低温氯化焙烧技术：用于从废弃LiCoO<sub>2</sub>正极材料中同步回收有价金属

石俊杰; 候长乐; 董静静; 陈东; 李建中

doi:10.1007/s12613-024-2898-4

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文章导航 > 矿物冶金与材料学报（英文） > 2025 > 二校

Junjie Shi, Changle Hou, Jingjing Dong, Dong Chen, and Jianzhong Li, Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO₂ cathode material, Int. J. Miner. Metall. Mater.,(2025). https://doi.org/10.1007/s12613-024-2898-4

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Junjie Shi, Changle Hou, Jingjing Dong, Dong Chen, and Jianzhong Li, Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO2 cathode material, Int. J. Miner. Metall. Mater.,(2025). https://doi.org/10.1007/s12613-024-2898-4

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研究论文

低温氯化焙烧技术：用于从废弃LiCoO₂正极材料中同步回收有价金属

1)
东北大学多金属共生矿生态化冶金教育部重点实验室, 沈阳 110819, 中国
2)
东北大学冶金学院, 沈阳 110819, 中国

通讯作者:
石俊杰 E-mail: junjieshi@126.com

文章亮点

(1) 系统的研究了焙烧温度、焙烧时间、原料配比对有价金属回收率的影响。

(2) 开发了一种低温氯化焙烧技术并研究了其反应机理。

(3) 对废旧LiCoO₂正极材料焙烧前后微观组织进行了分析。

(4) 阐明了低温氯化焙烧工艺的反应机理。

中文摘要

随着废弃锂离子电池(LIBs)报废量的不断增加，适当回收废弃LIBs对于循环经济的发展变得至关重要。本研究对氯化焙烧动力学进行了系统分析，并提出了一种新的两步氯化焙烧工艺，该工艺整合了热力学原理，用于回收LIB正极材料。根据热重分析数据使用模型法、无模型法和Z(α)函数法获得的氯化反应的活化能为88.41 kJ/mol。结果表明，当转化率小于等于0.5时，反应主要由一阶（F1）模型主导，当转化率超过0.5时，反应转向二阶（F2）模型。通过深入研究焙烧温度、焙烧时间和NH₄Cl与LiCoO₂的质量比对反应的影响，确定了最佳条件。在最佳条件下，即400°C、20分钟和NH₄Cl/LiCoO₂质量比为3:1时，Li和Co的浸出效率分别达到了99.43%和99.05%。对焙烧产品的分析表明，LiCoO₂中的有价金属转化为CoCl₂和LiCl。此外，阐明了反应机制，为基于晶体结构视角的新型低温氯化焙烧技术提供了见解。这项技术可以指导开发低能耗、低二次污染、高回收效率和高附加值的LIB回收工艺。

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Research Article

Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO₂ cathode material

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Abstract

Abstract

With the continuous increase in the disposal volume of spent lithium-ion batteries (LIBs), properly recycling spent LIBs has become essential for the advancement of the circular economy. This study presents a systematic analysis of the chlorination roasting kinetics and proposes a new two-step chlorination roasting process that integrates thermodynamics for the recycling of LIB cathode materials. The activation energy for the chloride reaction was 88.41 kJ/mol according to thermogravimetric analysis–derivative thermogravimetry data obtained by using model-free, model-fitting, and Z(α) function (α is conversion rate). Results indicated that the reaction was dominated by the first-order (F1) model when the conversion rate was less than or equal to 0.5 and shifted to the second-order (F2) model when the conversion rate exceeded 0.5. Optimal conditions were determined by thoroughly investigating the effects of roasting temperature, roasting time, and the mass ratio of NH₄Cl to LiCoO₂. Under the optimal conditions, namely 400°C, 20 min, and NH₄Cl/LiCoO₂ mass ratio of 3:1, the leaching efficiency of Li and Co reached 99.43% and 99.05%, respectively. Analysis of the roasted products revealed that valuable metals in LiCoO₂ transformed into CoCl₂ and LiCl. Furthermore, the reaction mechanism was elucidated, providing insights for the establishment of a novel low-temperature chlorination roasting technology based on a crystal structure perspective. This technology can guide the development of LIB recycling processes with low energy consumption, low secondary pollution, high recovery efficiency, and high added value.
- spent lithium-ion battery;
- thermodynamics;
- chlorination roasting;
- kinetics;
- circular economy

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低温氯化焙烧技术：用于从废弃LiCoO₂正极材料中同步回收有价金属

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Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO₂ cathode material

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低温氯化焙烧技术：用于从废弃LiCoO2正极材料中同步回收有价金属

文章亮点

中文摘要

Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO2 cathode material

Abstract

References

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低温氯化焙烧技术：用于从废弃LiCoO₂正极材料中同步回收有价金属

Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO₂ cathode material