无钴富锂正极材料的氟化锂包覆改性研究

刘伟; 李金星; 徐涵颖; 李杰; 邱新平

doi:10.1007/s12613-022-2483-7

Volume 29 Issue 5

Apr. 2022

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文章导航 > 矿物冶金与材料学报（英文） > 2022 > 29(5): 917-924

Wei Liu, Jinxing Li, Hanying Xu, Jie Li, and Xinping Qiu, Stabilized cobalt-free lithium-rich cathode materials with an artificial lithium fluoride coating, Int. J. Miner. Metall. Mater., 29(2022), No. 5, pp. 917-924. https://doi.org/10.1007/s12613-022-2483-7

Cite this article as:

Wei Liu, Jinxing Li, Hanying Xu, Jie Li, and Xinping Qiu, Stabilized cobalt-free lithium-rich cathode materials with an artificial lithium fluoride coating, Int. J. Miner. Metall. Mater., 29(2022), No. 5, pp. 917-924. https://doi.org/10.1007/s12613-022-2483-7

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研究论文

无钴富锂正极材料的氟化锂包覆改性研究

1)
清华大学化学系有机光电子与分子工程重点实验室，北京 100084，中国
2)
北京科技大学冶金与生态工程学院，北京 100083，中国

通讯作者:
邱新平 E-mail: qiuxp@mail.tsinghua.edu.cn

文章亮点

(1) 开发了高温熔融法在无钴富锂锰基层状材料表面包覆LiF的方法。

(2) 系统地研究了在正极表面包覆LiF后对CEI界面的影响规律。

(3) 总结了材料循环稳定性和热稳定性提升的机理。

中文摘要

铁取代的无钴富锂锰基层状材料具有比容量高、安全性高和成本低等优点，被认为是最有潜力的下一代锂离子电池正极材料。然而，其在充放电过程中存在首圈库伦效率低、电压衰退和容量衰减等问题，严重制约了其商业化应用。在此，我们开发了一种通过高温熔融法在Li_1.2Ni_0.15Fe_0.1Mn_0.55O₂颗粒表面直接包覆LiF的方法，可以显著提高材料的循环稳定性和热稳定性。其中，表面包覆0.5wt%的LiF能显著提高其在高电位下的循环稳定性，在0.1 C下首次放电容量高达248 mAh∙g^–1，循环100次后容量保持率高达80.2%，放电平均点位衰减量仅为0.25 V，均远优于未包覆的材料。此外，表面包覆0.5wt%的LiF的材料的热安全性得到显著提升，T_onset从238C提升到274C，且放热量减少。分析结果表明，将阴极/电解质界面(cathode–electrolyte interphase, CEI)的主要成分LiF引入到正极材料表面，可以诱导在正极/电解质界面形成一层厚度约3 nm、均匀稳定的CEI膜，有效保护正极免受电解质的侵蚀，减少了过渡金属溶解，有效抑制了材料不可逆相变，并显著提升热安全性，为界面修饰提供了一种新的思路。

关键词:

Research Article

Stabilized cobalt-free lithium-rich cathode materials with an artificial lithium fluoride coating

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Abstract

Abstract

Iron-substituted cobalt-free lithium-rich manganese-based materials, with advantages of high specific capacity, high safety, and low cost, have been considered as the potential cathodes for lithium ion batteries. However, challenges, such as poor cycle stability and fast voltage fade during cycling under high potential, hinder these materials from commercialization. Here, we developed a method to directly coat LiF on the particle surface of Li_1.2Ni_0.15Fe_0.1Mn_0.55O₂. A uniform and flat film was successfully formed with a thickness about 3 nm, which can effectively protect the cathode material from irreversible phase transition during the deintercalation of Li⁺. After surface coating with 0.5wt% LiF, the cycling stability of Li_1.2Ni_0.15Fe_0.1Mn_0.55O₂ cycled at high potential was significantly improved and the voltage fade was largely suppressed.
- cobalt-free lithium-rich cathode materials;
- lithium fluoride coating;
- cycle stability;
- dissolution

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