Recent Development of LiMnPO4 as Cathode Materials of Lithium-ion Batteries

doi:10.6023/A14010007

Abstract

Similar to LiFePO₄, LiMnPO₄ possesses the following advantages: eco-friendliness, low cost and excellent safety performance. Moreover, high energy density (～700 Wh·kg^-1) of LiMnPO₄ is 20% larger than LiFePO₄, which is due to LiMnPO₄ with high operating voltage ～4.1 V vs. Li falling within the electrochemical stability window of conventional electrolyte solutions. Therefore, LiMnPO₄ is considered as a next generation cathode material for lithium-ion batteries. However, the lithium ion conductivity of LiMnPO₄ is lower than that of LiFePO₄. The main difference between the kinetics in the initial stage of charging of two olivine materials may originate from the formation energy of vacancy-polaron complex in LiMnPO₄ than in LiFePO₄. In addition, the anisotropic lattice distortion of MnO₆ octahedron during repeated charge/discharge process hinders lithium removal/uptake reactions in LiMnPO₄ and thus leads to the large volume change. This distortion is not a strict Jahn-Teller effect but is a preferential elongation of two of the equatorial Mn—O bonds (edge-sharing with the PO₄). These intrinsic defects result in rapid capacity fading upon extended cycling and poor rate capability during cycles. To overcome these problems, it is an effective approach to prepare nanometer-sized and rod/sheet-like materials through proper synthesis method. These special morphologies in LiMnPO₄ can stimulate the rate of Li extraction/insertion. However, the surface structural instability of particles may occur at size d<35 nm. The awkward situation may be solved by effective surface coating. Surface coating can decrease the disorder toward amorphous state and the poison of impurities on the surface of particles; especially, coating can promote the ionic and electronic conductivity. Therefore, a coating leads to a remarkable improvement of the electrochemical performance of LiMnPO₄. In addition, doping is also a method for improving the electrochemical property of LiMnPO₄. As a Fe-doped material, LiMn_yFe_1-yPO₄ has been widely investigated. In this paper, the recent advances in LiMnPO₄ as cathode materials of lithium-ion batteries are reviewed. The characteristics, morphologies, and possible reaction mechanisms of the material were summarized systematically. Some open questions (e.g. the facticity of Jahn-Teller effect in LiMnPO₄, the thermal stability of LiMnPO₄, etc.) are discussed in detail. Moreover, some improved methods (controlling the particle morphology, surface coating, and doping) for the electrochemical property of LiMnPO₄ are expounded.

Key words: LiMnPO₄, Jahn-Teller effect, thermal stability, morphology, synthesis processes, surface coating, doping

Cite this article

Wan Yang, Zheng Qiaoji, Lin Dunmin. Recent Development of LiMnPO₄ as Cathode Materials of Lithium-ion Batteries[J]. Acta Chimica Sinica, 2014, 72(5): 537-551.

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锂离子电池正极材料磷酸锰锂研究进展

Recent Development of LiMnPO₄ as Cathode Materials of Lithium-ion Batteries

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