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

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

Chemical Industry and Engineering Progress ›› 2022, Vol. 41 ›› Issue (8): 4530-4543.DOI: 10.16085/j.issn.1000-6613.2021-1940

• Resources and environmental engineering • Previous Articles Next Articles

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:2022-08-22 Published:2022-08-25
Contact: ZHENG Xiaohong,LI Li

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

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)

Abstract

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

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

CLC Number:

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.

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.

Figures/Tables 9

References 98

1	黄健航, 王永刚, 夏永姚. 新型储能化学电源研究进展[J]. 电源技术, 2020, 44(6): 793-798.
	HUANG Jianhang, WANG Yonggang, XIA Yongyao. Research progress of new energy storage electrochemical power sources[J]. Chinese Journal of Power Sources, 2020, 44(6): 793-798.
2	CHAYAMBUKA K, MULDER G, DANILOV D L, et al. Sodium-ion battery materials and electrochemical properties reviewed[J]. Advanced Energy Materials, 2018, 8(16): 1800079.
3	ARSHAD F, LI L, AMIN K, et al. A comprehensive review of the advancement in recycling the anode and electrolyte from spent lithium ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(36): 13527-13554.
4	SANTANA I L, MOREIRA T F M, LELIS M F F, et al. Photocatalytic properties of Co₃O₄/LiCoO₂ recycled from spent lithium-ion batteries using citric acid as leaching agent[J]. Materials Chemistry and Physics, 2017, 190: 38-44.
5	ARMAND M, TARASCON J M. Building better batteries[J]. Nature, 2008, 451(7179): 652-657.
6	罗明增, 周柯, 吴珏, 等. 二次电池储能机理的电化学谱学研究进展[J]. 厦门大学学报(自然科学版), 2020, 59(5): 726-746.
	LUO Mingzeng, ZHOU Ke, WU Jue, et al. Research progress of electrochemical spectroscopy on energy storage mechanism of rechargeable batteries[J]. Journal of Xiamen University (Natural Science), 2020, 59(5): 726-746.
7	RAZMJOU A, ASADNIA M, HOSSEINI E, et al. Design principles of ion selective nanostructured membranes for the extraction of lithium ions[J]. Nature Communications, 2019, 10: 5793.
8	YANG S X, ZHANG F, DING H P, et al. Lithium metal extraction from seawater[J]. Joule, 2018, 2(9): 1648-1651.
9	ZENG X L, LI J H. Emerging anthropogenic circularity science: principles, practices, and challenges[J]. iScience, 2021, 24(3): 102237.
10	The United States Geological Survey(USGS). Mineral commodity summaries [EB/OL]. [2021-08-12]. .
11	韩佳欢, 乜贞, 方朝合, 等. 中国锂资源供需现状分析[J]. 无机盐工业, 2021, 53(12): 61-66.
	HAN Jiahuan, NIE Zhen, FANG Chaohe, et al. Analysis of existing circumstance of supply and demand on China’s lithium resources[J]. Inorganic Chemicals Industry, 2021, 53(12): 61-66.
12	马哲, 李建武. 中国锂资源供应体系研究: 现状、问题与建议[J]. 中国矿业, 2018, 27(10): 1-7.
	MA Zhe, LI Jianwu. Analysis of China’s lithium resources supply system: status, issues and suggestions[J]. China Mining Magazine, 2018, 27(10): 1-7.
13	齐帅军, 肖克炎, 丁建华, 等. 中国锂矿资源分布和潜力分析[J]. 矿床地质, 2014, 33(S1): 809-810.
	QI Shuaijun, XIAO Keyan, DING Jianhua, et al. Analysis of distribution and potential on China’s lithium resources[J]. Mineral Deposits, 2014, 33(S1): 809-810.
14	ZOU H Y, GRATZ E, APELIAN D, et al. A novel method to recycle mixed cathode materials for lithium ion batteries[J]. Green Chemistry, 2013, 15(5): 1183.
15	DUNN J B, GAINES L, KELLY J C, et al. Life cycle analysis summary for automotive lithium-ion battery production and recycling[M]. Cham: Springer International Publishing, 2016: 73-79.
16	HOSSAIN R, KUMAR U, SAHAJWALLA V. Selective thermal transformation of value added cobalt from spent lithium-ion batteries[J]. Journal of Cleaner Production, 2021, 293: 126140.
