Research on the effect of microwave roasting on recovery of valuable metals from cathode materials of spent lithium ion batteries
LI Zhi-qin1, LI Shang-lue1, ZHUANG Xu-ning1,2,3, LI Fei4, GU Wei-hua2,3, BAI Jian-feng2,3, WANG Jing-wei2,3
1. School of Environmental and Materials Engineering, Shanghai Polytechnic University, Shanghai 201209, China; 2. Shanghai Collaborative Innovation Centre for WEEE recycling, Shanghai 201209, China; 3. Research Center of Resource Recycling Science and Engineering, Shanghai Polytechnic University, Shanghai 201209, China; 4. Environmental Science Research & Design Institute of Zhejiang Province, Hangzhou Zhejiang 310007, China
Abstract：Focusing on the metal recovery from the cathode material of spent lithium-ion batteries, microwave pre-treatment was proposed in this study to improve metals recovery efficiency. The results showed that different microwave power had its optimal treatment time, which could lead to high recovery efficiency of metals. Combined with process, energy consumption, cost and other factors, microwave roasting power with 600W and roasting time with 6min were determined to be the optimal pretreatment conditions. Under the conditions of H2SO4 +H2O2 as leaching system, solid-liquid ratio with 20g/L, reaction temperature with 80℃ and reaction time with 60min, the leaching rates of Li, Ni, Co and Mn reached 96%, 85%, 76% and 52%, respectively. The enhancement effect of microwave treatment on the leaching rate mainly came from the interaction of the following aspects:the instantaneous high temperature generated by the discharge of metal particles, the reduction reaction of metals and the removal of organics coating on the surface of material particles at the instantaneous high temperatures.
李之钦, 李商略, 庄绪宁, 李斐, 顾卫华, 白建峰, 王景伟. 微波焙烧强化废锂离子电池中的金属回收研究[J]. 中国环境科学, 2021, 41(10): 4712-4719.
LI Zhi-qin, LI Shang-lue, ZHUANG Xu-ning, LI Fei, GU Wei-hua, BAI Jian-feng, WANG Jing-wei. Research on the effect of microwave roasting on recovery of valuable metals from cathode materials of spent lithium ion batteries. CHINA ENVIRONMENTAL SCIENCECE, 2021, 41(10): 4712-4719.
Fan E, Li L, Wang Z, et al. Sustainable recycling technology for lithium-ion batteries and beyond:challenges and future prospects[J]. Chemical Reviews, 2020,120(14):7020-7063.
[2]
田庆华,邹艾玲,童汇,等.废旧三元锂离子电池正极材料回收技术研究进展[J]. 材料导报, 2021,35(1):1011-1022.Tian Q H, Zhou A L, Tong H, et al. Research progress on recycling technology of cathode materials for spent ternary lithium ion batteries[J]. Materials Reports, 2021,35(1):1011-1022.
[3]
中国科学院过程工程研究所.中国退役动力电池循环利用技术与产业发展报告[M]. 北京:人民出版社, 2019:3-4.Institute of Process Engineering, Chinese Academy of Sciences. Report on recycling technology and industrial development of retired power batteries in China[M]. Beijing:People's Publishing House, 2019:3-4.
[4]
国联汽车动力电池研究院有限责任公司,董扬.2019~2020年中国汽车动力电池及氢燃料电池产业发展年度报告[R]. 机械工业出版社, 2020.China Automotive Battery Research Institute, Dong Y. 2019~2020 Annual report on the development of China's automotive power cell and hydrogen fuel cell industry[R]. China Machine Press, 2020.
[5]
中国产业信息网.2019年动力电池回收行业需求情况、回收市场规模分析与预测[J]. 资源再生, 2019,(4):36-37.China Industrial Information Network. 2019 power battery recycling industry demand situation, recycling market size analysis and forecast[J]. Resource Recycling, 2019,(4):36-37.
[6]
郝涛,张英杰,董鹏,等.废旧三元动力锂离子电池正极材料回收的研究进展[J]. 硅酸盐通报, 2018,37(8):2451-2456.He T, Zhang Y J, Dong P, et al. Review on recycling cathode materials of spent ternary power lithium-ion batteries[J]. Bulletin of the Chinese Ceramic Society, 2018,37(8):2451-2456.
[7]
Zeng X, Li J, Shen B. Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid[J]. Journal of Hazardous Materials, 2015,295:112-118.
[8]
姚路.废锂离子电池正极材料回收再利用研究[D]. 新乡:河南师范大学, 2016.Yao L. Study on recycling of cathode material from waste lithium ion batteries[D]. Xinxiang:Henan Normal University, 2016.
[9]
蔡乐.废旧三元动力锂电池正极材料回收制备二氧化锰复合材料研究[D]. 上海:上海第二工业大学, 2018.Cai L. Research on the preparation of manganese dioxide composite materials by recycling the cathode material of the waste ternary power lithium battery[D]. Shanghai:Shanghai Polytechnic University, 2018.
[10]
孔德鹏.废旧锂离子电池三元正极材料回收与再利用工艺研究[D]. 北京:北京化工大学, 2019.Kong D P. Research on recovery and reuse process of NCM cathode material from spent LIBs[D]. Beijing:Beijing University of Chemical Technology, 2017.
