Composition and Structure Design of Poly(vinylidene fluoride)‐Based Solid Polymer Electrolytes for Lithium Batteries

Abstract Solid‐state lithium batteries have become the focus of the next‐generation high‐safety lithium batteries due to their dimensional, thermal, and electrochemical stability. Thus, the progress of solid electrolytes with satisfactory comprehensive performances has become the key to promoting the development of solid batteries. Herein, poly(vinylidene fluoride) (PVDF) solid polymer electrolytes (SPEs) possess excellent flexibility, mechanical property, and high electrochemical and thermal stability, which show huge application potentiality in solid‐state lithium batteries and obtain extensive research. But the PVDF SPEs have been suffering from low ionic conductivity, high crystallinity, and low reactive sites. The development of PVDF‐based composite solid polymer electrolytes (CSPEs) has been confirmed to be a forceful strategy to optimize the performance of electrolytes. In this review, based on different design strategies, the recent progress of PVDF‐based SPEs is introduced in detail, especially in the mechanism of ionic conductivity enhancement and interface regulation by modified fillers. Besides, the applications of PVDF‐based SPEs in Li‐S and Li‐O 2 battery systems are also introduced. Finally, this review presents some insights for promoting the development of high‐performance PVDF‐based SPEs.