废旧三元锂离子动力电池循环再生利用工艺概述

doi:10.19964/j.issn.1006-4990.2022-0487

Abstract

Abstract:

In the context of energy crisis and greenhouse effect，lithium-ion batteries are widely used in power batteries and energy storage.The service life of lithium-ion battery is only 3~5 years.After that，the battery will not meet the service requirements and needs to be decommissioned.However，the precious metals in ternary lithium-ion power batteries are much higher than the corresponding ore raw materials，so recycling the precious metals can not only alleviate the resource problems，but also protect the environment.The utilization process of waste ternary lithium ion power batteries was reviewed，including the cascade utilization，wet recovery of precious metals and regeneration process.The wet recovery was pretreating in the form of discharge and crushing，and then leaching with inorganic acid and reducing agent，and then removing impurities through chemical precipitation and similar phase solution principle，and then resynthesizing precursor through regeneration technology，and finally generating cathode materials through sintering.The advantages and disadvantages of existing application technologies were analyzed.The future development of recycling technology should be green，low-cost and environmentally friendly.

Key words: Lithium ion battery, ternary battery, step utilization, recycling and regeneration

CLC Number:

TQ131.11

YU Hui, WANG Yubin, LIAO Zhejun, YANG Yunguang. Overview of recycling and utilization process of waste ternary lithium-ion power batteries[J]. Inorganic Chemicals Industry, 2023, 55(7): 32-37.

