Application of magnetic separation in the recycling of cathode and anode materials from spent lithium batteries

doi:10.19799/j.cnki.2095-4239.2024.1049

Abstract

Abstract:

The rapid growth of industries like electric vehicles, mobile communications, and energy storage has led to a significant yearly increase in spent lithium batteries. These batteries contain high-value materials such as cobalt, lithium, and graphite, making their recycling essential for resource regeneration and environmental protection. Traditional recycling methods, including pyrometallurgical and hydrometallurgical processes, are effective but are often associated with high energy consumption, severe pollution, and lengthy recovery procedures. Magnetic separation technology offers a a green and efficient alternative for recycling, leveraging the physical property differences between materials to achieve separation. Frequently integrated with other recycling techniques, it shows great potential for recovering cathode and anode materials from spent lithium-ion batteries. This paper reviews the current applications of magnetic separation technology in battery recycling, highlighting the fundamental principles behind methods such as high-gradient magnetic separation, eddy current separation, and wet magnetic separation. It also examines how these technologies contribute to material separation and metal impurity removal. Challenges in scaling up magnetic separation technologies for industrial applications are also discussed, such as limitations in magnetic field strength, low levels of equipment integration, and limited adaptability to battery compositions. Finally, this paper provides insights into future development trends aimed at promoting green and closed-loop recycling of spent lithium-ion battery materials.

Key words: spent lithium-ion batteries, cathode and anode materials, magnetic separation, recycling

CLC Number:

TK 09

Yingjian CHEN, Shang WU, Yuancheng CAO, Baoshuai DU, Zhenxing WANG, Zhongwen OUYANG, Shun TANG. Application of magnetic separation in the recycling of cathode and anode materials from spent lithium batteries[J]. Energy Storage Science and Technology, 2025, 14(5): 1918-1927.

