Polymers with Intrinsic Microporosity as Solid Ion Conductors for Solid‐State Lithium Batteries

Abstract Solid‐state electrolytes (SSEs) with high ionic conductivity and superior stability are considered to be a key technology for the safe operation of solid‐state lithium batteries. However, current SSEs are incapable of meeting the requirements for practical solid‐state lithium batteries. Here we report a general strategy for achieving high‐performance SSEs by engineering polymers of intrinsic microporosity (PIMs). Taking advantage of the interconnected ion pathways generated from the ionizable groups, high ionic conductivity (1.06×10 −3 S cm −1 at 25 °C) is achieved for the PIMs‐based SSEs. The mechanically strong (50.0 MPa) and non‐flammable SSEs combine the two superiorities of outstanding Li + conductivity and electrochemical stability, which can restrain the dendrite growth and prevent Li symmetric batteries from short‐circuiting even after more than 2200 h cycling. Benefiting from the rational design of SSEs, PIMs‐based SSEs Li‐metal batteries can achieve good cycling performance and superior feasibility in a series of withstand abuse tests including bending, cutting, and penetration. Moreover, the PIMs‐based SSEs endow high specific capacity (11307 mAh g −1 ) and long‐term discharge/charge stability (247 cycles) for solid‐state Li−O 2 batteries. The PIMs‐based SSEs present a powerful strategy for enabling safe operation of high‐energy solid‐state batteries.