17	HU J T, ZHANG J L, LI H X, et al. A promising approach for the recovery of high value-added metals from spent lithium-ion batteries[J]. Journal of Power Sources, 2017, 351: 192-199.
18	HU X F, MOUSA E, TIAN Y, et al. Recovery of Co, Ni, Mn, and Li from Li-ion batteries by smelting reduction-Part I: A laboratory-scale study[J]. Journal of Power Sources, 2021, 483: 228936.
19	ATIA T A, ELIA G, HAHN R, et al. Closed-loop hydrometallurgical treatment of end-of-life lithium ion batteries: towards zero-waste process and metal recycling in advanced batteries[J]. Journal of Energy Chemistry, 2019, 35: 220-227.
20	黎华玲, 陈永珍, 宋文吉, 等. 湿法回收退役三元锂离子电池有价金属的研究进展[J]. 化工进展, 2019, 38(2): 921-932.
	LI Hualing, CHEN Yongzhen, SONG Wenji, et al. Research progress on the recovery of valuable metals in retired LiNi _x Co _y Mn _z O₂ batteries by wet process[J]. Chemical Industry and Engineering Progress, 2019, 38(2): 921-932.
21	GUO M M, LI K, LIU L Z, et al. Resource utilization of spent ternary lithium-ions batteries: synthesis of highly active manganese-based perovskite catalyst for toluene oxidation[J]. Journal of the Taiwan Institute of Chemical Engineers, 2019, 102: 268-275.
22	FAN E S, LI L, ZHANG X X, et al. Selective recovery of Li and Fe from spent lithium-ion batteries by an environmentally friendly mechanochemical approach[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(8): 11029-11035.
23	WANG M M, TAN Q Y, HUANG Q F, et al. Converting spent lithium cobalt oxide battery cathode materials into high-value products via a mechanochemical extraction and thermal reduction route[J]. Journal of Hazardous Materials, 2021, 413: 125222.
24	LI Z, HE L H, ZHU Y F, et al. A green and cost-effective method for production of LiOH from spent LiFePO₄ [J]. ACS Sustainable Chemistry & Engineering, 2020, 8(42): 15915-15926.
25	LI Z, LIU D F, XIONG J C, et al. Selective recovery of lithium and iron phosphate/carbon from spent lithium iron phosphate cathode material by anionic membrane slurry electrolysis[J]. Waste Management, 2020, 107: 1-8.
26	LYU H, HUANG H J, HUANG C, et al. Electric field driven de-lithiation: a strategy towards comprehensive and efficient recycling of electrode materials from spent lithium ion batteries[J]. Applied Catalysis B: Environmental, 2021, 283: 119634.
27	GEORGI-MASCHLER T, FRIEDRICH B, WEYHE R, et al. Development of a recycling process for Li-ion batteries[J]. Journal of Power Sources, 2012, 207: 173-182.
28	LIU C W, LIN J, CAO H B, et al. Recycling of spent lithium-ion batteries in view of lithium recovery: a critical review[J]. Journal of Cleaner Production, 2019, 228: 801-813.
29	ZENG X L, LI J H, SINGH N. Recycling of spent lithium-ion battery: a critical review[J]. Critical Reviews in Environmental Science and Technology, 2014, 44(10): 1129-1165.
30	XIAO J F, LI J, XU Z M. Recycling metals from lithium ion battery by mechanical separation and vacuum metallurgy[J]. Journal of Hazardous Materials, 2017, 338: 124-131.
31	QIU R J, HUANG Z, ZHENG J Y, et al. Energy models and the process of fluid-magnetic separation for recovering cobalt micro-particles from vacuum reduction products of spent lithium ion batteries[J]. Journal of Cleaner Production, 2021, 279: 123230.
32	TANG Y Q, XIE H W, ZHANG B L, et al. Recovery and regeneration of LiCoO₂-based spent lithium-ion batteries by a carbothermic reduction vacuum pyrolysis approach: controlling the recovery of CoO or Co[J]. Waste Management, 2019, 97: 140-148.
33	DIAZ F, WANG Y, MOORTHY T, et al. Degradation mechanism of nickel-cobalt-aluminum (NCA) cathode material from spent lithium-ion batteries in microwave-assisted pyrolysis[J]. Metals, 2018, 8(8): 565.
34	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: 121487.
