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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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。
With the recent rapid expand of LiNi_xCo_yMn_zO_2 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_xCo_yMn_zO_2 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_xCo_yMn_zO_2 batteries by wet process, with the focus placed on the leaching methods of valuable metals, separation and extraction of valuable metals, reutilization and leachingkinetics. The advantages and disadvantages of different processing methods are compared. In addition,economic analysis shows that the recovery of valuable metals from retired LiNi_xCo_yMn_zO_2 batteries hasconsiderable economic value. Finally, the methods for the recovery of the valuable metals of LiNi_xCo_yMn_zO_2 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_xCo_yMn_zO_2 batteries.
With the recent rapid expand of LiNi_xCo_yMn_zO_2 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_xCo_yMn_zO_2 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_xCo_yMn_zO_2 batteries by wet process, with the focus placed on the leaching methods of valuable metals, separation and extraction of valuable metals, reutilization and leachingkinetics. The advantages and disadvantages of different processing methods are compared. In addition,economic analysis shows that the recovery of valuable metals from retired LiNi_xCo_yMn_zO_2 batteries hasconsiderable economic value. Finally, the methods for the recovery of the valuable metals of LiNi_xCo_yMn_zO_2 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_xCo_yMn_zO_2 batteries.
引文
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[3]张笑笑,王鸯鸯,刘媛,等.废旧锂离子电池回收处理技术与资源化再生技术进展[J].化工进展, 2016, 35(12):4026-4032.ZHANG Xiaoxiao, WANG Yangyang, LIU Yuan, et al. Recent progressin disposal and recycling of spent lithium-ion batteries[J]. ChemicalIndustry and Engineering Progress, 2016, 35(12):4026-4032.
[4]郑莹,刘禹,王梦.报废锂离子电池有价金属回收现状研究[J].电源技术, 2014, 38(9):1758-1761.ZHENG Ying, LIU Yu, WANG Meng. Research on recycling valuablemetal from spent lithium-ion batteries[J]. Chinese Journal of PowerSources, 2014, 38(9):1758-1761.
[5]吴越,裴锋,贾路路,等.废旧锂离子电池中有价金属的回收技术进展[J].稀有金属, 2013, 37(2):320-329.WU Yue, PEI Feng, JIA Lulu, et al. Overview of recovery technique ofvaluable metals from spent lithium ion batteries[J]. Chinese Journal ofRare Metals, 2013, 37(2):320-329.
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[7] ZHANG T, HE Y, WANG F, et al. Chemical and process mineralogicalcharacterizations of spent lithium-ion batteries:an approach by multi-analytical techniques[J]. Waste Management, 2014, 34(6):1051-1058.
[8] NIE H, XU L, SONG D, et al. LiCoO2:recycling from spent batteriesand regeneration with solid state synthesis[J]. Green Chemistry, 2015,17(2):1276-1280.
[9] LI L, LU J, REN Y, et al. Ascorbic-acid-assisted recovery of cobaltand lithium from spent Li-ion batteries[J]. Journal of Power Sources,2012, 218(12):21-27.
[10]谢英豪,余海军,欧彦楠,等.废旧动力电池回收的环境影响评价研究[J].无机盐工业, 2015, 47(4):43-46.XIE Yinghao, YU Haijun, OU Yannan, et al. Environmental impactassessment of recycling waste traction battery[J]. Inorganic ChemicalsIndustry, 2015, 47(4):43-46.
[11] SHIN S M, KIM N H, SOHN J S, et al. Development of a metalrecovery process from Li-ion battery wastes[J]. Hydrometallurgy,2005, 79(3):172-181.
[12] SONG D W, WANG X Q, ZHOU E L, et al. Recovery and heattreatment of the Li(Ni1/3Co1/3Mn1/3)O2cathode scrap material for lithiumion battery[J]. Journal of Power Sources, 2013, 232:348-352.
[13] HANISCH C, LOELLHOEFFEL T, DIEKMANN J, et al. Recycling oflithium-ion batteries:a novel method to separate coating and foil ofelectrodes[J]. Journal of Cleaner Production, 2015, 108:301-311.
