LAUSR

All-solid-state lithium batteries using flexible solid electrolytes instead of combustible organic liquid electrolytes are the ultimate solution to address the safety problem of commercialized lithium ion batteries. In this study, a free-standing and thermostable polymer/plastic crystal composite electrolyte (PPCE) based on polymerized trimethylolpropane trimethacrylate (TMPTMA)-1, 6-hexanediol diacrylate (HDDA) matrix, and plastic crystal electrolyte was prepared for all-solid-state lithium batteries. The polymerized TMPTMA-HDDA-based matrix of a porous network structure coupled with plastic crystal electrolyte (PCE) in the pores reveals good compatibility. The as-synthesized PPCE possesses excellent flexible performance, thermostability, and high conductivity, showing that PPCE can reach 8.53 × 10−4 S cm−1 with 7.5 wt% monomers (PPCE-7.5%) at 25 °C under a stability electrochemical window above 5.2 V. The assembled lithium batteries Li|PPCE|LiFePO4 exhibit high capacity and highly cycling stability at room temperature, indicating great potential of all-solid-state lithium batteries.