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In this work, LiFePO4/C (LFP/C) cathode materials with superior electrochemical performance have been prepared by coaxial and uniaxial electrospinning method. The electrode materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Also, cyclic voltammetry (CV), galvanostatic charge-discharge, and electrochemical impedance spectroscopy (EIS) measurements were performed on these materials. The experimental results indicate that the electrochemical properties of LFP/C-C, such as specific capacity, coulombic efficiency, Li + diffusion coefficient and overpotential are significantly improved. The enhanced electrical conductivity and polarization of the LFP/C-C electrode are mainly due to its porous morphology and amorphous carbon coating layer.