Halogen chemistry of solid electrolytes in all-solid-state batteries

Abstract

All-solid-state batteries (ASSBs) using solid-state electrolytes, replacing flammable liquid electrolytes, are considered one of the most promising next-generation electrochemical energy storage devices because of their improved, inherent safety and energy density. A family of solid electrolytes incorporating halogens has attracted attention because of their potentially high ionic conductivity, good deformability and wide electrochemical windows. Although progress has been made for halogen-containing solid electrolytes (HSEs) in ASSBs, challenges in the preparations, characterizations and low-cost industrial scalability remain. In this Review, we focus on the development of halide battery chemistry, the preparation, modification and properties of HSEs, and issues with HSEs in ASSBs. The chemical action of halogen and ion transport mechanisms are discussed. Moreover, the main challenges and future development directions of halide-based ASSBs are discussed to pave the way for practical applications of HSEs for next-generation rechargeable batteries. The history of halogen-containing solid electrolytes is presented, and the advantages of halogen-chemistry for solid electrolytes related to crystal structures, migration pathways and ion transport mechanisms are summarized. Finally, the main challenges and future developments of halogen-containing solid electrolytes are discussed.