Progress of deep eutectic solvents in recovery of cathode materials from spent lithium ion batteries

doi:10.16085/j.issn.1000-6613.2021-1493

Abstract

Abstract:

With the development of large-scale energy storage and electric vehicle market, the demand for lithium-ion batteries is increasing, resulting in an explosive growth in the number of spent lithium-ion batteries. The cathode materials of spent lithium-ion batteries contain abundant valuable metal elements such as lithium, cobalt, nickel and manganese. The recovery of those metals has high economic value and significant environment benefits. As a green solvent, deep eutectic solvents (DESs) show great potential in the recovery of valuable metal elements from spent lithium-ion batteries. Based on a brief introduction of the properties and applications of DESs, this paper systematically reviews the research status of DESs in the recycling chain of cathode materials from spent lithium-ion batteries, mainly including the separation of cathode material, leaching of active substances and recovery of valuable metal. The current recycling methods and process flow are discussed, and the advantages and disadvantages of different kinds of DESs for leaching cathode active materials are compared as well. Finally, the common problems of the current DESs in the recycling spent lithium-ion batteries are analyzed, and the development direction of DESs recycling of lithium-ion batteries is proposed.

Key words: deep eutectic solvent, spent lithium ions batteries, separation, leaching, recovery

摘要：

大规模储能与电动汽车市场的发展壮大对锂离子电池的需求水涨船高，由此产生的废旧锂离子电池数量也即将迎来爆发式增长。废旧锂离子电池正极材料蕴含丰富的锂、钴、镍、锰等有价金属元素，回收经济价值高，环境效益显著。低共熔溶剂（DESs）作为一种绿色溶剂，在废旧锂离子电池有价金属元素回收方面显示出巨大的潜力。本文在简要介绍DESs性质及应用的基础上，系统综述了DESs在废旧锂离子电池正极材料回收链中的研究现状，主要包括正极材料的分离、活性物质的浸出以及有价金属的提取，着重介绍了现阶段回收的方法及工艺流程，比较了不同DESs浸出正极活性物质的优缺点，探讨了当前DESs在废旧锂离子电池回收中的共性问题，并展望了未来DESs回收锂离子电池的发展方向。

关键词: 低共熔溶剂, 废旧锂离子电池, 分离, 浸出, 回收

CLC Number:

TF11

CHENG Mingqiang, RU Juanjian, HUA Yixin, WANG Ding, GENG Xiao, ZHANG Wenwen, HUANG Haoming, WANG Daoxiang. Progress of deep eutectic solvents in recovery of cathode materials from spent lithium ion batteries[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3293-3305.

程明强, 汝娟坚, 华一新, 王丁, 耿笑, 张文文, 黄皓铭, 王道祥. 低共熔溶剂在废旧锂离子电池正极材料回收中的研究进展[J]. 化工进展, 2022, 41(6): 3293-3305.

Figures/Tables 11

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DESs	HBA/HBD摩尔比	密度/g?cm^-3	黏度/mPa?s	电导率/mS?cm^-1	测量温度/℃	参考文献
氯化胆碱/乙二醇	1∶2	1.1139	25	9.73	30	［35］
氯化胆碱/乙二醇	1∶2	1.12	36	7.61	20	［36］
氯化胆碱/乙二醇	1∶3	1.12	19	—	20	［37］
氯化胆碱/尿素	1∶2	1.1879	214	1.287	30	［35］
氯化胆碱/尿素	1∶2	1.24	169	0.199	40	［37］
氯化胆碱/草酸	1∶1	1.2371	89	2.35	30	［35］
氯化胆碱/苹果酸	1∶1	1.2796	11475	0.041	30	［35］
氯化胆碱/柠檬酸	1∶1	1.3313	45008	0.018	30	［35］
氯化胆碱/丙三酸	1∶1	—	721	0.55	25	［22］
氯化胆碱/对甲苯磺酸	1∶1	1.2074	183	1.138	30	［35］
氯化胆碱/甘油	1∶2	1.1854	177	1.647	49	［35］
氯化胆碱/甘油	1∶2	1.181	376	1.047	—	［37］
氯化胆碱/乙酰胺	1∶2	1.8052	127	2.71	30	［35］

DESs	HBA/HBD摩尔比	密度/g?cm^-3	黏度/mPa?s	电导率/mS?cm^-1	测量温度/℃	参考文献
氯化胆碱/乙二醇	1∶2	1.1139	25	9.73	30	［35］
氯化胆碱/乙二醇	1∶2	1.12	36	7.61	20	［36］
氯化胆碱/乙二醇	1∶3	1.12	19	—	20	［37］
氯化胆碱/尿素	1∶2	1.1879	214	1.287	30	［35］
氯化胆碱/尿素	1∶2	1.24	169	0.199	40	［37］
氯化胆碱/草酸	1∶1	1.2371	89	2.35	30	［35］
氯化胆碱/苹果酸	1∶1	1.2796	11475	0.041	30	［35］
氯化胆碱/柠檬酸	1∶1	1.3313	45008	0.018	30	［35］
氯化胆碱/丙三酸	1∶1	—	721	0.55	25	［22］
氯化胆碱/对甲苯磺酸	1∶1	1.2074	183	1.138	30	［35］
氯化胆碱/甘油	1∶2	1.1854	177	1.647	49	［35］
氯化胆碱/甘油	1∶2	1.181	376	1.047	—	［37］
氯化胆碱/乙酰胺	1∶2	1.8052	127	2.71	30	［35］

