An integrated “rigid–flexible” strategy by side chain engineering towards high ion-conduction cationic covalent organic framework electrolytes

In recent years, solid-state lithium metal batteries (SSLMBs) have become a new development trend, and it has become a top priority to design solid-state electrolytes (SSEs) that can rapidly and stably transport lithium ions in a variety of climatic environments. In this work, an integrated "rigid-flexible" dual-functional strategy is proposed to develop a cationic covalent organic framework (EO-BIm-iCOF) with well-defined flexible oligo(ethylene oxide) (EO) chains as an SSE for SSLMBs. As expected, the synergistic effects of the rigid cationic framework and flexible EO chains not only promote the dissociation of LiTFSI salts, but also greatly improve the transport of lithium ions, which endows LITFSI@EO-BIm-iCOF SSEs with a high Li⁺ conductivity of 1.08 × 10^-4 S cm^-1 and ionic transference number of 0.69 at room temperature. Besides, the molecular dynamics (MD) simulations have also elucidated the diffusion and transport mechanism of lithium ions in LITFSI@EO-BIm-iCOF SSEs. Interestingly, the assembled SSLMBs wherein LiFePO₄ is paired with LITFSI@EO-BIm-iCOF SSEs display decent electrochemical properties at higher and lower temperatures. This work provides a great development prospect for the application of cationic COFs in solid-state batteries.