Synthesis and modification of F-doped olivine LiFe0.5Mn0.5PO4 cathode materials for Li-ion batteries

doi:10.16085/j.issn.1000-6613.2023-1224

Abstract

Abstract:

At present, LiFePO₄ materials is difficult to meet the demand of high energy density. LiMn _x Fe_1-_x PO₄ (LMFP) cathode materials exhibit higher energy density compared with LiFePO₄, while maintain the advantage of low cost and high stability of olivine structure. However, the inferior rate and cycle performance limit its practical application, which is ascribed by poor Li-ion diffusion kinetic and Jahn-Teller effect of Mn³⁺. In this work, a F-doping strategy was proposed to construct 110nm nanoparticles of LMFP with highly ordered b-axis orientation. The basic physicochemical properties and electrochemical properties of materials were explored, finding that the exposed (010) crystal face acted as Li-ion diffusion channel can significantly improve the Li-ion transport efficiency, while the doped F ions can increase the Li—O bond distance and the PO₄^3- binding energy to enhance the stability of crystal structure. Therefore, the reversible specific discharge capacity of the F-doped LMFP was 153mA·h/g and 106mA·h/g at 0.1C and 5C, respectively. After 750 cycles at 1C, the capacity retention increased from 90.6% to 96.4% compared with the unmodified material.

Key words: electrochemistry, lithium iron manganese phosphate (LiMn_0.5Fe_0.5PO₄), cathode, lithium-ion battery, F-doping

摘要：

目前磷酸铁锂材料由于其较低的能量密度难以满足使用需求。磷酸锰铁锂具有比磷酸铁锂更高的能量密度，同时兼顾磷酸铁锂低成本和晶体结构稳定性的特点。然而缓慢的锂离子扩散动力学和Mn³⁺引起的Jahn-Teller效应导致材料的循环和倍率性能差，限制了磷酸锰铁锂实际应用。本工作通过引入F离子掺杂，构筑沿b轴取向生长的110nm纳米颗粒磷酸锰铁锂正极材料，探究了它们的基本物理化学性质与电化学性能，发现沿b轴取向生长并暴露的(010)晶面能够显著提升锂离子扩散动力学。此外，F离子引入显著增强了Li—O键以及PO₄^3-骨架结构，提高锂离子嵌入和脱出过程中晶体结构稳定性。因此，在0.1C和5C电流下，改性磷酸锰铁理正极材料可逆放电比容量分别为153mA·h/g和106mA·h/g。相比于未改性材料，1C循环750次后比容量保持率从90.6%提升到96.4%。

关键词: 电化学, 磷酸锰铁锂, 正极, 锂离子电池, 氟掺杂

CLC Number:

TB32

YU Songmin, JIN Hongbo, YANG Minghu, YU Haifeng, JIANG Hao. Synthesis and modification of F-doped olivine LiFe_0.5Mn_0.5PO₄ cathode materials for Li-ion batteries[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 302-309.

于松民, 金洪波, 杨明虎, 余海峰, 江浩. 氟掺杂改性LiMn_0.5Fe_0.5PO₄正极材料及其电化学性能[J]. 化工进展, 2024, 43(1): 302-309.

Figures/Tables 5

References 37

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Synthesis and modification of F-doped olivine LiFe_0.5Mn_0.5PO₄ cathode materials for Li-ion batteries

氟掺杂改性LiMn_0.5Fe_0.5PO₄正极材料及其电化学性能

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