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Interface stabilization of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether to high-voltage Li-rich Mn-based layered cathode materials

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Non-aqueous electrolyte solvents play a pivotal role in improving the cycling performance of high-voltage Li-rich Mn-based layered cathode materials. In this study, a fluoroether (1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, TFEPE) was added to 1.2 mol·L−1 LiPF6 EC/EMC/DEC at different concentrations to synthesize a series of electrolytes for enhancing the cycling performance of high-voltage Li1.18Mn0.50Ni0.26Co0.06O2 (LMNC). Effects of TFEPE on the electrochemical performance of LMNC at 0.1C and 1.0C rates were investigated. Scanning electron microscopy was used to observe the surface morphology of LMNC before and after cycling. X-ray photoelectron spectroscopy was conducted to analyze the surface compositions and chemical states, and transmission electron microscopy was performed to directly examine the changes in the structure of LMNC before and after cycling. Results suggested that TFEPE was preferentially oxidized and produced inorganic compounds (MeF and Li2CO3) on the surface of LMNC, which effectively inhibited the side reactions between LMNC and the electrolyte. MeF and Li2CO3 delayed the propagation of the phase transitions of LMNC primary particles from the surface to the bulk, thereby improving the cycling performance of LMNC.

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摘要

非水电解质溶剂对改善高压富锂锰基层状阴极材料的循环性能起着关键作用。在本研究中, 将不同浓度的氟代醚(1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚, TFEPE) 添加到1.2 mol·L−1 LiPF6 EC/EMC/DEC中, 配置了一系列电解液, 用于提升高压Li1.18Mn0.50Ni0.26Co0.06O2( LMNC) 的循环性能。研究了TFEPE在0.1C和1.0C下对LMNC电化学性能的影响, 并利用扫描电子显微镜观察循环前后LMNC的表面形貌, 同时采用X射线光电子能谱分析了LMNC的表面组成和化学状态, 最后用透射电子显微镜直接观察了LMNC在循环前后的结构变化。研究结果表明, TFEPE能优先被氧化, 并在LMNC表面生成无机化合物( MeF和Li2CO3) , 因此有效抑制了LMNC与电解液之间的副反应, 并减缓了LMNC一次颗粒从表面到体相的尖晶石相转变, 从而改善了LMNC的循环性能。

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Acknowledgements

This work was financially supported by the National Science Foundation for Young Scientists of China (No. 22005264), Beijing Natural Science Foundation Program (No. L182023) and the Youth Fund Project of GRINM (No. 12620203129011).

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Authors and Affiliations

  1. National Power Battery Innovation Center, Grinm Group Company Ltd, Beijing, 100088, China

    A-Lin Li, Guo-Hua Li, Shi-Gang Lu, Hao-Xiang Zhuo, Gang-Ning Zhang, Fu-Juan Han, Yi-Mian Xia, Jing Wang & Yi Zhang

  2. China Automotive Battery Research Institute Company Ltd, Beijing, 101407, China

    A-Lin Li, Guo-Hua Li, Shi-Gang Lu, Zhi-Min Ren, Jian-Tao Wang, Hao-Xiang Zhuo, Wei Quan, Gang-Ning Zhang, Fu-Juan Han, Yi-Mian Xia, Jing Wang & Yi Zhang

  3. General Research Institute for Nonferrous Metals, Beijing, 100088, China

    A-Lin Li, Guo-Hua Li, Shi-Gang Lu, Jian-Tao Wang, Hao-Xiang Zhuo, Gang-Ning Zhang, Fu-Juan Han, Yi-Mian Xia, Jing Wang & Yi Zhang

  4. Materials Genome Institute, Shanghai University, Shanghai, 200444, China

    Shi-Gang Lu

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  1. A-Lin Li
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Li, AL., Li, GH., Lu, SG. et al. Interface stabilization of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether to high-voltage Li-rich Mn-based layered cathode materials. Rare Met. 41, 822–829 (2022). https://doi.org/10.1007/s12598-021-01845-7

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