Solid electrolytes play a pivotal role in these batteries but are hindered by challenges such as low ion conductivity and inadequate mechanical properties. In this study, a synergistic multi-component system was fabricated using a microphase separation technique to integrate liquid crystal polymers with self-assembly characteristics and polyethylene oxide (PEO) known for its excellent ion transport performance. Molecular-level control was achieved by adjusting the ratio of liquid crystal monomers, facilitating the construction of ordered ion transport pathways that significantly enhance room temperature ion transport efficiency. The resulting solid polymer electrolyte adopts a semi-interpenetrating network structure, where the rigid framework of liquid crystalline polymers is interpenetrated with flexible PEO chains. It exhibits a high room-temperature ion conductivity of 4.7 × 10−4 S/cm and a lithium-ion migration number of 0.71. Benefitting from its tailored microstructure and mechanical properties, the assembled lithium symmetric battery demonstrated stable operation over 2800 h at a room temperature current density of 0.1 mA/cm−2. This research presents a promising pathway for the advancement of advanced electrolyte materials, providing valuable insights into improving the efficiency and safety of lithium metal batteries in practical applications.
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