Figures/Tables 10

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References 36

1	BISWAL B K, ZHANG B, THI MINH TRAN P, et al. Recycling of spent lithium-ion batteries for a sustainable future: Recent advancements[J]. Chemical Society Reviews, 2024, 53(11): 5552-5592. DOI: 10.1039/D3CS00898C.
2	RAJ T, CHANDRASEKHAR K, KUMAR A N, et al. Recycling of cathode material from spent lithium-ion batteries: Challenges and future perspectives[J]. Journal of Hazardous Materials, 2022, 429: 128312. DOI: 10.1016/j.jhazmat.2022.128312.
3	时玮, 张言茹, 陈大分, 等. 锰酸锂动力电池寿命测试方法[J]. 汽车工程, 2015, 37(1): 67-71, 119. DOI: 10.19562/j.chinasae.qcgc. 2015.01.012.
	SHI W, ZHANG Y R, CHEN D F, et al. Lifespan test method for LiMn₂O₄ traction batteries[J]. Automotive Engineering, 2015, 37(1): 67-71, 119. DOI: 10.19562/j.chinasae.qcgc.2015.01.012.
4	李棉, 程琍琍, 杨幼明, 等. 锂离子电池回收利用技术研究进展[J]. 稀有金属, 2022, 46(3): 349-366. DOI: 10.13373/j.cnki.cjrm.XY20020020.
	LI M, CHENG L L, YANG Y M, et al. Development of technology for spent lithium-ion batteries recycling: A review[J]. Chinese Journal of Rare Metals, 2022, 46(3): 349-366. DOI: 10.13373/j.cnki.cjrm.XY20020020.
5	王洋洋. 磷酸铁锂电池荷电状态影响因素的研究[J]. 芜湖职业技术学院学报, 2022, 24(4): 72-75.
	WANG Y Y. Research on the factors influencing the state of charge of lithium iron phosphate battery[J]. Journal of Wuhu Institute of Technology, 2022, 24(4): 72-75.
6	王翠. 磷酸铁锂与石墨电极活性材料的高效浮选分离基础研究[D]. 长沙: 中南大学, 2023.
	WANG C. Fundamental study on high-efficiency flotation separation of lithium iron phosphate and graphite electrode materials [D]. Changsha: Central South University, 2023.
7	SHIN S M, KIM N H, SOHN J S, et al. Development of a metal recovery process from Li-ion battery wastes[J]. Hydrometallurgy, 2005, 79(3/4): 172-181. DOI: 10.1016/j.hydromet.2005.06.004.
8	ZHANG T, HE Y Q, WANG F F, et al. Chemical and process mineralogical characterizations of spent lithium-ion batteries: An approach by multi-analytical techniques[J]. Waste Management, 2014, 34(6): 1051-1058. DOI: 10.1016/j.wasman.2014.01.002.
9	江友周, 王宜, 李淑珍, 等. 退役锂电池有价金属湿化学分离技术研究进展[J]. 化学工业与工程, 2021, 38(6): 23-33. DOI: 10.13353/j.issn.1004.9533.20210822.
	JIANG Y Z, WANG Y, LI S Z, et al. Progress in hydrometallurgical separation and recovery of valuable metals from spent lithium-ion batteries[J]. Chemical Industry and Engineering, 2021, 38(6): 23-33. DOI: 10.13353/j.issn.1004.9533.20210822.
10	YIN R S, HU S H, YANG Y. Life cycle inventories of the commonly used materials for lithium-ion batteries in China[J]. Journal of Cleaner Production, 2019, 227: 960-971. DOI: 10. 1016/j.jclepro.2019.04.186.
11	XIONG S Q, JI J P, MA X M. Environmental and economic evaluation of remanufacturing lithium-ion batteries from electric vehicles[J]. Waste Management, 2020, 102: 579-586. DOI: 10. 1016/j.wasman.2019.11.013.
12	甘涛. 废旧锂离子电池电极材料磁性分离机制和工艺研究[D]. 广州: 广东工业大学, 2021. DOI: 10.27029/d.cnki.ggdgu.2021.001249.
	GAN T. Study on magnetic separation mechanism and technology of electrode materials for waste lithium ion batteries[D]. Guangzhou: Guangdong University of Technology, 2021. DOI: 10.27029/d.cnki.ggdgu.2021.001249.
13	HE L P, SUN S Y, SONG X F, et al. Recovery of cathode materials and Al from spent lithium-ion batteries by ultrasonic cleaning[J]. Waste Management, 2015, 46: 523-528. DOI: 10. 1016/j.wasman.2015.08.035.
14	HAGELÜKEN C. Recycling of electronic scrap at umicore's integrated metals smelter and refinery[J]. World of Metallurgy - ERZMETALL, 2006, 59(3): 152-161.
15	ZHANG Y C, WANG W Q, FANG Q, et al. Improved recovery of valuable metals from spent lithium-ion batteries by efficient reduction roasting and facile acid leaching[J]. Waste Management, 2020, 102: 847-855. DOI: 10.1016/j.wasman. 2019.11.045.
16	AN L. Recycling of spent lithium-ion batteries: processing methods and environmental impacts[M]. Cham: Springer, 2019.
17	CHEN X P, MA H R, LUO C B, et al. Recovery of valuable metals from waste cathode materials of spent lithium-ion batteries using mild phosphoric acid[J]. Journal of Hazardous Materials, 2017, 326: 77-86. DOI: 10.1016/j.jhazmat.2016.12.021.
18	PORVALI A, AALTONEN M, OJANEN S, et al. Mechanical and hydrometallurgical processes in HCl media for the recycling of valuable metals from Li-ion battery waste[J]. Resources, Conservation and Recycling, 2019, 142: 257-266. DOI: 10.1016/j.resconrec.2018.11.023.
19	赵嘉艺, 王星星, 祁磊, 等. 高梯度磁选理论与技术进展[J]. 矿产保护与利用, 2024, 44(3): 117-126. DOI: 10.13779/j.cnki.issn1001-0076.2024.03.013.
	ZHAO J Y, WANG X X, QI L, et al. Progress in the theory and technology of highgradient magnetic separation[J]. Conservation and Utilization of Mineral Resources, 2024, 44(3): 117-126. DOI: 10.13779/j.cnki.issn1001-0076.2024.03.013.
20	YAMAJI Y, DODBIBA G, MATSUO S, et al. A novel flow sheet for processing of used lithium-ion batteries for recycling[J]. Resources Processing, 2011, 58(1): 9-13. DOI: 10.4144/rpsj.58.9.
21	HU Z C, LIU J G, GAN T, et al. High-intensity magnetic separation for recovery of LiFePO₄ and graphite from spent lithium-ion batteries[J]. Separation and Purification Technology, 2022, 297: 121486. DOI: 10.1016/j.seppur.2022.121486.
22	耿洪臣, 冯泉, 郭小飞. 磁选技术的现状与发展趋势[J]. 磁性材料及器件, 2010, 41(3): 10-13, 25. DOI: 10.3969/j.issn.1001-3830. 2010.03.002.
	GENG H C, FENG Q, GUO X F. Present status and development trend of magnetic separation technology[J]. Journal of Magnetic Materials and Devices, 2010, 41(3): 10-13, 25. DOI: 10.3969/j.issn.1001-3830.2010.03.002.
23	马苏杰. 我国磁选设备的现状和发展[J]. 山东工业技术, 2018(4): 65. DOI: 10.16640/j.cnki.37-1222/t.2018.04.058.
	MA S J. The Present Situation and Development of magnetic separation equipment in China[J]. Shandong Industrial Technology, 2018(4): 65. DOI: 10.16640/j.cnki.37-1222/t. 2018. 04.058.
24	甘涛, 宋卫锋, 刘勇, 等. 废旧电池电极材料的磁性分离机制及其提纯工艺[J]. 中国有色金属学报, 2021, 31(12): 3664-3674.
	GAN T, SONG W F, LIU Y, et al. Magnetic separation mechanism and purification process of spent battery electrode materials[J]. The Chinese Journal of Nonferrous Metals, 2021, 31(12): 3664-3674.
25	HUANG Z, LIN M, QIU R J, et al. A novel technology of recovering magnetic micro particles from spent lithium-ion batteries by ultrasonic dispersion and waterflow-magnetic separation[J]. Resources, Conservation and Recycling, 2021, 164: 105172. DOI: 10.1016/j.resconrec.2020.105172.
26	LI J, WANG G X, XU Z M. Environmentally-friendly oxygen-free roasting/wet magnetic separation technology for in situ recycling cobalt, lithium carbonate and graphite from spent LiCoO₂/graphite lithium batteries[J]. Journal of Hazardous Materials, 2016, 302: 97-104. DOI: 10.1016/j.jhazmat.2015.09.050.
27	HUANG Z, ZHU J, QIU R J, et al. A cleaner and energy-saving technology of vacuum step-by-step reduction for recovering cobalt and nickel from spent lithium-ion batteries[J]. Journal of Cleaner Production, 2019, 229: 1148-1157. DOI: 10.1016/j.jclepro.2019.05.049.
28	QIU R J, HUANG Z, ZHENG J Y, et al. Energy models and the process of fluid-magnetic separation for recovering cobalt micro-particles from vacuum reduction products of spent lithium ion batteries[J]. Journal of Cleaner Production, 2021, 279: 123230. DOI: 10.1016/j.jclepro.2020.123230.
29	HUANG Z, LIU F, MAKUZA B, et al. Metal reclamation from spent lithium-ion battery cathode materials: Directional conversion of metals based on hydrogen reduction[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(2): 756-765. DOI: 10.1021/acssuschemeng.1c05721.
30	SMITH Y R, NAGEL J R, RAJAMANI R K. Eddy current separation for recovery of non-ferrous metallic particles: A comprehensive review[J]. Minerals Engineering, 2019, 133: 149-159. DOI: 10.1016/j.mineng.2018.12.025.
31	REM P C, LEEST P A, VAN DEN AKKER A J. A model for eddy current separation[J]. International Journal of Mineral Processing, 1997, 49(3/4): 193-200. DOI: 10.1016/S0301-7516(96)00045-2.
32	RUAN J J, QIAN Y M, XU Z M. Environment-friendly technology for recovering nonferrous metals from e-waste: Eddy current separation[J]. Resources, Conservation and Recycling, 2014, 87: 109-116. DOI: 10.1016/j.resconrec.2014.03.017.
33	BI H J, ZHU H B, ZU L, et al. Eddy current separation for recovering aluminium and lithium-iron phosphate components of spent lithium-iron phosphate batteries[J]. Waste Management & Research, 2019, 37(12): 1217-1228. DOI: 10.1177/0734242X19871610.
34	BI H J, ZHU H B, ZU L, et al. A new model of trajectory in eddy current separation for recovering spent lithium iron phosphate batteries[J]. Waste Management, 2019, 100: 1-9. DOI: 10.1016/j.wasman.2019.08.041.
35	DHOLU N, NAGEL J R, COHRS D, et al. Eddy current separation of nonferrous metals using a variable-frequency electromagnet[J]. KONA Powder and Particle Journal, 2017, 34: 241-247. DOI: 10.14356/kona.2017012.
36	BAI Y X, ZHU H B, ZU L, et al. Eddy current separation of broken lithium battery products in consideration of the shape factor[J]. Journal of Material Cycles and Waste Management, 2023, 25(4): 2262-2275. DOI: 10.1007/s10163-023-01681-0.

