Hybrid polymer electrolytes with excellent performance at high temperatures are very promising for developing solid-state lithium batteries for high-temperature applications. Herein, we use a self-supporting hydroxyapatite (HAP) nanowire membrane as a filler to improve the performance of a poly(ethylene oxide) (PEO)-based solid-state electrolyte. The HAP membrane could comprehensively improve the properties of the hybrid polymer electrolyte, including the higher room-temperature ionic conductivity of 1.05 × 10 S cm, broad electrochemical windows of up to 5.9 V at 60 °C and 4.9 V at 160 °C, and a high lithium-ion migration of 0.69. In addition, the LiFePO//Li full battery with a solid electrolyte possesses good rate capability, cycling, and Coulomb efficiency at extreme high temperatures, that is, after 300 continuous charge and discharge cycles at 4 C rate, the discharge capacity retention rate is 77% and the Coulomb efficiency is 99%. The use of the flexible self-supporting HAP nanowire membrane to improve the PEO-based solid composite electrolyte provides new strategies and opportunities for developing rechargeable lithium batteries in extreme high-temperature applications.
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