Rational Design of LLZO/Polymer Solid Electrolytes for Solid‐State Batteries

Hybrid composite electrolytes incorporate polymer matrixes and garnet filler attract the focus of concern for all-solid-state batteries, which possess high ionic conductivity, superior electrochemical stability, and wide electrochemical window of ceramic electrolyte advantages, and exhibit excellent flexibility and tensile shear strength from polymer electrolyte benefits. Hence, the unique structure design of solid-state electrolytes resolves the existing defects that the use of either single garnet or polymer electrolytes implemented into battery devices. This review summarizes Li₇ La₃ Zr₂ O₁₂ (LLZO)/polymer solid composite electrolytes (SCEs), comprising LLZO/polymer SCEs with various structures and different ratios of LLZO fillers, LLZO/polymer with different kinds of polymers matrix and hybrid lithium-salt, and Li⁺ transport pathways within the LLZO/polymers SCEs interface. The purpose here is to propose the viewpoints and challenges of LLZO/polymer SCEs to promote the development of next-generation solid electrolytes.