回收方法	适用范围	环境影响	工艺特点	经济成本	参考文献
高梯度磁选	通过强磁场分离弱磁性和非磁性物质，适合分离含Co、Ni等顺磁性材料，但对非磁性材料效果有限	物理分离过程，无废水、废气排放，对环境友好。能耗高，有噪声污染	分选精度高，但回收率易受粒径和形状影响	投资成本高，能耗较大	[19, 21, 24-25]

湿式磁选	该方法通常包括氧化、还原、沉淀等物理化学处理步骤，用于改变物料的磁性，随后结合磁选法进行分离。可用于回收弱磁性或非磁性材料以及复杂的废料组合	回收过程中要消耗大量化学试剂，并且会产生废水、废气等污染物	回收率高，不受物料粒径、形状等物理特性的影响	成本和运行成本适中，但废水处理费用和设备的耐腐蚀性维护成本较高	[26-29]

涡流分选	基于电磁感应，通过涡流力分离高导电性金属和低导电性材料，适合回收正负极材料中的Al和Cu杂质	属于物理分离方法，无化学试剂参与，对环境污染小，能耗高，有噪声污染	通过永磁体产生交变磁场，磁场大小有限，对于粒径较小的物料分选效果不明显	成本较低，自动化程度高，适合大规模回收作业	[30, 32-33, 35-36]

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[4]	Hai WANG, Yuhua BIAN, Jiadong WANG, Zhaoyang LIU, Jie ZHANG, Jian YAO, Xuanwen GAO, Zhaomeng LIU, Wenbin LUO. Retired lithium battery recycling and battery-grade lithium carbonate preparation [J]. Energy Storage Science and Technology, 2023, 12(5): 1453-1460.
[5]	Huiqun YU, Zhehao HU, Daogang PENG, Haoyi SUN. Key technologies for retired power battery recovery and its cascade utilization in energy storage systems [J]. Energy Storage Science and Technology, 2023, 12(5): 1675-1685.
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