Figures/Tables 4

References 31

1	荆乾坤.典型锂离子电池正极材料的湿法回收与再生基础研究［D］.北京：北京科技大学，2021.
	JING Qiankun.Basic research on wet chemical recovery and regeneration of typical cathode materials of lithium-ion batteries［D］.Beijing：University of Science and Technology Beijing，2021.
2	张蕊.新能源车火爆催生千亿市场，电池回收“一天一价”：新注册企业增26倍行业急速扩张，新蓝海还是加速变红海？［N］.每日经济新闻，2022-01-11（5）.
3	李扬，王军.退役锂离子电池筛选分类方法设计与分析［J］.电池，2020，50（4）：403-407.
	LI Yang， WANG Jun.Design and analysis of screening and classification methods for retired Li-ion battery［J］.Battery Bimonthly，2020，50（4）：403-407.
4	谭震，范茂松，赵光金，等.动力电池梯次利用国家标准体系分析［J］.电池，2022，52（4）：443-446.
	TAN Zhen， FAN Maosong， ZHAO Guangjin，et al.Analysis of national standard system for power battery echelon utilization［J］.Battery Bimonthly，2022，52（4）：443-446.
5	肖武坤，张辉.中国废旧车用锂离子电池回收利用概况［J］.电源技术，2020，44（8）：1217-1222.
	XIAO Wukun， ZHANG Hui.Recycling status of spent lithium-ion batteries for electric vehicle in China［J］.Chinese Journal of Power Sources，2020，44（8）：1217-1222.
6	梁新成，张勉.车载退役锂离子电池回收研究［J］.电源学报，2022，20（4）：86-91.
	LIANG Xincheng， ZHANG Mian.Study on recycling of ex-service lithium-ion batteries used in electric vehicles［J］.Journal of Power Supply，2022，20（4）：86-91.
7	杨健，秦吉涛，李芳成，等.废旧锂离子电池的湿法回收研究进展［J］.中南大学学报（自然科学版），2020，51（12）：3261-3278.
	YANG Jian， QIN Jitao， LI Fangcheng，et al.Review of hydrometallurgical processes for recycling spent lithium-ion batteries［J］.Jo-
	urnal of Central South University（Science and Technology），2020，51（12）：3261-3278.
8	HANISCH C， LOELLHOEFFEL T， DIEKMANN J，et al.Recycling of lithium-ion batteries：A novel method to separate coating and foil of electrodes［J］.Journal of Cleaner Production，2015，108：301-311.
9	HE Lipo， SUN Shuying， SONG Xingfu，et al.Recovery of cathode materials and Al from spent lithium-ion batteries by ultrasonic cleaning［J］.Waste Management，2015，46：523-528.
10	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 Qinghua， ZOU Ailing， TONG Hui，et al.Research progress on recycling technology of cathode materials for spent ternary lithium-ion batteries［J］.Materials Reports，2021，35（1）：1011-1022.
11	LU Mi， ZHANG Houan， WANG Bingchen，et al.The re-synthesis of LiCoO₂ from spent lithium ion batteries separated by vacuum-assisted heat-treating method［J］.International Journal of Electrochemical Science，2013，8（6）：8201-8209.
12	董仲珍，冯强，李本盛.三元锂离子电池正极材料浸出回收工艺进展［J］.中国环境管理干部学院学报，2018，28（6）：59-62，70.
	DONG Zhongzhen， FENG Qiang， LI Bensheng.Leaching and reco-
	very process of cathode materials for ternary lithium ion battery［J］.Journal of Environmental Management College of China，2018，28（6）：59-62，70.
13	HE Lipo， SUN Shuying， SONG Xingfu，et al.Leaching process for recovering valuable metals from the LiNi_1/3Co_1/3Mn_1/3O₂ cathode of lithium-ion batteries［J］.Waste Management，2017，64：171- 181.
14	邹超，潘君丽，刘维桥，等.湿法回收锂离子电池三元正极材料的进展［J］.电池，2018，48（2）：130-134.
	ZOU Chao， PAN Junli， LIU Weiqiao，et al.Progress in hydrometallurgical process for recycling ternary cathode material of Li-ion battery［J］.Battery Bimonthly，2018，48（2）：130-134.
15	袁双，卢立峰，张宁远，等.废旧锂离子电池正极材料中钴的回收与高值化利用［J］.中国科技论文，2020，15（12）：1359-1363.
	YUAN Shuang， LU Lifeng， ZHANG Ningyuan，et al.Recovery and high value utilization of cobalt in cathode materials of spent lithium-ion battery［J］.China Sciencepaper，2020，15（12）： 1359-1363.
16	ZHAO Jingjing， ZHANG Beilei， XIE Hongwei，et al.Hydrometallurgical recovery of spent cobalt-based lithium-ion battery cathodes using ethanol as the reducing agent［J］.Environmental Research，2020，181：108803.
17	赵磊.废旧锂离子电池有机酸浸出回收钴、锂金属研究［D］.扬州：扬州大学，2021.
	ZHAO Lei.Study on recovery of cobalt and lithium metals by organic acid leaching of waste lithium ion batteries［D］.Yangzhou：Yangzhou University，2021.
18	VIROLAINEN S， FALLAH FINI M， LAITINEN A，et al.Solvent extraction fractionation of Li-ion battery leachate containing Li，Ni，and Co［J］.Separation and Purification Technology，2017，179：274-282.
19	JOO S H， SHIN D，OH C，et al.Extraction of Manganese by alkyl monocarboxylic acid in a mixed extractant from a leaching solution of spent lithium-ion battery ternary cathodic material［J］.Journal of Power Sources，2016，305：175-181.
20	JOO S H， SHIN D J，OH C，et al.Selective extraction and separation of nickel from cobalt，manganese and lithium in pre-treated leach liquors of ternary cathode material of spent lithium-ion batteries using synergism caused by Versatic 10 acid and LIX
	84-I［J］.Hydrometallurgy，2016，159：65-74.
21	李本盛.废旧锂离子电池中Li，Ni，Co的湿法工艺回收与利用［D］.赣州：江西理工大学，2020.
	LI Bensheng.Recycling and utilization of Li，Ni and Co from spent lithium-ion batteries by wet precess［D］.Ganzhou：Jiangxi University of Science and Technology，2020.
22	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 Xiaoxiao.Recycling and resource utilization of spent lithium-ion batteries［D］.Beijing：Beijing Institute of Technology，2016.
23	NIE Min， XIA Yunfei， WANG Zhenbo，et al.Effects of precursor particle size on the performance of LiNi_0.5Co_0.2Mn_0.3O₂ cathode material［J］.Ceramics International，2015，41（10）：15185-15192.
24	ZHANG Zheming， HE Wenzhi， LI Guangming，et al.Ultrasound-assisted hydrothermal renovation of LiCoO₂ from the cathode of spent lithium-ion batteries［J］.International Journal of Electrochemical Science，2014，9（7）：3691-3700.
25	王珊.高镍正极材料LiNi_1- _x Mg _x O₂的制备及改性研究［D］.哈尔滨：哈尔滨工业大学，2021.
	WANG Shan.Synthesis and structure optimization of LiNi_1- _x Mg _x O₂ high nickel binary cathode material［D］.Harbin：Harbin Institute of Technology，2021.
26	谭燚，缪畅，聂炎，等.废旧锂离子电池三元正极材料的回收与再利用工艺研究进展［J］.人工晶体学报，2020，49（10）：1944-1951.
	TAN Yi， MIAO Chang， NIE Yan，et al.Review on recycling and utilizing processes of ternary cathode materials in spent lithium-ion batteries［J］.Journal of Synthetic Crystals，2020，49（10）：1944-1951.
27	吴小龙，王晨麟，陈曦，等.废旧锂离子电池市场规模及回收利用技术［J］.环境科学与技术，2020，43（S2）：179-183.
	WU Xiaolong， WANG Chenlin， CHEN Xi，et al.Market scale and recycling technology of waste lithium-ion batteries［J］.Environmental Science & Technology，2020，43（S2）：179-183.
28	贺觉渊.工信部：今年新能源车销量料达500万辆［N］.证券时报，2022-01-13（A02）.
29	祝嫣然.工信部：加快推进动力电池回收利用立法［N］.第一财经日报，2021-10-20（A02）.
30	杨洁，李嫒嫒.重点行业碳达峰实施方案明确［N］.中国证券报，2021-12-04（A05）.
31	孙立极，史一棋.建好动力电池回收网［N］.人民日报，2021-08-02（7）.

