废锂离子电池正极材料中锂元素选择性回收的研究进展

doi:10.16085/j.issn.1000-6613.2021-1940

化工进展 ›› 2022, Vol. 41 ›› Issue (8): 4530-4543.DOI: 10.16085/j.issn.1000-6613.2021-1940

废锂离子电池正极材料中锂元素选择性回收的研究进展

王玥¹^,²(), 郑晓洪²^,³(), 陶天一², 刘秀庆⁴, 李丽¹(), 孙峙²

^1.北京理工大学材料学院，北京 100081
^2.中国科学院过程工程研究所，绿色过程与工程重点实验室，北京市
^1.过程污染控制工程技术研究中心，北京 100190，中国地质大学(北京)材料科学与工程学院，北京非金属矿物
^1.与固体废物材料利用重点实验室，矿物材料国家重点实验室，北京 100083，华友资源再生科技有限公司 ;浙江衢州 324000

收稿日期:2021-09-09 修回日期:2021-12-20 出版日期:2022-08-25 发布日期:2022-08-22
通讯作者: 郑晓洪,李丽
作者简介:王玥（1997—），女，硕士研究生，研究方向为锂离子电池资源化回收。E-mail：1679441065@qq.com。
基金资助:
国家自然科学基金(52002371);中国科学院绿色过程制造创新研究院项目(LAGM-2019-A15);中科院过程工程研究所南京绿色制造产业创新研究院重点研发项目(E0010715);中国科学院重点部署项目(ZDRM-CN-2020-1)

Review on selective recovery of lithium from cathode materials in spent lithium-ion batteries

WANG Yue¹^,²(), ZHENG Xiaohong²^,³(), TAO Tianyi², LIU Xiuqing⁴, LI Li¹(), SUN Zhi²

^1.School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China
^2.Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^3.Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences (Beijing), Beijing 100083, China
^4.Quzhou Huayou Resource Recycling Technology Company Limited, Quzhou 324000, Zhejiang, China

Received:2021-09-09 Revised:2021-12-20 Online:2022-08-25 Published:2022-08-22
Contact: ZHENG Xiaohong,LI Li

摘要/Abstract

摘要：

随着新能源汽车市场的蓬勃发展，锂离子电池作为新能源汽车的关键部件，面临着关键金属资源尤其是锂资源供给不足的风险，回收废锂离子电池中所含的二次锂资源将成为解决锂资源供需问题、推动行业可持续发展的重要途经。因此为实现废锂离子电池中锂元素的高效提取，分步或优先提取的选择性提锂工艺备受研究者们关注。本文介绍了火法、湿法、机械化学法和电化学法四种当前主流的选择性提锂工艺，在阐述其基础反应机理的基础上，总结归纳了各工艺最新的研究成果，并从提取过程中的工艺能耗、物耗、回收率、选择性、环境影响等多个角度对各工艺的优势和不足进行了深入分析。最后，对废锂离子电池中有价金属资源化回收的发展趋势及前景进行了展望，为未来研发更加清洁高效的回收工艺提供参考。

关键词: 锂, 锂离子电池, 回收, 选择性, 火法冶金, 湿法冶金, 电化学, 机械化学

Abstract:

With the vigorous development of the energy vehicle market, lithium-ion battery, as the key component of the new energy vehicles, has been facing the risk with insufficient supply of critical metal resources especially lithium resource. Recycling secondary lithium resources contained in waste lithium-ion batteries will become an indispensable way to solve the problem of unbalanced supply and demand of lithium resources and promote the sustainable development of the industry. Therefore, selective extraction of lithium by step or priority, which could promote efficient extraction of lithium from spent lithium-ion batteries, has attracted much attention of researchers. This review introduces four current mainstream methods of selective extraction including pyrometallurgy, hydrometallurgy, mechanochemical method and electrochemical method. And based on explaining their basic reaction mechanism, the results of the latest researches are summarized separately and the advantages and disadvantages of each extraction method are deeply analyzed from the several quantitative indexes such as energy consumption, material consumption, recovery ratio, selectivity and environmental impact. Finally, the development trend and prospect of the recovery of valuable metals in spent lithium-ion batteries are put forward, aiming at providing references for the development of cleaner and more efficient recycling process in the future.