35	ZHAO Y Z, LIU B G, ZHANG L B, et al. Microwave pyrolysis of macadamia shells for efficiently recycling lithium from spent lithium-ion batteries[J]. Journal of Hazardous Materials, 2020, 396: 122740.
36	WU Z, ZHU H, BI H, et al. Recycling of electrode materials from spent lithium-ion power batteries via thermal and mechanical treatments[J]. Waste Management & Research, 2021, 39(4): 607-619.
37	LOMBARDO G, EBIN B, FOREMAN M R St J, et al. Chemical transformations in Li-ion battery electrode materials by carbothermic reduction[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(16): 13668-13679.
38	LIU P C, XIAO L, CHEN Y F, et al. Recovering valuable metals from LiNi _x Co _y Mn_1- _x_- _y O₂ cathode materials of spent lithium ion batteries via a combination of reduction roasting and stepwise leaching[J]. Journal of Alloys and Compounds, 2019, 783: 743-752.
39	WANG W Q, ZHANG Y C, LIU X G, et al. A simplified process for recovery of Li and co from spent LiCoO₂ cathode using Al foil as the in situ reductant[J]. ACS Sustainable Chemistry & Engineering, 2019, 7: 12222-12230.
40	WANG W Q, ZHANG Y C, ZHANG L, et al. Cleaner recycling of cathode material by in situ thermite reduction[J]. Journal of Cleaner Production, 2020, 249: 119340.
41	YANG C, ZHANG J L, YU B Y, et al. Recovery of valuable metals from spent LiNi _x Co _y Mn _z O₂ cathode material via phase transformation and stepwise leaching[J]. Separation and Purification Technology, 2021, 267: 118609.
42	LIU F P, PENG C, MA Q X, et al. Selective lithium recovery and integrated preparation of high-purity lithium hydroxide products from spent lithium-ion batteries[J]. Separation and Purification Technology, 2021, 259: 118181.
43	LIU P C, XIAO L, TANG Y W, et al. Study on the reduction roasting of spent LiNi _x Co _y Mn _z O₂ lithium-ion battery cathode materials[J]. Journal of Thermal Analysis and Calorimetry, 2019, 136(3): 1323-1332.
44	SAIT H H, SALEMA A A. Microwave dielectric characterization of Saudi Arabian date palm biomass during pyrolysis and at industrial frequencies[J]. Fuel, 2015, 161: 239-247.
45	MAO J K, LI J, XU Z M. Coupling reactions and collapsing model in the roasting process of recycling metals from LiCoO₂ batteries[J]. Journal of Cleaner Production, 2018, 205: 923-929.
46	XIAO J F, LI J, XU Z M. Novel approach for in situ recovery of lithium carbonate from spent lithium ion batteries using vacuum metallurgy[J]. Environmental Science & Technology, 2017, 51(20): 11960-11966.
47	LI J, WANG G X, XU Z M. Environmentally-friendly oxygen-free roasting/wet magnetic separation technology for in situ recycling cobalt, lithium carbonate and graphite from spent LiCoO₂/graphite lithium batteries[J]. Journal of Hazardous Materials, 2016, 302: 97-104.
48	ZHANG H L, XU J Q, ZHANG J J. Surface-coated LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathode materials by Al₂O₃, ZrO₂, and Li₂O-2B₂O₃ thin-layers for improving the performance of lithium ion batteries[J]. Frontiers in Materials, 2019, 6: 309.
49	XIAO J F, NIU B, XU Z M. Highly efficient selective recovery of lithium from spent lithium-ion batteries by thermal reduction with cheap ammonia reagent[J]. Journal of Hazardous Materials, 2021, 418: 126319.
50	YANG C, ZHANG J L, CAO Z H, et al. Sustainable and facile process for lithium recovery from spent LiNi _x Co _y Mn _z O₂ cathode materials via selective sulfation with ammonium sulfate[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(41): 15732-15739.
51	LIN J, LIU C W, CAO H B, et al. Environmentally benign process for selective recovery of valuable metals from spent lithium-ion batteries by using conventional sulfation roasting[J]. Green Chemistry, 2019, 21(21): 5904-5913.
