Design Strategies and Performance Enhancements of PVDF-based Flexible Electrolytes for High-Performance All-Solid State Lithium Metal Batteries

Lithium metal is considered one of the most promising anode materials for lithium batteries due to its high theoretical specific capacity (3860 mA h g-1) and low redox potential (-3.04 V). However, uncontrolled lithium dendrite growth and severe interfacial side reactions during cycling result in poor performance and safety risks, significantly limiting its practical applications. Replacing liquid electrolytes with solid polymer electrolytes (SPEs) offers a solution, as SPEs provide flexibility and good electrode compatibility, effectively inhibiting dendrite growth and reducing interfacial reactions. Among SPEs, poly(vinylidene fluoride) (PVDF)-based solid electrolytes offer excellent thermal stability and mechanical strength, making them highly suitable for high-energy-density flexible batteries. This review presents recent advances in PVDF-based solid-state electrolytes (SSEs) for stable, high-performance lithium metal batteries (LMBs). We focus on modification strategies that enhance the performance of PVDF-based SSEs in solid-state LMBs and highlight how synthesis methods, nano/microstructural design, and electrochemical properties are interrelated. Lastly, we discuss the challenges and prospects for PVDF-based SSEs in next-generation high-performance LMBs.