Solvothermal-assisted morphology evolution of nanostructured LiMnPO4 as high-performance lithium-ion batteries cathode

doi:10.1016/j.jmst.2018.04.017

Abstract

Abstract:

As a potential substitute for LiFePO₄, LiMnPO₄ has attracted more and more attention due to its higher energy, showing potential application in electric vehicle (EV) or hybrid electric vehicle (HEV). In this work, solvothermal method was used to prepare nano-sized LiMnPO₄, where ethylene glycol was used as solvent, and lithium acetate (LiAc), phosphoric acid (H₃PO₄) and manganese chloride (MnCl₂) were used as precursors. The crystal structure and morphology of the obtained products were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The electrochemical performance was evaluated by charge-discharge cycling, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the molar ratio of LiAc:H₃PO₄:MnCl₂ plays a critical role in directing the morphology of LiMnPO₄. Large plates transform into irregular nanoparticles when the molar ratio changes from 2:1:1 to 6:1:1. After carbon coating, the product prepared from the 6:1:1 precursor could deliver discharge capacities of 156.9, 122.8, and 89.7 mAh g^-1 at 0.05C, 1C and 10C, respectively. The capacity retention can be maintained at 85.1% after 200 cycles at 1C rate for this product.

Key words: Lithium manganese phosphate, Cathode, Solvothermal reaction, Lithium-ion battery, Electrochemical performance

Chongjia Zhu, Zhiqiu Wu, Jian Xie, Zhen Chen, Jian Tu, Gaoshao Cao, Xinbing Zhao. Solvothermal-assisted morphology evolution of nanostructured LiMnPO₄ as high-performance lithium-ion batteries cathode[J]. J. Mater. Sci. Technol., 2018, 34(9): 1544-1549.

Figures/Tables 9

Fig. 1. (a) Crystal structure of olivine-type LiMnPO4 projected along the [010] and (b) lithium-ion diffusion pathway parallel to [010].

Fig. 2. XRD patterns of (a) LiMnPO4 and (b) LiMnPO4/C.

Fig. 3. SEM images of as-obtained LiMnPO4: (a) LMP-2; (b) LMP-2.5; (c) LMP-3; (d) LMP-4; (e) LMP-5; (f) LMP-6.

Fig. 4. (a) TEM, (b) HRTEM images and (c) SAED pattern of carbon-coated LMP-5.

Fig. 5. Discharge profiles of (a) LMP-2, (b) LMP-2.5, (c) LMP-3, (d) LMP-4, (e) LMP-5, (f) LMP-6, (g) rate performance of LMP-x and (h) median voltage (voltage at half of discharge capacity) vs. current rate.

Fig. 6. Cycling performance of carbon-coated LMP-x at (a) 1C and (b) 5C.

Fig. 7. (a) CV plots of LMP-5 and (b) linear response of cathodic peak current density as a function of square root of scan rate (R: goodness of fit; m: weight of active material on the electrode).

Fig. 8. (a) EIS plots of cells after 5 cycles at 0.05C and (b) corresponding equivalent circuit.

Fig. 9. Comparison of rate capability of sample and some typical LiMnPO4/C materials reported previously. The inset gives the LiMnPO4/conductive carbon/binder weight ratio.

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Solvothermal-assisted morphology evolution of nanostructured LiMnPO₄ as high-performance lithium-ion batteries cathode

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