废旧锂离子电池中有价金属的回收研究进展

摘要随着锂离子电池在电动能源及储能领域的大量使用，废旧锂离子电池所带来的环境及资源问题日益突出。废旧锂离子电池中有价金属绿色高效的回收，在资源综合利用、节能环保及可持续发展等方面具有重大的现实意义，并逐渐成为世界各国的研究热点。综述了近年来国内外废旧锂离子电池中有价金属的回收现状，主要流程包括预处理、电极材料的溶解浸出及浸出液中有价金属的分离回收等环节，分析比较了各种回收途径的优缺点，并在此基础上对废旧锂离子电池回收工艺的发展趋势及应用前景做出了分析展望。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	张梦龙
	何几文
	田欢
	魏昊
	赵卓

关键词：废旧锂离子电池钴锂回收

Abstract： With the large-scale applying of lithium-ion batteries in the fields of electric energy and energy storage, the environmental and resource problems caused by the spent lithium ion batteries (LIBs) have become increasingly prominent. The recycling of valuable metals in spent LIBs has great practical significance in comprehensive utilization of resources, energy conservation, environmental protection and sustainable development, and has gradually become a hot topic in the world. In this paper, the recovery status of valuable metals in spent LIBs at home and abroad in recent years is reviewed. The main processes include pretreatment, dissolution and leaching of electrode materials as well as separation and recovery of valuable metal elements in the leaching solution. The advantages and disadvantages of various methods are analyzed and compared. On this basis, the development trend and application prospect of recovery process in spent LIBs are analyzed and prospected.

Keywords： spent lithium ions batteries； cobalt； lithium； recovery

Received 2018-05-28;

Fund:国家自然科学基金（51574003；51704011）；安徽省高校优秀青年人才支持计划（重点）项目（gxyqZD2018031）。

Corresponding Authors: 赵卓,E-mail:zhaozhuo1018@163.com。 Email: zhaozhuo1018@163.com

About author: 张梦龙(1995-),男,硕士研究生,现从事稀贵金属的提取与分离方面的研究。

引用本文:

张梦龙, 何几文, 田欢, 魏昊, 赵卓.废旧锂离子电池中有价金属的回收研究进展[J]. 化学工业与工程, 2019,36(4): 23-30

Zhang Menglong, He Jiwen, Tian Huan, Wei Hao, Zhao Zhuo.Research Progress on Recovery of Valuable Metals from Spent Lithium Ion Batteries[J]. Chemcial Industry and Engineering, 2019,36(4): 23-30

