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A unique co-recovery strategy of cathode and anode from spent LiFePO4 battery

废旧磷酸铁锂电池的正负极同步再利用策略

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Abstract

Along with the explosive growth in the market of new energy electric vehicles, the demand for Li-ion batteries (LIBs) has correspondingly expanded. Given the limited life of LIBs, numbers of spent LIBs are bound to be produced. Because of the severe threats and challenges of spent LIBs to the environment, resources, and global sustainable development, the recycling and reuse of spent LIBs have become urgent. Herein, we propose a novel green and efficient direct recycling method, which realizes the concurrent reuse of LiFePO4 (LFP) cathode and graphite anode from spent LFP batteries. By optimizing the proportion of LFP and graphite, a hybrid LFP/graphite (LFPG) cathode was designed for a new type of dualion battery (DIB) that can achieve co-participation in the storage of both anions and cations. The hybrid LFPG cathode combines the excellent stability of LFP and the high conductivity of graphite to exhibit an extraordinary electrochemical performance. The best compound, i.e., LFP:graphite = 3:1, with the highest reversible capacity (∼130 mA h g−1 at 25 mA g−1), high voltage platform of 4.95 V, and outstanding cycle performance, was achieved. The specific diffusion behavior of Li+ and PF6− in the hybrid cathode was studied using electrode kinetic tests, further clarifying the working mechanism of DIBs. This study provides a new strategy toward the large-scale recycling of positive and negative electrodes of spent LIBs and establishes a precedent for designing new hybrid cathode materials for DIBs with superior performance using spent LIBs.

摘要

考虑到废旧锂离子电池对环境、 资源和全球可持续性发展存在严重的威胁和挑战, 有必要开发出合适的回收技术实现废旧锂离子电池的回收和再利用. 因此, 我们提出了一种全新的绿色高效的直接回收方法, 实现了废旧磷酸铁锂电池中正极LiFePO4 (LFP)和负极石墨的双重回收, 并将其按不同比例复合设计了一种新型双离子电池(DIB)的复合正极材料(LiFePO4/石墨, 简写为LFPG). 这种复合正极能够实现阴离子和阳离子的共同参与脱嵌, 从而贡献更高的容量. 结合LFP的高容量、 高稳定性和石墨的高导电性、 高电压性, 这种复合正极表现出优异的电化学性能. 在不同配比的复合材料中, LFP:graphite = 3:1的复合材料在25 mA g−1的电流密度下展示出接近130 mA h g−1的可逆容量, 达到4.95 V的高电压平台, 并表现出优异的循环性能(在100 mA g−1的电流密度下进行700次循环后仍具有良好的容量保持率), 倍率性能相比回收的单一LiFePO4也得到明显提升. 通过电极动力学研究, 揭示了Li+和PF6−在复合正极中的特定扩散行为, 进一步阐明了DIB的阴/阳离子分阶段嵌入/脱出的工作机理. 本研究为废旧锂离子电池正极和负极材料的大规模回收提供了一种新的策略, 并为利用废锂离子电池设计出性能优良的新型复合型锂离子电池正极材料提供了指导.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (52173246 and 91963118) and the 111 Project (B13013).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Faculty of Chemistry, Northeast Normal University, Changchun, 130024, China

    Kai-Di Du  (杜凯迪), Yun-Feng Meng  (孟云峰), Xin-Xin Zhao  (赵欣欣), Xiao-Xi Luo  (罗晓曦), Wei Zhang  (张薇) & Xing-Long Wu  (吴兴隆)

  2. MOE Key Laboratory for UV Light-Emitting Materials and Technology, Northeast Normal University, Changchun, 130024, China

    Xiao-Tong Wang  (王晓彤) & Xing-Long Wu  (吴兴隆)

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  1. Kai-Di Du  (杜凯迪)
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Contributions

Author contributions Wu XL contributed the concept; Du KD and Meng YF prepared the materials and performed the experiments; Zhao XX and Wang XT supervised the revision of the paper; Luo XX and Zhang W finished the theoretical calculation; Du KD and Wu XL wrote the paper; Wu XL supervised the analysis of the whole work. All authors took part in the general discussion.

Corresponding author

Correspondence to Xing-Long Wu  (吴兴隆).

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Conflict of interest

The authors declare that they have no conflict of interest.

Kai-Di Du received her bachelor’s degree from Hebei Normal University in 2019. Now she is pursuing her master’s degree under the supervision of professor Xing-Long Wu at the Department of Chemistry, Northeast Normal University. Her research interests focus on the recovery and reuse of spent lithium-ion batteries.

Xing-Long Wu is currently a professor at the Northeast Normal University, China. He received his PhD degree from the Institute of Chemistry, Chinese Academy of Sciences (ICCAS), in 2011. After continuing a two-year postdoctoral work in ICCAS, he moved to the Northeast Normal University as an associate professor in 2013 and became a full professor in 2018. His current research interests focus on high-performance materials for advanced secondary batteries such as Na/K/Li-ion batteries and dual-ion batteries, as well as the reuse and recycle of spent Li-ion batteries.

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Du, KD., Meng, YF., Zhao, XX. et al. A unique co-recovery strategy of cathode and anode from spent LiFePO4 battery. Sci. China Mater. 65, 637–645 (2022). https://doi.org/10.1007/s40843-021-1772-6

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