Key words: lithium, lithium-ion batteries, recovery, selectivity, pyrometallurgy, hydrometallurgy, electrochemistry, mechanochemistry

中图分类号:

王玥, 郑晓洪, 陶天一, 刘秀庆, 李丽, 孙峙. 废锂离子电池正极材料中锂元素选择性回收的研究进展[J]. 化工进展, 2022, 41(8): 4530-4543.

WANG Yue, ZHENG Xiaohong, TAO Tianyi, LIU Xiuqing, LI Li, SUN Zhi. Review on selective recovery of lithium from cathode materials in spent lithium-ion batteries[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4530-4543.

图/表 9

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国家	储量/10⁴t
阿根廷	1930
玻利维亚	2100
智利	960
澳大利亚	640
美国	790
中国	510
刚果	300

国家	储量/10⁴t
阿根廷	1930
玻利维亚	2100
智利	960
澳大利亚	640
美国	790
中国	510
刚果	300

企业	所属国家	回收工艺	回收产品
AEA	英国	电化学	氧化钴、氢氧化锂
Recupyl	法国	湿法	氢氧化钴、碳酸锂/磷酸锂
Accurec	德国	火法	钴基合金、富锂残渣
Umicore	比利时	火法	高值合金（钴/镍/铜）、富锂残渣
Inmetco	美国	火法	钴基合金

企业	所属国家	回收工艺	回收产品
AEA	英国	电化学	氧化钴、氢氧化锂
Recupyl	法国	湿法	氢氧化钴、碳酸锂/磷酸锂
Accurec	德国	火法	钴基合金、富锂残渣
Umicore	比利时	火法	高值合金（钴/镍/铜）、富锂残渣
Inmetco	美国	火法	钴基合金

电池	浸出试剂	温度/℃	时间/min	浸出效率	参考文献
LiCoO₂	磷酸+葡萄糖	80	120	Li 100%，Co 98%	［75］
LiNi _x Co _y Mn _z O₂	硫酸+亚硫酸氢钠	95	240	Li 96.7%，Co 91.6%，Ni 96.4%，Mn 87.9%	［76］
LiCoO₂	柠檬酸+过氧化氢	90	60	Li 100%，Co 99%	［77］
LiNi _x Co _y Mn _z O₂	甲酸+过氧化氢	60	120	Li 100%，Co 85%，Ni 85%，Mn 85%	［78］
LiCoO₂	盐酸	80	90	Li 100%，Co 100%	［79］

废锂离子电池正极材料中锂元素选择性回收的研究进展

Review on selective recovery of lithium from cathode materials in spent lithium-ion batteries

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工艺	优点	缺点
火法	工艺流程短（焙烧+浸出+沉淀），锂回收率高（≥90%），选择性高（≥99%），提锂条件温和（常温浸出）	能耗高（焙烧温度普遍大于500℃），环境风险高（CO₂、SO _x 、NO _x 、HCl尾气排放），高温下锂易以气态形式挥发，易损失
湿法	工艺流程短（浸出+沉淀），锂回收率高（≥92%），浸出温度低（30~90℃），能耗低，工艺流程简单，易于工业化应用	易造成其他金属的浸出，选择性低；药剂消耗量大，需消耗大量的酸/碱，环境风险高（H₂SO₄、HCl、HNO₃酸雾排放，高盐废水排放）
机械化学法	工艺流程短（焙烧+浸出+沉淀），锂回收率高（≥92%），选择性高（≥99%），提锂条件温和（常温浸出）	设备规模化受限，药剂消耗量大，需添加大量的助磨剂，工艺流程会产生高盐废水
电化学法	工艺流程短（浸出+沉淀），锂回收率高（≥98%），选择性高（≥99%），提锂条件温和（常温浸出），无化学试剂消耗	设备规模化受限，电能消耗较高

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