Advanced Composite Solid Electrolytes for Lithium Batteries: Filler Dimensional Design and Ion Path Optimization

Abstract Composite solid electrolytes are considered to be the crucial components of all‐solid‐state lithium batteries, which are viewed as the next‐generation energy storage devices for high energy density and long working life. Numerous studies have shown that fillers in composite solid electrolytes can effectively improve the ion‐transport behavior, the essence of which lies in the optimization of the ion‐transport path in the electrolyte. The performance is closely related to the structure of the fillers and the interaction between fillers and other electrolyte components including polymer matrices and lithium salts. In this review, the dimensional design of fillers in advanced composite solid electrolytes involving 0D–2D nanofillers, and 3D continuous frameworks are focused on. The ion‐transport mechanism and the interaction between fillers and other electrolyte components are highlighted. In addition, sandwich‐structured composite solid electrolytes with fillers are also discussed. Strategies for the design of composite solid electrolytes with high room temperature ionic conductivity are summarized, aiming to assist target‐oriented research for high‐performance composite solid electrolytes.