Organic solid electrolytes compatible with all-solid-state Li metal batteries (LMBs) are essential to ensuring battery safety, high energy density, and long-term cycling performance. However, it remains a challenge to develop an approach to provide organic solid electrolytes with capabilities for the facile dissociation of strong Li-ion pairs and fast transport of ionic components. Herein, a diethylene glycol-modified pyridinium covalent organic framework (DEG-PMCOF) with a well-defined periodic structure is prepared as a multicomponent solid electrolyte with a cationic moiety of high polarity, an additional flexible ion-transporter, and an ordered ionic channel for all-solid-state LMBs. The DEG-containing pyridinium groups of DEG-PMCOF allow a lower dissociation energy of Li salts and a smaller energy barrier of Li-ion transport, leading to high ion conductivity (1.71 × 10-4 S cm-1) and a large Li-ion transfer number (0.61) at room temperature in the solid electrolyte. The DEG-PMCOF solid electrolyte exhibits a wide electrochemical stability window and effectively suppresses the formation of Li dendrites and dead Li in all-solid-state LMBs. Molecular dynamics and density functional theory simulations provide insights into the mechanisms for the enhanced Li-ion transport driven by the integrated diffusion process based on hopping motion, vehicle motion, and free diffusion of DEG-PMCOF. The all-solid-state LMB assembled with a DEG-PMCOF solid electrolyte displays a high specific capacity with a retention of 99% and an outstanding Coulombic efficiency of 99% at various C-rates during long-term cycling. This DEG-PMCOF approach can offer an effective route to design various solid-state Li batteries.
Keywords: all-solid-state lithium metal battery; and organic solid electrolyte; covalent organic framework; dendrite-free; multicomponent ionic conductor.