Cation Framework Nanowires Enabling Composite Solid‐State Electrolyte with Anion Exchange Platform for Rapid Li⁺ Conduction

Abstract All‐solid‐state lithium metal batteries (ASSLMBs) have attracted significant attention due to their high energy density and improved safety performance. However, the application of ASSLMBs in energy storage fields is hindered by their low ionic conductivity, which arises from the limited availability of free Li⁺ in composite solid‐state electrolytes (CSEs). Herein, a unique nanowire with the 3D cation framework is employed as an inorganic filler to increase the availability of free Li⁺ with the anion exchange platform. The cation framework with active Cl⁻ can serve as the exchange platform to attract the TFSI⁻, thereby promoting the dissociation of LiTFSI and the release of additional free Li⁺. Furthermore, cation framework nanowires exhibit the stable framework structure and highly ordered channels, which form the 1D continuous organic–inorganic interface, facilitating the practical pathways for directional Li⁺ conduction. As a result, the YBFPL electrolyte exhibits the high ionic conductivity (0.267 mS cm⁻¹) at room temperature, the high Li⁺ transference number (0.63), and the more mobile Li⁺ ratio (40%). This study designs the 1D continuous cation framework nanostructure, which realizes the rapid Li⁺ transport through the anion exchange platform at the organic and inorganic interface.