Imidazolium-Type Poly(ionic liquid) Endows the Composite Polymer Electrolyte Membrane with Excellent Interface Compatibility for All-Solid-State Lithium Metal Batteries

Developing a poly(ethylene oxide) (PEO)-based polymer electrolyte with high ionic conductivity and robust mechanical property is beneficial for real applications of all-solid-state lithium metal batteries (ASSLMBs). Herein, an excellent organic/inorganic interface compatibility of all-solid-state composite polymer electrolytes (CPEs) is achieved using a novel imidazolium-type poly(ionic liquid) with strong electrostatic interactions, providing insights into the achievement of highly stable CPEs. The key properties such as micromorphologies, thermal behavior, crystallinity, t_Li⁺, mechanical property, lithium anode surficial morphology, and electrochemical performance are systematically investigated. The combined experimental and density functional theory (DFT) simulation results exhibit that the strong electrostatic interaction and ion–dipole interaction cooperated to improve the compatibility of the CPE, with a high ionic conductivity of 1.46 × 10^–4 S cm^–1 at 40 °C and an incredible mechanical strain of 2000% for dendrite-free and highly stable all-solid-state LMBs. This work affords a promising strategy to accelerate the development of PEO-based polymer electrolytes for real applications in ASSLMBs.