Designing Cooperative Ion Transport Pathway in Ultra‐Thin Solid‐State Electrolytes toward Practical Lithium Metal Batteries

Abstract Solid polymer electrolytes (SPEs) are promising for high‐energy‐density solid‐state Li metal batteries due to their decent flexibility, safety, and interfacial stability. However, their development was seriously hindered by the interfacial instability and limited conductivity, leading to inferior electrochemical performance. Herein, we proposed to design ultra‐thin solid‐state electrolyte with long‐range cooperative ion transport pathway to effectively increase the ionic conductivity and stability. The impregnation of PVDF−HFP inside pores of fluorinated covalent organic framework (CF3−COF) can disrupt its symmetry, rendering rapid ion transportation and inhibited anion immigration. The functional groups of CF3−COF can interact with PVDF−HFP to form fast Li+ transport channels, which enables the uniform and confined Li+ conduction within the electrolyte. The introduction of CF3−COF also enhances the mechanical strength and flexibility of SPEs, as well as ensures homogeneous Li deposition and inhibited dendrite growth. Hence, a remarkably high conductivity of 1.21×10−3 S cm−1 can be achieved. Finally, the ultra‐thin SPEs with an extremely long cycle life exceed 9000 h can be obtained while the NCM523/Li pouch cell demonstrates a high capacity of 760 mAh and 96 % capacity retention after cycling, holding great promises to be utilized for practical solid‐state Li metal batteries.