Ceramic-Topological Polymer Composite Electrolytes: Interfacial Engineering via Dynamic Coordination-Driven Networks for Long-Life, High-Voltage Solid-State Lithium Metal Batteries

Abstract

Polymer-ceramic composite solid-state electrolytes offer transformative potential for high-energy-density lithium metal batteries but face challenges such as ceramic agglomeration and interfacial incompatibility. Herein, we report a ceramic-topological polymer composite electrolyte synthesized via in situ thermally initiated free radical polymerization. By the weak coordination-inducing effect between surface-modified Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP@M) particles and a poly(ethylene carbonate) matrix, uniform ceramic dispersion and interfacial adhesion are achieved. Simultaneously, a topological polymer architecture establishes a "dynamic interfacial continuum", bridging ceramic domains and supporting efficient Li⁺ conduction. The resultant electrolyte exhibits a ceramic-rich "polymer-in-ceramic" structure, in which the LATP@M phase acts as the conducting network, suppressing dendrite growth while ensuring rapid ion transport. The optimized electrolyte demonstrates exceptional ionic conductivity (0.72 mS cm^-1), a high Li⁺ transference number (0.75), and an ultra-wide electrochemical stability window (5.7 V vs. Li/Li⁺). Full cells paired with LiFePO₄ and LiCoO₂ cathodes deliver outstanding cycling stability and Coulombic efficiency (> 99.5%), while flexible pouch cells retain functionality under mechanical abuse. This work provides a scalable strategy to harmonize ionic conduction, interfacial compatibility, and mechanical robustness in solid-state batteries, advancing the development of safe, long-lifespan energy storage systems.