[11]
Harper G, Sommerville R, Kendrick E, et al. Recycling lithium-ion batteries from electric vehicles[J]. Nature, 2019,575(7781):75-86.
[12]
毕诗文,杨毅宏.微波加热在冶金领域中应用研究现状[J]. 材料与冶金学报, 2004.3(2):117-120.Bi S W, Yang Y H. Present situation of study on microwave heating application in metallurgy[J]. Journal of Materials and Metallurgy, 2004,3(2):117-120.
[13]
陈伟,丁德馨,胡南,等.微波焙烧预处理难浸含金硫精矿[J]. 中国有色金属学报, 2015,25(7):2000-2005.Chen W, Ding D X, Hu N, et al. Pretreatment of refractory gold-bearing sulfur concentrates by microwave roasting[J]. The Chinese Journal of Nonferrous Metals, 2015,25(7):2000-2005.
[14]
Standish N, Worner H. Microwave application in the reduction of metal oxides with carbon[J]. Microwave Power and Electromagnetic Energy, 1990,25(3):177-180.
[15]
Huang Y F, Pan M W, Lo S L. Hydrometallurgical metal recovery from waste printed circuit boards pretreated by microwave pyrolysis[J]. Resources, Conservation & Recycling, 2020,163:1-7.
[16]
孙静.微波诱导热解废旧印刷线路板(WPCB)的实验和机理研究[D]. 济南:山东大学, 2012.Sun J. Experimental and mechanism research on microwave-induced pyrolysis of waste printed circuit boards (WPCB)[D]. Jinan:Shandong University, 2012.
[17]
Zhao Y Z, Liu B G, Zhang L B, et al. Microwave-absorbing properties of cathode material during reduction roasting for spent lithium-ion battery recycling[J]. Journal of Hazardous Materials, 2020,384:1-8.
[18]
Pindar S, Dhawan N. Recycling of mixed discarded lithium-ion batteries via microwave processing route[J]. Sustainable Materials and Technologies, 25:1-10.
[19]
朱曙光.废锂离子电池中钴酸锂材料超声修复研究[D]. 上海:同济大学, 2012.Zhu S G. Research on the renovation of lithium cobalt oxide from the cathode of spent lithium-ion batteries by ultrasonic irradiation[D]. Shanghai:Tongji University, 2012.
[20]
张笑笑.废旧锂离子电池的回收处理与资源化利用[D]. 北京:北京理工大学, 2016.Zhang X X. Recycling and resource utilization of spent lithium ion batteries[D]. Beijing:Beijing Institute of Technology, 2016.
[21]
胡亚飞.废旧三元锂离子电池(18650型)中有价金属湿法回收的研究[D]. 北京:北京化工大学, 2020.Hu Y F. Study on hydrometallurgical recovery of valuable metal from spent ternary lithium-ion batteries (type 18650)[D]. Beijing:Beijing University of Chemical Technology, 2020.
[22]
王超.废旧三元锂电池的还原氨浸及有价金属的回收利用[D]. 哈尔滨:哈尔滨工业大学, 2020.Wang C. Reduction ammonia leaching and recycling valuable metals from spent lithium-ion batteries[D]. Harbin:Harbin Institute of Technology, 2020.
[23]
Zhang X X, Ersha, et al. Toward sustainable and systematic recycling of spent rechargeable batteries[J]. Chemical Society reviews, 2018, 47(19):7239-7302.
[24]
王彪.微波加热过程中热点效应的试验与模拟研究[D]. 济南:山东大学, 2017.Wang B. Experimental and simulation study on hot-spot effects in microwave heating[D]. Jinan:Shandong University, 2017.
[25]
Demirskyi D, Agrawal D, Ragulya A. Neck formation between copper spherical particles under single-mode and multimode microwave sintering[J]. Materials Science & Engineering A, 2010,527(7/8):2142-2145.
[26]
刘鹏程.废旧三元电池材料的回收过程动力学与再生LiNi0.5Co0.2Mn0.3工艺研究[D]. 株洲:湖南工业大学, 2019.Liu P C. Study on kinetics in the recovering process of spent LiNixCoyMn1-x-yO2 lithium-ion battery cathode materials and its regeneration of LiNi0.5Co0.2Mn0.3O2[D]. Zhuzhou:Hunan University of Technology, 2019.
[27]
林利红,李雨龙,李聪波,等.工业电阻炉多参数能耗建模与预测[J]. 重庆大学学报, 2021,44(2):107-119.Lin L H, Li Y L, Li C B, et al. Multi-parameter energy consumption modeling and prediction of an industrial resistance furnace[J]. Journal of Chongqing University, 2021,44(2):107-119.
[28]
贺欣.柠檬酸还原性体系浸出废旧钴酸锂电池正极材料的研究[D]. 上海:上海第二工业大学, 2018.He X. Efficient leaching of valuable metals from LiCoO2 cathode material of spent lithium-ion batteries with citric acid reducing system[D]. Shanghai:Shanghai Polytechnic University, 2018.
