Challenges toward higher temperature operation of LiFePO4

► Charge-discharge properties of LiFePO4 at 60 °C-115 °C were investigated. ► Elevating temperature up to 100 °C significantly enhanced reaction speed of LiFePO4. ► Side reaction to form resistive surface layer impede high-rate performance above 100 °C. ► Trade-off between fast kinetics and side reaction is to be considered at higher temperature. ► Miscibility gap do not shrink for samples with >40 nm at 115 °C.