去顶角八面体LiFe0.12Mn1.88O4正极材料制备及电化学性能

杨梅; 陈奕妃; 刘红雷; 向明武; 郭昱娇; 刘晓芳; 郭俊明

硅酸盐学报, 2022, 50 (7): 1865, 网络出版: 2022-12-06

去顶角八面体LiFe_0.12Mn_1.88O₄正极材料制备及电化学性能

Preparation and Electrochemical Properties of Truncated Octahedral LiFe_0.12Mn_1.88O₄ Cathode Materials

论文大纲

杨梅 ¹陈奕妃 ¹刘红雷 ¹向明武 ¹郭昱娇 ^1,2刘晓芳 ¹郭俊明 ¹

作者单位

¹ 云南民族大学化学与环境学院，云南民族大学云南省高校绿色化学材料重点实验室，昆明 650500

² 昆明市生态环境局五华分局生态环境监测站，昆明 650031

摘要

尖晶石型LiMn2O4正极材料由于Jahn-Teller效应和Mn溶解，在充放电过程中容量衰减严重，循环稳定性差。联合元素掺杂和单晶形貌调控策略，采用固相燃烧法制备了具有{111}、{100}和{110}晶面的去顶角八面体单晶LiFe0.12Mn1.88O4正极材料。研究结果表明，Fe掺杂没有改变尖晶石型LiMn2O4的晶体结构，有效抑制了Jahn-Teller效应，促进了材料的结晶性及{400}和{440}衍射峰晶面的择优生长，表现出良好的倍率性能和容量保持率。在25 ℃，1 C和5 C倍率下LiFe0.12Mn1.88O4的首次放电比容量分别为105.2 mA·h/g和92.4 mA·h/g，1 000次循环后容量保持率分别为71.1%和75.2%；在高倍率10 C下，经1 000次循环后，其容量保持率可达到88.4%。在55 ℃和1 C条件下，首次放电比容量为108.6 mA·h/g，经150次循环后，容量保持率为79.1%。通过循环伏安和电化学阻抗分析，Fe掺杂材料具有较好的循环可逆性和较大的Li+扩散系数。Fe掺杂去顶角八面体LiMn2O4材料既抑制了Jahn-Teller效应，又减缓了Mn的溶解，稳定晶体结构，同时增加Li+迁移通道，提高电化学倍率性能及长循环寿命。

Abstract

Spinel LiMn2O4 cathode materials suffer a serious capacity decay and a poor cycle stability during the charge-discharge process due to the Jahn-Teller effect and Mn dissolution. A cathode material of truncated octahedral single crystal LiFe0.12Mn1.88O4 with {111}, {100} and {110} surfaces was prepared by a solid-state combustion method and element doping and single crystal morphology controlling strategies. The results show that the crystal structure of spinel LiMn2O4 is not changed by Fe doping, the Jahn-Teller effect is effectively inhibited, the crystallinity and the selective growth of {400} and {440} diffraction peak crystal planes are promoted, and the material has superior rate performance and capacity retention. The initial discharge specific capacities at 1 C and 5 C at 25 ℃ are 105.2 mA·h/g and 92.4 mA·h/g, and the capacity retentions after 1 000 cycles are 71.1% and 75.2%, respectively. Moreover, the capacity retention reaches 88.4% after 1 000 cycles at 10 C. The initial discharge capacity of the material is 108.6 mA·h/g at 55 ℃ and 1 C, and the capacity retention rate is 79.1% after 150 cycles, and the capacity retention rate is 79.1% after 150 cycles. By using cyclic voltammetry and electrochemical impedance spectroscopy, we found that the Fe-doped sample has superior circulation reversibility and large Li+ diffusion coefficient. The Fe-doped material of truncated octahedral LiMn2O4 inhibits the Jahn-Teller effect, and slows down the Mn dissolution, thus stabilizing the crystal structure, increasing the Li+ migration channel, and improving the electrochemical rate performance and long cycle life.

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杨梅, 陈奕妃, 刘红雷, 向明武, 郭昱娇, 刘晓芳, 郭俊明. 去顶角八面体LiFe_0.12Mn_1.88O₄正极材料制备及电化学性能[J]. 硅酸盐学报, 2022, 50(7): 1865. YANG Mei, CHEN Yifei, LIU Honglei, XIANG Mingwu, GUO Yujiao, LIU Xiaofang, GUO Junming. Preparation and Electrochemical Properties of Truncated Octahedral LiFe_0.12Mn_1.88O₄ Cathode Materials[J]. Journal of the Chinese Ceramic Society, 2022, 50(7): 1865.

去顶角八面体LiFe_0.12Mn_1.88O₄正极材料制备及电化学性能

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