亚微米LiFe0.05Mn1.95O4正极材料的制备及电化学性能

doi:10.16085/j.issn.1000-6613.2020-1718

摘要/Abstract

摘要：

采用固相燃烧法合成了亚微米单晶多面体LiFe_0.05Mn_1.95O₄正极材料。借助XRD、FE-SEM、TEM、XPS和恒电流充放电等手段对样品的结构、形貌、物相组成和电化学性能进行测试。结果表明，Fe掺杂未改变尖晶石型LiMn₂O₄的立方晶系结构，其{400}和{440}衍射峰相对应的晶面出现显著的择优生长，形成了形貌为{111}、{110}和{100}晶面的单晶去顶角八面体晶粒。LiFe_0.05Mn_1.95O₄正极材料表现出比纯LiMn₂O₄材料更为优异的电化学性能，在1C和5C时有着114.7mA·h/g、104.7mA·h/g首次放电比容量，10C倍率下经1000次循环后，容量保持率为83.9%。循环伏安与阻抗分析得出掺杂后的样品有着较大的锂离子扩散系数与较小的活化能。对5C倍率循环1000次后Fe掺杂样品的极片分析发现，其晶体结构基本无变化，适量的Fe掺杂能够有效抑制尖晶石型LiMn₂O₄在充放电循环过程中的Jahn-Teller效应以及Mn的溶解，提升材料的结构稳定性与容量保持率。

关键词: 尖晶石型LiMn₂O₄, Fe掺杂, 单晶多面体, 亚微米, 正极材料, Mn溶解, 电化学, 动力学

Abstract:

The cathode material of submicron LiFe_0.05Mn_1.95O₄ single crystal was synthesized by a solid state combustion method. The structure, morphology, phase composition and electrochemical performance of the sample were investigated by XRD, FE-SEM, TEM, XPS and galvanostatic charge and discharge. The results showed that, Fe-doping did not change the cubic crystal structure of spinel LiMn₂O₄, but the crystal surface corresponding to {400} and {440} diffraction peak exhibited a significant selective growth, and the single crystal deciding-angle octahedral grains with the morphologies of {111}, {110} and {100} crystal surface were formed. The LiFe_0.05Mn_1.95O₄ cathode material exhibited better electrochemical performance than the undoped sample of LiMn₂O₄. The initial specific discharge capacities were 114.7mA·h/g and 104.7mA·h/g at 1C and 5C, respectively. The capacity retention was 83.9% at 10C after 1000 cycles. By analyzing the cyclic voltammogram and electrochemical impedance spectroscopy, we found that the Fe-doped sample possessed large lithium ion diffusion coefficient and low apparent activation energy. The spinel structure of the sample's electrode slice was almost unchanged after 1000 cycles at 5C. Appropriate Fe-doping can effectively inhibit the Jahn-Teller effect and the Mn dissolution of spinel LiMn₂O₄in the process of charge and discharge cycles, and hence improve the capacity retention and structural stability of the material.

Key words: spinel LiMn₂O₄, Fe-doping, single crystal polyhedron, submicron, cathode material, Mn dissolution, electrochemistry, kinetics

中图分类号:

TM912

刘红雷, 郭俊明, 向明武, 白玮, 白红丽, 刘晓芳, 段开娇. 亚微米LiFe_0.05Mn_1.95O₄正极材料的制备及电化学性能[J]. 化工进展, 2021, 40(7): 3915-3922.

LIU Honglei, GUO Junming, XIANG Mingwu, BAI Wei, BAI Hongli, LIU Xiaofang, DUAN Kaijiao. Synthesis and electrochemical performance of submicron LiFe_0.05Mn_1.95O₄ cathode material[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3915-3922.

图/表 9

图1 LMO和LFMO样品的XRD图谱

图2 LMO和LFMO的SEM图及LFMO的结构图

图3 LFMO的XPS全谱图、Fe 2p的谱图以及LFMO、LMO的Mn 2p3/2拟合曲线

图4 LMO和LFMO样品的放电曲线

图5 LMO和LFMO在1C、25℃循环前后极片的XRD图谱

表1 LMO和LFMO样品在1C、25℃循环前后的XRD谱图中的峰强度比

衍射峰强度的比值	LMO	LFMO
R_（111）	0.57	0.92
R_（311）	0.62	0.84
R_（400）	0.46	0.65

图6 25℃条件下LMO与LFMO充放电前与5C倍率1000次后的CV图

图7 25℃条件下LMO与LFMO电极在充放电前与5C条件下充放电循环1000次后的交流阻抗图及Z′与ω-1/2在低频区域拟合图

图8 LMO与LFMO电极在不同温度下的交流阻抗图及相应曲线的lgi0与1000/T的Arrhenius关系图

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亚微米LiFe_0.05Mn_1.95O₄正极材料的制备及电化学性能

Synthesis and electrochemical performance of submicron LiFe_0.05Mn_1.95O₄ cathode material

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