正极活性物质	DES	温度/℃	时间/h	固液比/mg·g^-1	浸出效率/%				参考文献
正极活性物质	DES	温度/℃	时间/h	固液比/mg·g^-1	Li	Co	Ni	Mn	参考文献
LiCoO₂	ChCl-EG（1∶2）	180	24	20	89.8	50.3	—	—	［46］
	ChCl-EG（1∶2）	220	24	20	—	94.1	—	—	［46］
	PTSA?1H₂O?ChCl	90	15	100	85	88	—	—	［57］
	PTSA?2H₂O?ChCl	90	15	100	100	100	—	—
	PTSA?3H₂O?ChCl	90	15	100	91	97	—	—
	ChCl-Urea（1∶2）	180	12	20	94.7	97.9	—	—	［58］
	ChCl-甲酸（1∶2）	90	12	20	99.8	99.1	—	—	［59］
	ChCl-乙酸（1∶2）	90	12	20	63	18	—	—
	ChCl-丙酸（1∶2）	90	12	20	39	15	—	—
	ChCl-正丁酸（1∶2）	90	12	20	33	12	—	—
	PEG∶硫脲（1∶2）	160	24	20	—	71.5	—	—	［60］
LiCoO₂/Al/Cu Al∶LiCoO₂=12%（质量分数） Cu∶LiCoO₂=24%（质量分数）	ChCl-CA（1∶1）	60	4	20	—	99.6	—	—	［61］
	ChCl-EG（1∶1）	60	4	20	—	2.1	—	—
	ChCl-丙酸（1∶1）	60	4	20	—	81.2	—	—
	ChCl-丙酸脂（1∶1）	60	4	20	—	24.4	—	—
	ChCl-OA（1∶1）	60	4	20	—	19.6	—	—
	ChCl-CA（1∶2）	40	1	20	93	98	—	—
LiMn₂O₄	ChCl-OA（1∶1）	100	0.25	16.7	99			95	［62］
Li _a Ni _b Mn _c Co _d O₂（a+b+c+d=2）	ChCl-EG（1∶2）	180	24	4	71	32	7	60	［46］
LiNi_1/3Mn_1/3Co_1/3O₂	ChCl-EG（1∶2）	160	24	20	—	90	—	10	［63］

正极活性物质	DES	温度/℃	时间/h	固液比/mg·g^-1	浸出效率/%				参考文献
正极活性物质	DES	温度/℃	时间/h	固液比/mg·g^-1	Li	Co	Ni	Mn	参考文献
LiCoO₂	ChCl-EG（1∶2）	180	24	20	89.8	50.3	—	—	［46］
	ChCl-EG（1∶2）	220	24	20	—	94.1	—	—	［46］
	PTSA?1H₂O?ChCl	90	15	100	85	88	—	—	［57］
	PTSA?2H₂O?ChCl	90	15	100	100	100	—	—
	PTSA?3H₂O?ChCl	90	15	100	91	97	—	—
	ChCl-Urea（1∶2）	180	12	20	94.7	97.9	—	—	［58］
	ChCl-甲酸（1∶2）	90	12	20	99.8	99.1	—	—	［59］
	ChCl-乙酸（1∶2）	90	12	20	63	18	—	—
	ChCl-丙酸（1∶2）	90	12	20	39	15	—	—
	ChCl-正丁酸（1∶2）	90	12	20	33	12	—	—
	PEG∶硫脲（1∶2）	160	24	20	—	71.5	—	—	［60］
LiCoO₂/Al/Cu Al∶LiCoO₂=12%（质量分数） Cu∶LiCoO₂=24%（质量分数）	ChCl-CA（1∶1）	60	4	20	—	99.6	—	—	［61］
	ChCl-EG（1∶1）	60	4	20	—	2.1	—	—
	ChCl-丙酸（1∶1）	60	4	20	—	81.2	—	—
	ChCl-丙酸脂（1∶1）	60	4	20	—	24.4	—	—
	ChCl-OA（1∶1）	60	4	20	—	19.6	—	—
	ChCl-CA（1∶2）	40	1	20	93	98	—	—
LiMn₂O₄	ChCl-OA（1∶1）	100	0.25	16.7	99			95	［62］
Li _a Ni _b Mn _c Co _d O₂（a+b+c+d=2）	ChCl-EG（1∶2）	180	24	4	71	32	7	60	［46］
LiNi_1/3Mn_1/3Co_1/3O₂	ChCl-EG（1∶2）	160	24	20	—	90	—	10	［63］

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