AbstractThe nanosized rod‐like LiMnPO4/C cathode materials have successfully in situ synthesized on the surface of flaky structure MnPO4·H2O self‐sacrificing template by the hydrothermal method. The crystal microstructure, micro shape, and electrochemical parameters of LiMnPO4/C are comprehensively studied by XRD, SEM, TEM, and electrochemical measurement methods. The physical and chemical properties analysis confirms that the vinyl acetate solution (VAc‐H2O) with a proper molar ratio is beneficial to generate orthorhombic olivine structure LiMnPO4 with microporous structure and nanorod‐shaped morphology. The electrochemical measurement results indicate that LMP‐X1‐AA sample delivers an initial discharge capacity of 148.1 mAh g−1 at 0.05 C, the capacity retention rate still maintains at 89.2% after 200 cycles. As the discharge rate increases to 1 C, the discharge capacity still remains at 133.4 mAh g−1. The results indicate that the synergistic effect of nanosized rod‐like morphology and conductive carbon coating is beneficial to improving the lithium ions diffusivity and electrochemical properties of LiMnPO4 materials.