[14] YANG L, XI G X, XI Y B. Recovery of Co, Mn, Ni, and Li from spentlithium ion batteries for the preparation of LiNix Coy Mnz O2cathodematerials[J]. Ceramics International, 2015, 41(9):11498-11503.
[15] CHEN X P, ZHOU T. Hydrometallurgical process for the recovery ofmetal values from spent lithium-ion batteries in citric acid media[J].Waste Management&Research, 2014, 32(11):1083-1093.
[16] HU J T, ZHANG J L, LI H X, et al. A promising approach for therecovery of high value-added metals from spent lithium-ion batteries[J]. Journal of Power Sources, 2017, 351:192-199.
[17]李长东,余海军,陈清后.从废旧锂电池中回收制备三元正极材料的研究[J].资源再生, 2011(8):62-65.LI Changdong, YU Haijun, CHEN Qinghou. Study on treatmentprocese of retired lithium batteries and preparation of ternary positivematerials[J]. Resource Recycling, 2011(8):62-65.
[18] WANG Hailin, NIE Lie, LI Jing, et al. Characterization andassessment of volatile organic compounds(VOCs)emissions fromtypical industries[J]. Chinese Science Bulletin, 2013, 589(7):724-730.
[19]吕小三,雷立旭,余小文,等.一种废旧锂离子电池成分分离的方法[J].电池, 2007, 37(1):79-80.LüXiaosan, LEI Lixu, YU Xiaowen, et al. A separate method forcomponents of spent Li-ion battery[J]. Battery Bimonthly, 2007, 37(1):79-80.
[20] GU Fang, LI Junsheng. Preparation of LiCoO2from spent lithium-ionbatteries[J]. Journal of Harbin University of Commerce, 2010, 183-185:1553-1557.
[21] HANISCH C, HASELRIEDER W, KWADE A. Recovery of activematerials from spent lithium-ion electrodes and electrode productionrejects[M]. Berlin Heidelberg:Springer, 2011:85-89.
[22] LI J H, LI X H, HU Q Y, et al. Study of extraction and purification ofNi, Co and Mn from spent battery material[J]. Hydrometallurgy, 2009,99(1/2):7-12.
[23]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 andrecovery of Ni, Co and Mn from spent lithium-ion batteries[J]. TheChinese Journal of Nonferrous Metals, 2011, 21(5):1192-1198.
[24] MESHRAM P, PANDEY B D, MANKHAND T R. Hydrometallurgicalprocessing of spent lithium ion batteries(LIBs)in the presence of areducing agent with emphasis on kinetics of leaching[J]. ChemicalEngineering Journal, 2015, 281:418-427.
[25] YANG Y, XU S M, HE Y H. Lithium recycling and cathode material regeneration from acid leach liquor of spent lithium-ion battery via facile co-extraction and co-precipitation processes[J]. WasteManagement, 2017, 64:219-227.
[26] MESHRAM P, ABHILASH, PANDEY B D, et al. Acid baking of spentlithium ion batteries for selective recovery of major metals:a two-stepprocess[J]. Journal of Industrial and Engineering Chemistry, 2016, 43:117-126.
[27] SENCANSKI J, BAJUK-BOGDANOVIC D, MAJSTOROVIC D, et al.The synthesis of Li(Co-Mn-Ni)O2cathode material from spent-Li ionbatteries and the proof of its functionality in aqueous lithium andsodium electrolytic solutions[J]. Journal of Power Sources, 2017, 342:690-703.
[28] LI L, FAN E S, GUAN Y B A, et al. Sustainable recovery of cathodematerials from spent lithium-ion batteries using lactic acid leachingsystem[J]. ACS Sustainable Chemistry&Engineering, 2017, 5(6):5224-5233.
[29] MESHRAM P, ABHILASH, PANDEY B D, et al. Comparision ofdifferent reductants in leaching of spent lithium ion batteries[J]. JOM,2016, 68(10):2613-2623.
[30] GAO W F, ZHANG X H, ZHENG X H, et al. Lithium carbonaterecovery from cathode scrap of spent lithium-ion battery:a closed-loop process[J]. Environmental Science&Technology, 2017, 51(3):1662-1669.
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