Research progress of positive electrode material recycling technology for retired lithium batteries

doi:10.16085/j.issn.1000-6613.2022-1239

Abstract

Abstract:

The rapid development of the new energy vehicle industry drives the increasing consumption of lithium-ion batteries, which directly leads to the serious shortage of cobalt, lithium, nickel and other energy metals used in the production of battery materials. In the future, the output of retired lithium-ion batteries will increase exponentially. The resource recycling can not only alleviate the shortage of battery materials, but also solve the damage caused by the accumulation of spent batteries. In this paper, the latest research status of discharge pretreatment and two hydrometallurgy and pyrometallurgy resource recovery technologies of retired lithium-ion battery were reviewed, and the future development trend was discussed. On the basis of the existing pyrometallurgy recycle process, a new method was proposed to recover valuable metals by using high-temperature melting smelting slag to treat waste lithium ion batteries. By adding suitable chlorination agent to transform lithium from slag into high-temperature volatile LiCl, a new idea of enrichment and efficient recovery of lithium from dust was realized, and the technical defect of secondary extraction of lithium from slag by traditional fire process was solved.

Key words: lithium-ion battery, discharge processing, resource recovery, hydrometallurgy, pyrometallurgy

摘要：

新能源汽车产业快速发展带动锂离子电池消费不断增加，直接导致用于生产电池材料的钴、锂、镍等能源金属严重短缺。未来退役锂离子电池产量将呈指数增加，其资源化回收受到广泛关注。资源化回收不仅可以缓解电池材料紧缺现状，还解决了废旧电池堆积而引起的危害。本文针对退役锂离子电池放电预处理和湿法、火法两种资源化回收工艺最新研究现状进行了综述，并就未来发展趋势进行了讨论。在现有火法回收工艺基础上提出一种利用高温熔融冶炼渣处理废旧锂离子电池回收有价金属的新方法，通过添加适宜的氯化剂将渣中锂转化为高温易挥发的LiCl，实现从烟尘中富集并高效回收锂的新思路，解决了传统火法工艺需从渣中对锂进行二次提取的技术缺陷。

关键词: 锂离子电池, 放电处理, 资源化回收, 湿法回收, 火法回收

CLC Number:

TF803.21

WANG Hao, HUO Jinda, QU Guorui, YANG Jiaqi, ZHOU Shiwei, LI Bo, WEI Yonggang. Research progress of positive electrode material recycling technology for retired lithium batteries[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2702-2716.

王昊, 霍进达, 曲国瑞, 杨家琪, 周世伟, 李博, 魏永刚. 退役锂电池正极材料资源化回收技术研究进展[J]. 化工进展, 2023, 42(5): 2702-2716.

Figures/Tables 8

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成分	所用材料	成本占比/%	化学特性	潜在危害性
正极材料	钴酸锂/锰酸锂/镍酸锂/磷酸铁锂	30~35	与水、酸、还原剂或强氧化剂发生反应	重金属污染
负极材料	碳材料/石墨	10~15	遇明火或高温易爆炸	粉尘污染
电解质	LiPF₆/LiBF₄/LiAsF₆	10~15	强腐蚀性，遇水生成HF，氧化产生P₂O₅等有毒物质	氟污染，有害气体污染
电解质溶剂	碳酸乙烯酯/碳酸二甲酯	10~15	水解产生醛和酸，燃烧产生CO、CO₂等	有机物污染
隔膜材料	聚丙烯/聚乙烯	20~30	燃烧可产生CO、醛等	有机物污染
黏合剂	聚偏氟乙烯/偏氟乙烯	10~15	受热分解产生HF	氟污染

成分	所用材料	成本占比/%	化学特性	潜在危害性
正极材料	钴酸锂/锰酸锂/镍酸锂/磷酸铁锂	30~35	与水、酸、还原剂或强氧化剂发生反应	重金属污染
负极材料	碳材料/石墨	10~15	遇明火或高温易爆炸	粉尘污染
电解质	LiPF₆/LiBF₄/LiAsF₆	10~15	强腐蚀性，遇水生成HF，氧化产生P₂O₅等有毒物质	氟污染，有害气体污染
电解质溶剂	碳酸乙烯酯/碳酸二甲酯	10~15	水解产生醛和酸，燃烧产生CO、CO₂等	有机物污染
隔膜材料	聚丙烯/聚乙烯	20~30	燃烧可产生CO、醛等	有机物污染
黏合剂	聚偏氟乙烯/偏氟乙烯	10~15	受热分解产生HF	氟污染

材料	钴酸锂电池（LCO） /%	锰酸锂电池（LMO） /%	镍、锰、钴三元电池（NMC） /%	磷酸铁锂电池（LFP） /%	镍钴铝三元电池（NCA） /%
活性正极材料	35.3	40.8	34.7	32.7	30.6
石墨	20.9	16.8	21.7	19	24.2
黏结剂	3.0	3.0	3.0	2.7	2.9
铜	16.1	15.0	15.7	13.9	16.7
铝	8.1	7.8	8.2	7.5	8.6
电解液	14.2	14.4	14.6	22.2	14.9
其他（塑料隔膜）	2.4	2.1	2.1	1.9	2.3

材料	钴酸锂电池（LCO） /%	锰酸锂电池（LMO） /%	镍、锰、钴三元电池（NMC） /%	磷酸铁锂电池（LFP） /%	镍钴铝三元电池（NCA） /%
活性正极材料	35.3	40.8	34.7	32.7	30.6
石墨	20.9	16.8	21.7	19	24.2
黏结剂	3.0	3.0	3.0	2.7	2.9
铜	16.1	15.0	15.7	13.9	16.7
铝	8.1	7.8	8.2	7.5	8.6
电解液	14.2	14.4	14.6	22.2	14.9
其他（塑料隔膜）	2.4	2.1	2.1	1.9	2.3

方法	机理	优点	缺点	浸出溶液	参考文献
酸浸出
无机酸浸出	利用溶液的酸特性，氢离子溶解并与电池材料发生反应，使电池材料中的有价金属成分转移到浸出液中	浸出速度快、浸出效率高、成本低、适用面广	会产生有毒废气以及酸性废水、对设备要求较高	盐酸、硫酸、磷酸、硝酸等	[40-42]
有机酸浸出	利用溶液的酸特性，氢离子溶解并与电池材料发生反应，使电池材料中的有价金属成分转移到浸出液中	更加绿色环保、减少废气和废水的排放	浸出不完全、浸出速度慢、有机酸成本较高	柠檬酸、抗坏血酸、草酸、苹果酸等	[37,43]
碱浸出	利用溶液中强碱性环境下氨根离子与金属离子之间的相互络合作用	浸出后不会产生强酸废水、低毒性和高选择性	成本较高、浸出速率较慢	硫酸铵、碳酸铵、氯化铵、氨水溶液	[44-46]
生物浸出	通过微生物代谢产生酸，将不溶性金属氧化物转化为可溶金属离子	绿色环保无污染	浸出效率低、反应过程缓慢、周期长、耗时久	硫氧化铁杆菌、黑曲霉等	[47-49]