锂离子电池拆解回收技术及进展

doi:10.16085/j.issn.1000-6613.2023-1208

摘要/Abstract

摘要：

锂离子电池的广泛使用带来了越来越多的电池废弃物，如何环保、安全、低成本地处理这些废旧锂离子电池成了该领域的热点问题。本文以废旧锂离子电池的危害和资源利用价值为背景，重点介绍了废旧锂离子电池拆解回收的工艺流程，其中包括了预处理、主流回收方法、金属分离回收和再生利用等部分，以相关技术原理为基础，重点归纳了近几年湿法回收为主的废旧锂离子电池回收利用各环节工艺流程的学术成果，并对工艺过程中各个方法进行了优势与不足的分析，其次对于物理回收和火法回收等方面作了简要介绍。最后，在现有的回收现状上，对锂离子电池未来进行展望，提出建立大型预处理生产线、在相邻领域再利用回收材料、重复使用化学试剂等合理的发展方向。

关键词: 废旧锂离子电池, 废物处理, 回收, 浸出, 再生

Abstract:

The extensive use of lithium-ion batteries has generated more and more lithium-ion battery waste, and how to deal with this lithium-ion battery waste in an environmentally friendly, safe and cost-effective manner has become a hot issue in the field. This paper took the hazards and resource utilization value of waste lithium-ion batteries as the background, focused on the process of dismantling and recycling of waste lithium-ion batteries, which included pre-treatment, mainstream recycling methods, metal separation, recovery and recycling, based on the relevant technical principles, It focused on summarizing the progress of academic achievement on the process of recycling of waste lithium-ion batteries mainly by wet recycling in recent years, and analyzed the advantages and shortcomings of each method in the process, followed by a brief introduction to physical recycling and fire recycling. Finally, based on the existing recycling status quo, the future outlook of lithium-ion batteries was made, and reasonable development directions were suggested such as the establishment of a large-scale pretreatment production line, the reuse of recycled materials in adjacent fields and the reuse of chemical reagents.

Key words: spent lithium-ion batteries, waste treatment, recovery, leaching, regeneration

中图分类号:

TM911

黎伟杰, 路蕾蕾, 李得科, 王春航, 张祖铭, 谭强. 锂离子电池拆解回收技术及进展[J]. 化工进展, 2024, 43(8): 4601-4613.

LI Weijie, LU Leilei, LI Deke, WANG Chunhang, ZHANG Zuming, TAN Qiang. Lithium-ion battery disassembly and recycling technology and progress[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4601-4613.

图/表 9

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序号	无机浸出剂	还原剂	固液比/mL·g^-1	时间/min	温度 /℃	浸出效率/%				参考文献
序号	无机浸出剂	还原剂	固液比/mL·g^-1	时间/min	温度 /℃	锂	镍	锰	钴	参考文献
1	硫酸（2.0mol·L^-1）	双氧水（0.97mol·L^-1）	10	30	80	100	100	94	100	[51]
2	硫酸（1.0mol·L^-1）	亚硫酸氢钠（0.075mol·L^-1）	50	240	95	96.7	96.4	87.9	91.6	[52]
3	硫酸（1.0mol·L^-1）	双氧水（体积分数1%）	25	60	40	99.7	99.7	99.7	99.7	[53]
4	硫酸（1.0mol·L^-1）	—	10	60	90	100	100	93.0	100	[54]
5	硫酸（2.0mol·L^-1）	双氧水（体积分数2%）	10	60	75	99.1	—	—	70	[55]
6	盐酸（3.0mol·L^-1）	—	50	90	80	99.4	—	—	—	[56]
7	盐酸（2.0mol·L^-1）	双氧水（体积分数5%）	33	150	60	>99	>99	>99	>99	[57]
8	硝酸（1.0mol·L^-1）	双氧水（体积分数1.7%）	50	60	75	85	—	—	85	[58]
9	磷酸（0.7mol·L^-1）	双氧水（体积分数4.0%）	20	60	40	>99	—	—	>99	[59]

