Interfacial Reconstruction Unlocks Inherent Ionic Conductivity of Li‐La‐Zr‐Ta‐O Garnet in Organic Polymer Electrolyte for Durable Room‐Temperature All‐Solid‐State Batteries

Abstract Rigid‐flexible coupled composite polymer electrolytes (CPEs, e.g., polyethylene oxide/Li6.4La3Zr1.4Ta0.6O12, PEO/LLZTO) hold the promise of integrating the respective merits of organic polymer electrolyte and inorganic ceramic fillers to achieve better all‐solid‐state batteries (ASSBs), but commonly suffer from poor synergistic effect owing to the ionically/electronically resistive layer on the ceramic surface. Representatively, the Li2CO3 passivation layer‐isolated LLZTO not only contributes minimally to the Li+ conduction in PEO/LLZTO CPE, but also narrows the available electrochemical window. Herein, an interfacial reconstruction strategy is disclosed based on mild liquid‐phase chemical reaction and subsequent self‐assembly, allowing the detrimental Li2CO3 to fully react with succinic anhydride (SA), and simultaneously constructing a robust ultra‐thin lithium succinate (SALi) ionic conductor shell to eradicate its regeneration. Accordingly, the obtained PEO/LLZTO@SALi (PLS) CPE shows a high room‐temperature ionic conductivity (1.2 × 10−4 S cm−1), a wide electrochemical window (4.8 V), a notable Li+ transference number (0.37), as well as nonflammability and exceptional compatibility with Li metal in Li/Li symmetric cells (2000 h at 0.2 mA cm−2). More encouragingly, the Li/PLS CPE/LiFePO4 full ASSB maintains an ultrahigh capacity retention of 84.3% after 1400 cycles at room temperature. This work propels the design of high‐performance CPEs through the interfacial modulation of inorganic ceramic fillers.