Research progress on the recovery of valuable metals in retired LiNi x Co y Mn z O2 batteries by wet process

doi:10.16085/j.issn.1000-6613.2018-0359

Abstract

Abstract:

With the recent rapid expand of LiNi _x Co _y Mn _z O₂ battery market, the retired lithium ion batteries will gain explosive growth in the future. Therefore, the recovery of valuable metals such as cobalt, nickel and lithium in the electrode materials of LiNi _x Co _y Mn _z O₂ batteries has become another hot spot in the battery industry. This paper reviews the technological process and main methods for the recovery of the valuable metals from LiNi _x Co _y Mn _z O₂ batteries by wet process, with the focus placed on the leaching methods of valuable metals, separation and extraction of valuable metals, reutilization and leaching kinetics. The advantages and disadvantages of different processing methods are compared. In addition, economic analysis shows that the recovery of valuable metals from retired LiNi _x Co _y Mn _z O₂ batteries has considerable economic value. Finally, the methods for the recovery of the valuable metals of LiNi _x Co _y Mn _z O₂ batteries by wet process are summarized, and the important technologies in the future are briefly described, including chemical purification, automatic disassembling and classified recovery, which provides reference for the future development of recovery of LiNi _x Co _y Mn _z O₂ batteries.

Key words: lithium ion batteries, ternary materials, valuable metals, leaching, recovery, regeneration

摘要：

近年来，随着三元体系锂离子电池市场份额的快速增加，退役三元锂离子电池将在未来出现爆发式增长，因此，回收三元锂离子电池电极材料中高价值的钴、镍、锂等有价金属成为电池行业的又一研究热点。本文详述了湿法回收三元电池电极材料有价金属的工艺流程和主要方法，重点介绍了有价金属的浸取方法、金属的分离提取、再合成利用和浸取动力学机理的研究进展，比较了工艺流程中不同处理方法的优缺点。并对回收退役三元电池材料的有价金属作了经济性分析，结果表明，三元电池材料有价金属回收具有可观的经济效益。最后对湿法回收三元电池材料中的有价金属方法进行总结，并简述了未来湿法回收处理方法的重要技术，包括化学纯化、自动化拆解以及完善的分类回收技术等，为未来三元电池材料回收技术发展提供参考。

关键词: 锂离子电池, 三元材料, 有价金属, 浸取, 回收, 再生

CLC Number:

TM911

Hualing LI, Yongzhen CHEN, Wenji SONG, Ziping FENG. Research progress on the recovery of valuable metals in retired LiNi _x Co _y Mn _z O₂ batteries by wet process[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 921-932.

黎华玲, 陈永珍, 宋文吉, 冯自平. 湿法回收退役三元锂离子电池有价金属的研究进展[J]. 化工进展, 2019, 38(02): 921-932.

Figures/Tables 11

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产品名称	2017年产量/万吨	2016年产量/万吨	同比增长/%
三元材料	12.6	6.5	93.85
磷酸铁锂	10.1	7.4	36.49
钴酸锂	6.0	5.1	17.65
锰酸锂	3.6	2.6	38.46
合计	32.3	21.6	49.54
消耗碳酸锂量	11.0	7.3	52.14

产品名称	2017年产量/万吨	2016年产量/万吨	同比增长/%
三元材料	12.6	6.5	93.85
磷酸铁锂	10.1	7.4	36.49
钴酸锂	6.0	5.1	17.65
锰酸锂	3.6	2.6	38.46
合计	32.3	21.6	49.54
消耗碳酸锂量	11.0	7.3	52.14

电池材料	金属含量（当量）/%			金属价值/万元
电池材料	Co	Ni	Li₂CO₃当量	Co	Ni	Li₂CO₃
LiFePO₄	0	0	23.24	0	0	2.89
LiMn₂O₄	0	0	20.28	0	0	2.52
LiCoO₂	60.21	0	37.47	23.03	0	4.66
LiNi_0.33Co_0.33Mn_0.33O₂	20.28	20.20	38.26	7.75	1.65	4.76
LiNi_0.8Co_0.15Al_0.05O₂	9.20	48.87	38.21	3.52	3.99	4.76
LiNi_0.8Co_0.1Mn_0.1O₂	6.06	48.26	38.00	2.32	3.94	4.73

电池材料	金属含量（当量）/%			金属价值/万元
电池材料	Co	Ni	Li₂CO₃当量	Co	Ni	Li₂CO₃
LiFePO₄	0	0	23.24	0	0	2.89
LiMn₂O₄	0	0	20.28	0	0	2.52
LiCoO₂	60.21	0	37.47	23.03	0	4.66
LiNi_0.33Co_0.33Mn_0.33O₂	20.28	20.20	38.26	7.75	1.65	4.76
LiNi_0.8Co_0.15Al_0.05O₂	9.20	48.87	38.21	3.52	3.99	4.76
LiNi_0.8Co_0.1Mn_0.1O₂	6.06	48.26	38.00	2.32	3.94	4.73

项目名称	具体内容	成本/元·吨^-1
原料	退役三元电池、碱、酸等化学试剂	20000
燃料动力	水、电等	700
设备维护	设备维修费、折旧费	600
环境处理	废气、废水、废渣等处理	700
人工	工资	600
其他费用	场地费、公摊费、税费等	6000
合计		28600

Research progress on the recovery of valuable metals in retired LiNi _x Co _y Mn _z O₂ batteries by wet process

湿法回收退役三元锂离子电池有价金属的研究进展

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