序号	无机浸出剂	还原剂	固液比/mL·g^-1	时间/min	温度 /℃	浸出效率/%				参考文献
序号	无机浸出剂	还原剂	固液比/mL·g^-1	时间/min	温度 /℃	锂	镍	锰	钴	参考文献
1	硫酸（2.0mol·L^-1）	双氧水（0.97mol·L^-1）	10	30	80	100	100	94	100	[51]
2	硫酸（1.0mol·L^-1）	亚硫酸氢钠（0.075mol·L^-1）	50	240	95	96.7	96.4	87.9	91.6	[52]
3	硫酸（1.0mol·L^-1）	双氧水（体积分数1%）	25	60	40	99.7	99.7	99.7	99.7	[53]
4	硫酸（1.0mol·L^-1）	—	10	60	90	100	100	93.0	100	[54]
5	硫酸（2.0mol·L^-1）	双氧水（体积分数2%）	10	60	75	99.1	—	—	70	[55]
6	盐酸（3.0mol·L^-1）	—	50	90	80	99.4	—	—	—	[56]
7	盐酸（2.0mol·L^-1）	双氧水（体积分数5%）	33	150	60	>99	>99	>99	>99	[57]
8	硝酸（1.0mol·L^-1）	双氧水（体积分数1.7%）	50	60	75	85	—	—	85	[58]
9	磷酸（0.7mol·L^-1）	双氧水（体积分数4.0%）	20	60	40	>99	—	—	>99	[59]

序号	有机浸出剂	还原剂	固液比/mL·g^-1	时间/min	温度/℃	浸出效率/%				参考文献
序号	有机浸出剂	还原剂	固液比/mL·g^-1	时间/min	温度/℃	锂	镍	锰	钴	参考文献
1	DL-苹果酸（1.2mol·L^-1）	双氧水（体积分数1.5%）	25	30	80	98.9	95.1	96.4	94.3	[61]
2	DL-苹果酸（1.0mol·L^-1）	双氧水（体积分数4.0%）	200	30	80	98	97.8	97.3	97.6	[62]
3	柠檬酸（1.2mol·L^-1）	硫代硫酸钠（0.3 mol·L^-1）	50	30	70	99	—	—	96	[63]
4	柠檬酸（0.5mol·L^-1）	双氧水（体积分数1.5%）	50	60	90	>95	>95	>95	>95	[64]
5	抗坏血酸（1.24mol·L^-1）	—	31.30	59.79	69.26	92.75	56.83	89.91	96.78	[65]
6	草酸（1.0mol·L^-1）	—	67	150	95	98	—	—	97	[66]
8	乙酸（3.0mol·L^-1）	双氧水（体积分数7.5%）	50	40	70	99.9	—	99.5	98.7	[67]
9	酒石酸（4倍LiCoO₂的物质的量）	—	67	300	90	91.9	—	—	93.0	[68]

序号	有机浸出剂	还原剂	固液比/mL·g^-1	时间/min	温度/℃	浸出效率/%				参考文献
序号	有机浸出剂	还原剂	固液比/mL·g^-1	时间/min	温度/℃	锂	镍	锰	钴	参考文献
1	DL-苹果酸（1.2mol·L^-1）	双氧水（体积分数1.5%）	25	30	80	98.9	95.1	96.4	94.3	[61]
2	DL-苹果酸（1.0mol·L^-1）	双氧水（体积分数4.0%）	200	30	80	98	97.8	97.3	97.6	[62]
3	柠檬酸（1.2mol·L^-1）	硫代硫酸钠（0.3 mol·L^-1）	50	30	70	99	—	—	96	[63]
4	柠檬酸（0.5mol·L^-1）	双氧水（体积分数1.5%）	50	60	90	>95	>95	>95	>95	[64]
5	抗坏血酸（1.24mol·L^-1）	—	31.30	59.79	69.26	92.75	56.83	89.91	96.78	[65]
6	草酸（1.0mol·L^-1）	—	67	150	95	98	—	—	97	[66]
8	乙酸（3.0mol·L^-1）	双氧水（体积分数7.5%）	50	40	70	99.9	—	99.5	98.7	[67]
9	酒石酸（4倍LiCoO₂的物质的量）	—	67	300	90	91.9	—	—	93.0	[68]

方法	优势	劣势
共沉淀法	获得正极材料颗粒细小、形态规则、元素分布均匀，有良好的电化学性能	设备要求高、工艺复杂、成本高
溶胶-凝胶法	可以在不添加锂源的情况下合成正极材料，高度可控性	制造时间长、成本高等不足大大限制了其工业化发展
固相合成法	流程简单、成本低	很难除去其中的杂质，杂质的含量及分布将会影响其电化学性能
水热法	无杂质引入，步骤简单	需注意废液处理，防止环境污染