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Fluorine migration and in-situ doping for regeneration of Ni-rich LiNi0.9Co0.05Mn0.05O2 cathode material from spent lithium-ion batteries

废旧锂电池回收过程中氟的迁移及其原位掺杂再生制备LiNi0.9Co0.05Mn0.05O2正极材料

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Abstract

Recycling of spent lithium-ion batteries (LIBs) has raised wide concerns vis-à-vis resource value and environmental protection. Benefiting from the short process and high added value of the recycled products, the regeneration of cathode materials from spent LIBs is a popular approach. However, due to the lack of studies on fluorine (F) migration and the impact thereof on recycled materials, F control relies on deep removal and becomes a considerable challenge, limiting the generation of high-quality cathode materials. Herein, the migration-transformation behaviors of F are investigated in the integrated pyrolysis-leaching-regeneration process of spent LIBs. It is indicated that 45.71% of the amount of F is released into the atmosphere during pyrolysis and some amount of F in the leaching solution is adsorbed into coprecipitated precursors through coordination with metal ions and then regularly entering the lattices of the regenerated LiNi0.9Co0.05Mn0.05O2. Regarding the effects of F on the regenerated LiNi0.9Co0.05Mn0.05O2, a moderate F concentration (approximately 0.30 g L−1) in the leaching solution can boost the regenerated LiNi0.9Co0.05Mn0.05O2 material’s cycling stability (the capacity retention of 95.7% after 100 cycles at 1 C), due to the stabilizing effect of F-doping on the regenerated material’s structure. This study reveals the migration-transformation mechanisms of F during the recycling of spent LIB and provides a rational in-situ F-doping strategy for the regeneration of LiNi0.9Co0.05Mn0.05O2.

摘要

氟是废旧锂电池回收难以回避的典型杂质元素, 其迁移转化行 为复杂, 制约了高品质正极材料的可控再生制备. 本研究通过揭示废旧 锂电池在热解、浸出及高镍LiNi0.9Co0.05Mn0.05O2材料再生过程中氟的 迁移转化规律, 为氟的定向调控及材料的可控再生制备奠定理论基础. 实验结果表明: 热解过程中部分氟(45.71%)以气态热解产物的形式释 放到大气中, 而另一部分氟(52.34%)则向废三元材料的晶格内发生迁 移, 并随着湿法浸出溶解到镍钴锰的浸出液中. 浸出液中少量的氟会在 共沉淀制备前驱体过程中迁移到Ni0.9Co0.05Mn0.05(OH)2前驱体材料, 并 随着配锂烧结掺杂到再生LiNi0.9Co0.05Mn0.05O2材料表面. 进一步通过 调控氟含量发现, 当浸出液中氟浓度控制在0.30 g L−1时, 引入到再生 LiNi0.9Co0.05Mn0.05O2材料中的氟不仅不会引起不利相变, 而且能够稳 定材料结构, 从而有效提升再生高镍材料的循环稳定性(1 C电流密度 下循环100圈的容量保持率高达95.7%). 因此, 本研究不仅揭示了废旧 锂电池回收过程中氟的迁移转化行为, 而且可控再生制备了高性能氟 掺杂高镍LiNi0.9Co0.05Mn0.05O2正极材料, 为废旧锂离子电池回收过程 中氟的调控提供了理论依据.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (51904340), the Natural Science Foundation of Hunan (2021JJ2020066), the National Key Research and Development Program (2019YFC1907801, 2019YFC1907803 and 2019YFC1907804), and the Central South University Innovation-Driven Research Programme (2023CXQD009).

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Authors and Affiliations

  1. School of Minerals Processing and Bioengineering, Central South University, Changsha, 410083, China

    Tianyu Wang  (王天宇), Chenxing Yi  (易晨星), Peng Ge  (葛鹏), Li Wang  (王丽), Wei Sun  (孙伟), Meirong Wu  (吴美容) & Yue Yang  (杨越)

  2. School of Chemical Engineering, Zhengzhou University, Zhengzhou, 450001, China

    Chi Zhang  (张驰)

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  1. Tianyu Wang  (王天宇)
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Contributions

Yang Y conceived the idea, supervised the project, guided the experiment, and revised the manuscript; Wang T performed the experiments, processed and analyzed the data, wrote the original manuscript, and revised the manuscript with support from Ge P, Yi C, Wu M, Zhang C, Wang L and Sun W. All authors contributed to the general discussion.

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Correspondence to Yue Yang  (杨越).

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Supporting data are available in the online version of the paper.

Tianyu Wang received his Master’s degree from the Central South University in 2019. He is currently pursuing his PhD degree at the School of Minerals Processing and Bioengineering, Central South University. His research interests focus on recycling of spent LIBs and regeneration of high-energy cathode materials.

Chenxing Yi received his Master’s degree from Kunming University of Science and Technology in 2018. He is currently pursuing his PhD degree at the School of Minerals Processing and Bioengineering, Central South University. His research interests focus on recycling of spent LIBs.

Yue Yang received his PhD degree from the Institute of Nuclear and New Energy Technology, Tsinghua University in 2017. After graduation, he has been working at the School of Minerals Processing and Bioengineering, Central South University. His research interests focus on the recycling of spent LIBs and the preparation of energy materials.

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40843_2023_2512_MOESM1_ESM.pdf

Fluorine migration and in-situ doping for regeneration of Ni-rich LiNi0.9Co0.05Mn0.05O2 cathode material from spent lithium-ion batteries

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Wang, T., Yi, C., Ge, P. et al. Fluorine migration and in-situ doping for regeneration of Ni-rich LiNi0.9Co0.05Mn0.05O2 cathode material from spent lithium-ion batteries. Sci. China Mater. 66, 3433–3444 (2023). https://doi.org/10.1007/s40843-023-2512-1

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