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Recently, the application of LiFePO4 (LFP) batteries in electric vehicles has attracted extensive attention from researchers. This work presents a composite of LFP particles trapped in reduced graphene oxide (rGO) nanosheets obtained through the high-temperature reduction strategy. The obtained LiFePO4/rGO composites indicate spherical morphology and uniform particles. As to the structure mode of the composite, LFP distributes in the interlayer structure of rGO, and the rGO evenly covers the surface of the particles. The LFP/rGO cathodes demonstrate a reversible specific capacity of 165 mA h g−1 and high coulombic efficiency at 0.2 C, excellent rate capacity (up to 10 C), outstanding long-term cycling stability (98%) after 1000 cycles at 5 C. The combined high electron conductivity of the layered rGO coating and uniform LFP particles contribute to the remarkable electrochemical performance of the LFP/rGO composite. The unique LFP/rGO cathode provides a potential application in high-power lithium-ion batteries. [ABSTRACT FROM AUTHOR]