Olivine-type LiMnPO4/C nanorods were successfully synthesized in a chloride/ethylene glycol-based deep eutectic solvent (DES) at 130 °C for 4 h under atmospheric pressure. As-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and electrochemical tests. The prepared LiMnPO4/C nanorods were coated with a thin carbon layer (approximately 3 nm thick) on the surface and had a length of 100–150 nm and a diameter of 40–55 nm. The prepared rod-like LiMnPO4/C delivered a discharge capacity of 128 mAh·g−1 with a capacity retention ratio of approximately 93% after 100 cycles at 1 C. Even at 5 C, it still had a discharge capacity of 106 mAh·g−1, thus exhibiting good rate performance and cycle stability. These results demonstrate that the chloride/ethylene glycol-based deep eutectic solvents (DES) can act as a new crystal-face inhibitor to adjust the oriented growth and morphology of LiMnPO4. Furthermore, deep eutectic solvents provide a new approach in which to control the size and morphology of the particles, which has a wide application in the synthesis of electrode materials with special morphology.

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