[1] Wu Z, Ren W, Wen L, et al. Graphene anchored with Co₃O₄ nanoparticles as anode of lithium ion batteries with enhanced reversible capacity and cyclic performance[J]. ACS Nano, 2010, 4(6):3187-3194
[2] Whittingham M S. Chalcogenide battery:US,19760673696[P]. 1977-02-22
[3] Whittingham M S. Electrical energy storage and intercalation chemistry[J]. Science, 1976, 192(4244):1126-1127
[4] Nagaura T, Tozawa K. Lithium ion rechargeable battery[J]. Prog Batteries Solar Cells, 1990, 9:209-217
[5] Slimm M, Spurrett R, Thwaite C, et al. Lithium-Ion batteries for space[J]. Space Power, 2002, 502(416):477-482
[6] Isaacson M J, Teofilo V L. Lithium ion aerospace batteries[C]//Seventeenth Annual Battery Conference on Applications and Advances. Proceedings of Conference (Cat. No.02TH8576), Seventeenth Annual Battery Conference on Applications and Advances, Long Beach, CA, USA, 2002
[7] Marsh R A, Vukson S, Surampudi S, et al. Li ion batteries for aerospace applications[J]. Journal of Power Sources, 2001, 97/98:25-27
[8] Bruce G C, Marcoux L. Large lithium ion batteries for aerospace and aircraft applications[J]. IEEE Aerospace and Electronic Systems Magazine, 2001, 16(9):24-28
[9] Martin C T, Kelly C O, Friend H D, et al. Lithium-Ion battery development at Eagle-Picher[C]//Fourteenth Annual Battery Conference on Applications and Advances. Proceedings of the Conference (Cat. No.99TH8371), Fourteenth Annual Battery Conference on Applications and Advances. Proceedings of the Conference (Cat. No.99TH8371), Long Beach, CA, USA, January 12-15, 1999
[10] 黎宇科. 有效利用并完善我国车用动力电池回收体系[J]. 低碳世界, 2012(3):30-31 Li Yuke. Effectively using and perfecting the vehicle battery recovery system in China[J]. Low Carbon World, 2012(3):30-31(in Chinese)
[11] 金玉健, 梅光军, 李树元. 废旧锂离子电池回收利用的研究现状[J]. 再生资源研究, 2005(6):22-25 Jin Yujian, Mei Guangjun, Li Shuyuan. Current study status on recycling of spent lithium-ion batteries[J]. Recycling Research, 2005(6):22-25(in Chinese)
[12] 欧秀芹, 孙新华, 程耀丽. 废锂离子电池的综合处理方法[J]. 天津化工, 2002, 16(4):35-36 Ou Xiuqin, Sun Xinhua, Cheng Yaoli. Comprehensive treatment of the waste lithium batteries[J]. Tianjin Chemical Industry, 2002, 16(4):35-36(in Chinese)
[13] Hagelüken C. Recycling of electronic scrap at Umicore's integrated metals smelter and refinery[J]. World of Metallurgy-Erzmetall, 2006, 59(3):152-161
[14] Cardarelli F, Dube J. Method for recycling spent lithium metal polymer rechargeable batteries and related materials:US,20030129112[P]. 2007-03-20
[15] 南俊民, 韩东梅, 崔明, 等. 溶剂萃取法从废旧锂离子电池中回收有价金属[J]. 电池, 2004, 34(4):309-311 Nan Junmin, Han Dongmei, Cui Ming, et al. Recycling of valuable metal from spent Li-ion batteries by solvent extraction[J]. Battery Bimonthly, 2004, 34(4):309-311(in Chinese)
[16] 郑洪河, 徐仲榆. 非水电解液中LiPF₆的光化学不稳定性[J]. 电池, 2004, 34(1):4-6 Zheng Honghe, Xu Zhongyu. Photochemical instability of LiPF₆ in non-aqueous electrolytes[J]. Battery Bimonthly, 2004, 34(1):4-6(in Chinese)
[17] 宋秀玲, 戴书琪, 徐永胜, 等. 废旧锂离子电池放电的实验研究[J]. 应用化工, 2015, 44(4):594-597 Song Xiuling, Dai Shuqi, Xu Yongsheng, et al. Experimental study on the discharge of the waste lithium ion battery[J]. Applied Chemical Industry, 2015, 44(4):594-597(in Chinese)
[18] 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
[19] Li J, Shi P, Wang Z, et al. A combined recovery process of metals in spent lithium-ion batteries[J]. Chemosphere, 2009, 77(8):1132-1136
[20] Sun L, Qiu K Q. Vacuum pyrolysis and hydrometallurgical process for the recovery of valuable metals from spent lithium-ion batteries[J]. Journal of Hazardous Materials, 2011, 194:378-384
[21] 孙亮. 废旧锂离子电池回收利用新工艺的研究[D]. 长沙:中南大学, 2012 Sun Liang. A novel reclamation process for spent lithium-ion batteries[D]. Changsha:Central South University, 2012(in Chinese)
[22] 梁立君. 废旧锂离子电池正极材料LiFePO₄的回收及合成的研究[D]. 辽宁大连:大连交通大学, 2012 Liang Lijun. Study on recovery and synthesis of LiFePO₄ cathode materials for spent lithium ion batteries[D]. Liaoning Dalian:Dalian Jiaotong University, 2012(in Chinese)
