退役磷酸铁锂电池与三元锂电池正极材料直接修复研究进展

doi:10.16085/j.issn.1000-6613.2023-0845

化工进展 ›› 2024, Vol. 43 ›› Issue (6): 3336-3346.DOI: 10.16085/j.issn.1000-6613.2023-0845

• 资源与环境化工 • 上一篇

退役磷酸铁锂电池与三元锂电池正极材料直接修复研究进展

王厚然¹^,²^,³^,⁴(), 李德念¹^,³^,⁴(), 董楠航², 阳济章¹^,³^,⁴, 倪轩辕¹^,³^,⁴, 叶嘉鸿¹^,³^,⁴, 袁浩然¹^,³^,⁴(), 陈勇¹^,³^,⁴

^1.中国科学院广州能源研究所，广东广州 510640
^2.东北电力大学能源与动力工程学院，吉林吉林 132000
^3.广东省新能源和可再生能源研究开发与应用重点实验室，广东广州 510640
^4.中国科学院可再生能源重点实验室，广东广州 510640

收稿日期:2023-05-22 修回日期:2023-07-19 出版日期:2024-06-15 发布日期:2024-07-02
通讯作者: 袁浩然
作者简介:王厚然（1990—），男，硕士研究生，研究方向为废旧锂离子电池资源化利用。E-mail：347619195@qq.com
李德念（1987—），男，博士，副研究员，研究方向为有机废物资源化利用。E-mail：lidn@ms.giec.ac.cn。
基金资助:
国家重点研发计划(2022YFC3902600)

Advances in direct repair of cathode materials from retired lithium iron phosphate battery and ternary lithium battery

WANG Houran¹^,²^,³^,⁴(), LI Denian¹^,³^,⁴(), DONG Nanhang², YANG Jizhang¹^,³^,⁴, NI Xuanyuan¹^,³^,⁴, YE Jiahong¹^,³^,⁴, YUAN Haoran¹^,³^,⁴(), CHEN Yong¹^,³^,⁴

^1.Guangzhou Institute of Energy Research, Chinese Academy of Science，Guangzhou 510640, Guangdong, China
^2.School of Energy and Power Engineering, Northeast Electric Power University, Jilin 132000, Jilin, China
^3.Guangdong Provincial Key Laboratory of New Energy and Renewable Energy Research, Development and Application, Guangzhou 510640, Guangdong, China
^4.Key Laboratory of Renewable Energy, Chinese Academy of Science, Guangzhou 510640, Guangdong, China

Received:2023-05-22 Revised:2023-07-19 Online:2024-06-15 Published:2024-07-02
Contact: YUAN Haoran

摘要/Abstract

摘要：

锂电池产业的迅猛发展以及新型储能对锂离子电池需求的进一步增长预期引起了各界对相关资源与环境问题的广泛担忧，因此退役锂离子电池的回收利用已成为当前产业体系中的重要一环。锂离子电池的正极材料是锂电池中最具价值的部分，相比于目前已投入生产的湿法回收与火法回收工艺，针对退役正极材料直接修复的研究目前仍处于起步阶段，因其相比于传统回收方法具有绿色廉价等优势，未来仍然存在可观的开发空间。本文介绍了磷酸铁锂电池与三元锂电池及两种锂离子电池正极材料的主要失效原因，以及针对此两种锂离子电池退役后其正极材料的几种直接修复方法，并对不同直接修复方法存在的问题进行了梳理，进而对正极材料直接修复提出相关建议，以期直接修复可以在锂电行业有更广阔的发展。

关键词: 锂电池, 正极材料, 修复, 再生

Abstract:

The rapid development of the lithium battery industry and the new energy storage demand for lithium-ion batteries have drawn much attention in the resource and environmental field. Therefore, the recycling of retired lithium-ion batteries is necessary in the current industrial system. The cathode materials are the most valuable part of lithium-ion batteries, while the direct repair of waste cathode electrode materials is still in its early stages compared to the hydrometallurgy and pyrometallurgy methods. The prospect of a direct repair method is better than traditional methods due to its low cost and green environmental protection. This review introduced two major batteries, including lithium iron phosphate battery and ternary lithium battery, as well as the reason for the cathode materials failure of these two batteries. Meanwhile, several direct repair methods for the cathode materials of these two retired batteries and the problems existing in different direct repair methods were reviewed. Some relevant suggestions were also proposed to promote development of direct repair in the lithium battery industry.

