with Bi and I for high‐performance ASSLMBs. Owing to the strong Bi‒S bonds that are thermodynamically stable to water, increased unit cell volume and Li+ concentration caused by P5+ substitution with Bi3+, and the in situ formed robust solid electrolyte interphase layer LiI at lithium surface, the as‐prepared Li3.12P0.94Bi0.06S3.91I0.18 SSE achieved excellent air stability with a H2S concentration of only 0.205 cm3 g−1 (after 300 min of air exposure), outperforming Li3PS4 (0.632 cm3 g−1) and the most reported sulfide SSEs, together with high ionic conductivity of 4.05 mS cm−1. Furthermore, the Li3.12P0.94Bi0.06S3.91I0.18 effectively improved lithium metal stability. With this SSE, an ultralong cyclability of 700 h at 0.1 mA cm−2 was realized in a lithium symmetrical cell. Moreover, the Li3.12P0.94Bi0.06S3.91I0.18‐based ASSLMBs with LiNi0.8Mn0.1Co0.1O2 cathode achieved ultrastable capacity retention rate of 95.8% after 300 cycles at 0.1 C. This work provides reliable strategy for designing advanced sulfide SSEs for commercial applications in ASSLMBs.