[23] Hanisch C, Haselrieder W, Kwade A. Recovery of active materials from spent lithium-ion electrodes and electrode production rejects[M]//Hanisch C, Haselrieder W, Kwade A. eds. Glocalized Solutions for Sustainability in Manufacturing. Berlin, Heidelberg:Springer Berlin Heidelberg, 2011
[24] 潘晓勇, 彭玲, 陈伟华, 等. 废旧锂离子电池中钴和锂的回收及综合利用[J]. 中国有色金属学报, 2013, 23(7):2047-2054 Pan Xiaoyong, Peng Ling, Chen Weihua, et al. Recovery of Co and Li from spent lithium-ion batteries and their comprehensive utilization[J]. The Chinese Journal of Nonferrous Metals, 2013, 23(7):2047-2054(in Chinese)
[25] 陈亮, 唐新村, 张阳, 等. 从废旧锂离子电池中分离回收钴镍锰[J]. 中国有色金属学报, 2011, 21(5):1192-1198 Chen Liang, Tang Xincun, Zhang Yang, et al. Separation and recovery of Ni, Co and Mn from spent lithium-ion batteries[J]. The Chinese Journal of Nonferrous Metals, 2011, 21(5):1192-1198(in Chinese)
[26] 陆修远, 张贵清, 曹佐英, 等. 采用硫酸-还原剂浸出工艺从废旧锂离子电池中回收LiNi_0.6Mn_0.2Co_0.2O₂[J]. 稀有金属与硬质合金, 2017, (6):14-23 Lu Xiuyuan, Zhang Guiqing, Cao Zuoying, et al. Recovery of LiNi_0.6Mn_0.2Co_0.2O₂ from spent lithium ion batteries by leaching with H₂SO₄ and reductants[J]. Rare Metals and Cemented Carbides, 2017, (6):14-23(in Chinese)
[27] 邓朝勇, 张谊, 杨茂麟, 等. 硫酸-双氧水浸出废旧锂离子电池中的钴[J]. 电池, 2011, 41(3):170-171 Deng Chaoyong, Zhang Yi, Yang Maolin, et al. Leaching cobalt from spent Li-ion battery by sulfuric acid-hydrogen peroxide[J]. Battery Bimonthly, 2011, 41(3):170-171(in Chinese)
[28] Mishra D, Kim D J, Ralph D E, et al. Bioleaching of metals from spent lithium ion secondary batteries using Acidithiobacillus Ferrooxidans[J]. Waste Management, 2008, 28(2):333-338
[29] Marcin A?G áková R, Kaduková J, Mra?íková A, et al. Metal bioleaching from spent lithium-ion batteries using acidophilic bacterial strains[J]. Inzynieria Mineralna, 2016, 17(1):117-120
[30] Swain B, Jeong J, Lee J C, et al. Separation of Co(Ⅱ) and Li(I) by supported liquid membrane using Cyanex 272 as mobile carrier[J]. Journal of Membrane Science, 2007, 297(1/2):253-261
[31] 吴芳. 从废旧锂离子二次电池中回收钴和锂[J]. 中国有色金属学报, 2004, 14(4):697-701 Wu Fang. Recovery of cobalt and lithium from spent lithium-ion secondary batteries[J]. The Chinese Journal of Nonferrous Metals, 2004, 14(4):697-701(in Chinese)
[32] Kang J, Senanayake G, Sohn J, et al. Recovery of cobalt sulfate from spent lithium ion batteries by reductive leaching and solvent extraction with Cyanex 272[J]. Hydrometallurgy, 2010, 100(3/4):168-171
[33] Pranolo Y, Zhang W, Cheng C Y. Recovery of metals from spent lithium-ion battery leach solutions with a mixed solvent extractant system[J]. Hydrometallurgy, 2010, 102(1/2/3/4):37-42
[34] Zhao J, Shen X, Deng F, et al. Synergistic extraction and separation of valuable metals from waste cathodic material of lithium ion batteries using Cyanex272 and PC-88A[J]. Separation and Purification Technology, 2011, 78(3):345-351
[35] 张新乐, 徐金球, 张晓琳. 酸浸-萃取-沉淀法回收废锂离子电池中的钴[J]. 化工环保, 2016, 36(3):326-331 Zhang Xinle, Xu Jinqiu, Zhang Xiaolin. Recovery of cobalt from spent lithium ion batteries by acid leaching-extraction-precipitation process[J]. Environmental Protection of Chemical Industry, 2016, 36(3):326-331(in Chinese)
[36] Sun L, Qiu K. Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries[J]. Waste Management, 2012, 32(8):1575-1582
[37] 李金惠, 曾现来, 申冰玉, 等. 一种以草酸为提取液的废锂离子电池回收处理方法及装置:CN, 103594754A[P]. 2014-02-19
[38] Myoung J, Jung Y, Lee J, et al. Cobalt oxide preparation from waste LiCoO₂ by electrochemical-hydrothermal method[J]. Journal of Power Sources, 2002, 112(2):639-642
[39] Freitas M B J G, Garcia E M. Electrochemical recycling of cobalt from cathodes of spent lithium-ion batteries[J]. Journal of Power Sources, 2007, 171(2):953-959
[40] 冯佳, 章骅, 邵立明, 等. 废旧锂离子电池中钴的离子交换法回收[J]. 环境卫生工程, 2008, 16(6):1-3 Feng Jia, Zhang Hua, Shao Liming, et al. Cobalt recovery from lithium-ion battery by ion-exchange method[J]. Environmental Sanitation Engineering, 2008, 16(6):1-3(in Chinese)
[41] 金玉健, 梅光军, 李树元. 盐析法从锂离子电池正极浸出液中回收钴盐的研究[J]. 环境科学学报, 2006, 26(7):1122-1125 Jin Yujian, Mei Guangjun, Li Shuyuan. Study on cobaltous recovery from cathode leachate of lithium-ion battery by salting out[J]. Acta Scientiae Circumstantiae, 2006, 26(7):1122-1125(in Chinese)