正极材料	主要成分	理论能量密度/ （mA·h·g^-1）	实际能量密度/ （mA·h·g^-1）	电压/ V	循环性能/ 次数	资源	环保性	安全性能	适用温度/ ℃
镍酸锂	LiNiO₂	274	190~210	2.5~4.1	差	丰富	镍有毒	差	N/A
钴酸锂	LiCoO₂	274	135~140	3.6	＞300	匮乏	钴有毒	差	-20~55
锰酸锂	LiMnO₂	286	200	3.4~4.3	差	丰富	无毒	良好	高温不稳定
磷酸铁锂	LiFePO₄	170	130~140	3.2~3.7	＞2 000	非常丰富	无毒	好	-20~75
镍钴锰三元材料	LiNiCoMnO₂	278	155~165	3.0~4.5	＞800	匮乏	镍、钴有毒	良好	-20~55

[1]	ZHU Zhihong, ZHU Yongfang. Study on preparation and properties of silicon doped lithium manganate by self-propagating combustion [J]. Inorganic Chemicals Industry, 2023, 55(5): 66-70.
[2]	LIU Jinhang,YANG Zhipeng,CHEN Xiudong,LUO Yuxuan,YU Langhua,WANG Yawei,ZHAN Changchao,CAO Xiaohua. Preparation of new porous carbon and its lithium storage performance [J]. Inorganic Chemicals Industry, 2022, 54(9): 85-89.
[3]	KUANG Xinliang,LIU Chuixiang,XIONG Peng. Industry analysis and market prospect of lithium ion battery [J]. Inorganic Chemicals Industry, 2022, 54(8): 12-19.
[4]	ZHOU Lei,YUAN Yongshun,LI Lu,LIU Bingguang,LI Jiansheng. Research progress on preparation and application of lithium ion sieve from spent lithium ion batteries [J]. Inorganic Chemicals Industry, 2022, 54(8): 33-39.
[5]	Sun Xinhua,Hou Lei,Qin Kai. Market analysis of lithium hexafluorophosphate liquid electrolytes in lithium-ion battery [J]. Inorganic Chemicals Industry, 2021, 53(3): 7-11.
[6]	HU Yue,XU Lele,ZHOU Yanfang,XU Zhe,TIAN Shoushuai,LIAO Fan,YANG Xiaojun. Research progress on alkaline substance on surface of nickel-rich ternary cathode materials [J]. Inorganic Chemicals Industry, 2021, 53(12): 74-79.
[7]	LU Chao,LI Mingming,WU Xiaoqiang,AN Xuguang,KONG Qingquan,WANG Xiaolian. Research progress on modification of solid inorganic electrolyte of Li₇La₃Zr₂O₁₂ [J]. Inorganic Chemicals Industry, 2021, 53(11): 10-16.
[8]	Liu Yang,Cai Zongying,Cao Weigang,Liu Yuzhao. Research progress on lithium sodium titanate for lithium ion batteries [J]. Inorganic Chemicals Industry, 2021, 53(10): 36-40.
[9]	Wang Kuangbin,Xu Shengxia,Wang Yongqin. Research on purification process of lithium difluorosulfimide optimized by response surface method [J]. Inorganic Chemicals Industry, 2020, 52(9): 62-65.
[10]	Wang Jiatai,Zhao Duan,Ma Lianhua,Zhang Caihong. Research progress of LiFePO₄ cathode materials for Li-ion battery [J]. Inorganic Chemicals Industry, 2020, 52(4): 18-22.
[11]	Luo Chengguo,Xiao Jun,Fan Guangxin. Current situation and development of precursors for LiMn₂O₄ cathode used in lithium ion batteries [J]. Inorganic Chemicals Industry, 2020, 52(1): 26-29.
[12]	Sun Peiliang,Chen Shijuan,Yuan Li. Preparation and electrochemical properties of lithium difluorophosphate [J]. Inorganic Chemicals Industry, 2019, 51(5): 45-48.
[13]	LIANG Da-Yu. Effect of PVDF binder content on rheological properties of cathode slurry for lithium ion batteries [J]. INORGANICCHEMICALSINDUSTRY, 2016, 48(8): 77-.
[14]	BIAN Du-Cheng, LIU Shu-Lin, TIAN Yuan. Reusing of spent LiFePO4 cathode materials by solid phase lithium refilling method and electrochemical performance there of [J]. INORGANICCHEMICALSINDUSTRY, 2016, 48(2): 71-.
[15]	SANG Jun-Li, ZHAO Qing-Yun, LIU Da-Fan. Preparation and characterization of LiBF4 electrolyte of lithium ion batteries [J]. INORGANICCHEMICALSINDUSTRY, 2015, 47(7): 75-.

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Overview of recycling and utilization process of waste ternary lithium-ion power batteries

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