Key words: lithium battery, cathode material, repair, regeneration

中图分类号:

TM911

王厚然, 李德念, 董楠航, 阳济章, 倪轩辕, 叶嘉鸿, 袁浩然, 陈勇. 退役磷酸铁锂电池与三元锂电池正极材料直接修复研究进展[J]. 化工进展, 2024, 43(6): 3336-3346.

WANG Houran, LI Denian, DONG Nanhang, YANG Jizhang, NI Xuanyuan, YE Jiahong, YUAN Haoran, CHEN Yong. Advances in direct repair of cathode materials from retired lithium iron phosphate battery and ternary lithium battery[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3336-3346.

图/表 7

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性能	LFP	NCM
化学式	LiFePO₄	Li(Ni _x Co _y Mn₁_-x-y )O₂
晶体结构	橄榄石结构	层状结构
空间点群	Pmnb	R-3m
锂离子表观扩散系数/cm²·s^-1	1.8×10^-16~2.2×10^-14	10^-1~10^-11
理论容量/mAh·g^-1	170	273~285
实际容量/mAh·g^-1	130~140	155~220
平均电压/V	3.4	3.6
循环性/次	2000~6000	800~2000
环保性	无毒	镍、钴有毒
安全性能	好	中
价格/10⁴CNY·t^-1	15~20	15.5~16.5
主要应用领域	电动汽车及大规模储能	电动工具、电动自行车、电动汽车及大规模储能

性能	LFP	NCM
化学式	LiFePO₄	Li(Ni _x Co _y Mn₁_-x-y )O₂
晶体结构	橄榄石结构	层状结构
空间点群	Pmnb	R-3m
锂离子表观扩散系数/cm²·s^-1	1.8×10^-16~2.2×10^-14	10^-1~10^-11
理论容量/mAh·g^-1	170	273~285
实际容量/mAh·g^-1	130~140	155~220
平均电压/V	3.4	3.6
循环性/次	2000~6000	800~2000
环保性	无毒	镍、钴有毒
安全性能	好	中
价格/10⁴CNY·t^-1	15~20	15.5~16.5
主要应用领域	电动汽车及大规模储能	电动工具、电动自行车、电动汽车及大规模储能

项目	LFP电池	NCM电池
回收方式	梯次利用：将剩余容量较高的退役电池在低要求的电池领域进行二次使用	拆解回收：对电池进行拆解处理，提取内部可回收金属
经济效益	回收材料经济效益较差	材料含有锂、镍、钴，回收价值高

项目	LFP电池	NCM电池
回收方式	梯次利用：将剩余容量较高的退役电池在低要求的电池领域进行二次使用	拆解回收：对电池进行拆解处理，提取内部可回收金属
经济效益	回收材料经济效益较差	材料含有锂、镍、钴，回收价值高

正极材料	修复方法	商业正极材料实际容量/mAh·g^-1	修复后正极材料最大放电容量/mAh·g^-1	参考文献
LFP	固相烧结法	130~140	154.3（0.1C）	[69]
			150.99（0.2C）	[70]
			144（0.1C）	[71]
			139（0.2C）	[52]
	电化学法		159（0.1C）	[28]
	电化学法		135.2（1.0C）	[72]
	水热法		144.02（0.1C）	[73]
			146.2（1.0C）	[74]
			161.4（0.2C）	[75]
			162（0.5C）	[53]
	化学法		160.1（0.5C）	[76]
NCM	固相烧结法	155~220	162（0.1C）	[77]
			154.87（0.2C）	[78]
			189.8（0.1C）	[79]
			162（0.2C）	[80]
	水热法		145.1（1.0C）	[81]
			166.1（0.1C）	[82]
			156.6（0.1C）	[83]
	共晶法		149.3（1.0C）	[84]
			146.3（1.0C）	[85]
			160（0.5C）	[86]
	氧化还原法		182.5（1.0C）	[87]

退役磷酸铁锂电池与三元锂电池正极材料直接修复研究进展

Advances in direct repair of cathode materials from retired lithium iron phosphate battery and ternary lithium battery

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