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高倍率容量LiAl0.03Co0.03Mn1.94O4正极材料制备及电化学性能研究
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1.云南民族大学 化学与环境学院 云南省高校绿色化学材料重点实验室,云南 昆明 650500;2.昆明理工大学 环境科学与工程学院,云南 昆明 650093;3.宁夏中环光伏材料有限公司,宁夏 银川 750000

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TM912

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国家自然科学基金(51972287)


Preparation and Electrochemical Properties of LiAl0.03Co0.03Mn1.94O4 Cathode Material with High-Rate Capacity
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1.Key Laboratory of Green-Chemistry Materials in University of Yunnan Province, School of Chemistry and Environment, Yunnan Minzu University, Kunming 650500, China;2.Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650093, China;3.Ningxia Zhonghuan Photovoltaic Materials Co., Ltd, Yinchuan 750000, China

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    摘要:

    尖晶石型LiMn2O4易发生Jahn-Teller畸变和Mn溶解,容量衰减较快,限制了商业化应用。通过低温固相燃烧法快速合成了Al-Co共掺LiAl0.03CoxMn1.97-xO4(x≤0.08)正极材料。结果表明,Al-Co共掺降低了截断八面体{111}、{100}、{110}晶面的表面能位垒,增加了异质形核的形成,促进了截断八面体晶体的发育,减缓了Mn溶解和扩展了Li+扩散通道。优化的LiAl0.03Co0.03Mn1.94O4正极材料具有更完整的截断八面体单晶颗粒形貌,其Mn平均化合价从+3.5增大到+3.545,有效抑制了Jahn-Teller畸变和稳定了晶体结构,提高了高倍率容量和长循环性能,在5和10 C下初次放电比容量分别为108.6和 104.9 mAh/g,长循环2000次后保持率高达70.4%和75.5%;更高倍率20 C下,500次循环后容量损失率仅为9.3%。且其具有较小活化能(22.84 kJ/mol)和较大锂离子扩散系数(5.47×10-16 cm2/s),表明其具有良好的锂离子迁移动力学性能。

    Abstract:

    The rapid capacity decay of spinel LiMn2O4 is attributed to the occurrence of Jahn-Teller distortion and Mn dissolution, which restricts commercial application. Herein, a low temperature solid state combustion method was employed to synthesize various LiAl0.03CoxMn1.97-xO4 (x≤0.08) cathode materials. The results show that Al-Co co-doping reduces the surface energy barrier of truncated octahedral {111}, {100} and {110} crystal faces, increases the heterogeneous nucleation, promotes the development of truncated octahedral crystals, reduces Mn dissolution and widens the Li+ diffusion channels. The optimal LiAl0.03Co0.03Mn1.94O4 cathode material has a single-crystal particle morphology of completely truncated octahedron and its average Mn valence increases from +3.5 to +3.545, thereby effectively inhibiting Jahn-Teller distortion, stabilizing the crystal structure, and improving the high-rate performance and long-cycle life of the material. At 5 and 10 C, it delivers the first discharge capacities of 108.6 and 104.9 mAh/g with the high capacity retentions of 70.4% and 75.5% after 2000 long cycles, respectively. At a higher rate of 20 C, it shows a low-capacity fade of 9.3% after 500 cycles. The LiAl0.03Co0.03Mn1.94O4 material has a low apparent activation energy (22.84 kJ/mol) and a relatively high Li+ diffusion coefficient (5.47×10-16 cm2/s), indicating that it has a good lithium-ion migration kinetics.

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钱志慧,朱琴,马姣,陶扬,郭昱娇,卢瑶,宁平,郭俊明.高倍率容量LiAl0.03Co0.03Mn1.94O4正极材料制备及电化学性能研究[J].稀有金属材料与工程,2025,54(5):1307~1316.[Qian Zhihui, Zhu Qin, Ma Jiao, Tao Yang, Guo Yujiao, Lu Yao, Ning Ping, Guo Junming. Preparation and Electrochemical Properties of LiAl0.03Co0.03Mn1.94O4 Cathode Material with High-Rate Capacity[J]. Rare Metal Materials and Engineering,2025,54(5):1307~1316.]
DOI:10.12442/j. issn.1002-185X.20240034

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  • 收稿日期:2024-01-16
  • 最后修改日期:2024-03-22
  • 录用日期:2024-03-26
  • 在线发布日期: 2025-05-23
  • 出版日期: 2025-05-22