Nanofiber‐Architected Imidazole COF Enabling Ultrafast Desolvation‐Dissociation Kinetics in Quasi‐Solid‐State Lithium Metal Batteries

Abstract Developing a novel gel polymer electrolyte (GPE) constitutes an effective strategy for addressing retarded Li ⁺ transport and enabling ultrafast‐charging quasi‐solid‐state lithium metal batteries (QSLMBs). Herein, a novel imidazolium cationic covalent organic framework (ICOF) incorporated into a nanofibrous skeleton GPE (ICOFNS‐GPE) is reported, which accelerates desolvation‐dissociation kinetics for rapid and uniform Li ⁺ transport. In ICOF, imine/triazole bonds facilitate Li ⁺ desolvation via lithiophilic coordination, whereas imidazolium cations promote anion anchoring to enhance dissociation, collectively optimizing desolvation‐dissociation kinetics and stabilizing the Li anode. Furthermore, incorporating ICOF into polyacrylonitrile nanofiber networks forms hierarchical ion channels, enabling fast Li ⁺ transport. As a result, ICOFNS‐GPE exhibits both a high σ of 1.95 mS cm ⁻¹ and a high of 0.74, which are attributed to the accelerated ionic migration kinetics. The assembled Li || NCM811 cells with ICOFNS‐GPE can reach 133.0 mAh g ⁻¹ at 5 C (capacity retention rate of 83.2% after 300 cycles). ICOFNS‐GPE enables QSLMBs to achieve 73% capacity within 10 min and ensures stable operation under mechanical stresses (folding, pricking, cutting). This work presents a novel approach to engineering functional composite GPEs for ultrafast‐charging QSLMBs.