52	LIN J, LI L, FAN E S, et al. Conversion mechanisms of selective extraction of lithium from spent lithium-ion batteries by sulfation roasting[J]. ACS Applied Materials & Interfaces, 2020, 12(16): 18482-18489.
53	DANG H, WANG B F, CHANG Z D, et al. Recycled lithium from simulated pyrometallurgical slag by chlorination roasting[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(10): 13160-13167.
54	PENG C, LIU F P, WANG Z L, et al. Selective extraction of lithium (Li) and preparation of battery grade lithium carbonate (Li₂CO₃) from spent Li-ion batteries in nitrate system[J]. Journal of Power Sources, 2019, 415: 179-188.
55	PRADHAN N, NAYAK R R, PRIYADARSHINI E, et al. Application of iron reducing bacteria for recovery of nickel and cobalt chromite overburden [C]//ⅩⅩⅥ International Mineral Processing Congress- IMPC 2012. India: 2012: 24-28.
56	石剑锋, 王志兴, 胡启阳, 等. 硫酸氢铵硫酸化焙烧法红土镍矿提取镍钴[J]. 中国有色金属学报, 2013, 23(2): 510-515.
	SHI Jianfeng, WANG Zhixing, HU Qiyang, et al. Recovery of nickel and cobalt from nickel laterite ore by sulfation roasting method using ammonium bisulfate[J]. The Chinese Journal of Nonferrous Metals, 2013, 23(2): 510-515.
57	KAR B B, SWAMY Y V. Some aspects of nickel extraction from chromitiferous overburden by sulphatization roasting[J]. Minerals Engineering, 2000, 13(14/15): 1635-1640.
58	PAULINO J F, BUSNARDO N G, AFONSO J C. Recovery of valuable elements from spent Li-batteries[J]. Journal of Hazardous Materials, 2008, 150(3): 843-849.
59	WANG D H, ZHANG X D, CHEN H J, et al. Separation of Li and Co from the active mass of spent Li-ion batteries by selective sulfating roasting with sodium bisulfate and water leaching[J]. Minerals Engineering, 2018, 126: 28-35.
60	XU P, LIU C W, ZHANG X H, et al. Synergic mechanisms on carbon and sulfur during the selective recovery of valuable metals from spent lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(5): 2271-2279.
61	FAN E S, LI L, LIN J, et al. Low-temperature molten-salt-assisted recovery of valuable metals from spent lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(19): 16144-16150.
62	XIAO J F, NIU B, SONG Q M, et al. Novel targetedly extracting lithium: an environmental-friendly controlled chlorinating technology and mechanism of spent lithium ion batteries recovery[J]. Journal of Hazardous Materials, 2021, 404: 123947.
63	HUANG Y, SHAO P H, YANG L M, et al. Thermochemically driven crystal phase transfer via chlorination roasting toward the selective extraction of lithium from spent LiNi_1/3Co_1/3Mn_1/3O₂ [J]. Resources, Conservation and Recycling, 2021, 174: 105757.
64	YAO Y L, ZHU M Y, ZHAO Z, et al. Hydrometallurgical processes for recycling spent lithium-ion batteries: a critical review[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(11): 13611-13627.
65	ZHANG P W, YOKOYAMA T, ITABASHI O, et al. Hydrometallurgical process for recovery of metal values from spent lithium-ion secondary batteries[J]. Hydrometallurgy, 1998, 47(2/3): 259-271.
66	GUO Y, LI F, ZHU H C, et al. Leaching lithium from the anode electrode materials of spent lithium-ion batteries by hydrochloric acid (HCl)[J]. Waste Management, 2016, 51: 227-233.
67	YAO L, YAO H S, XI G X, et al. Recycling and synthesis of LiNi_1/3Co_1/3Mn_1/3O₂ from waste lithium ion batteries using D,L-malic acid[J]. RSC Advances, 2016, 6(22): 17947-17954.
68	SUN L, QIU K Q. 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.
69	FERREIRA D A, PRADOS L M Z, MAJUSTE D, et al. Hydrometallurgical separation of aluminium, cobalt, copper and lithium from spent Li-ion batteries[J]. Journal of Power Sources, 2009, 187(1): 238-246.
70	PARK O K, CHO Y, LEE S, et al. Who will drive electric vehicles, olivine or spinel?[J]. Energy & Environmental Science, 2011, 4(5): 1621.
71	KUMAR J, NEIBER R R, PARK J, et al. Recent progress in sustainable recycling of LiFePO₄-type lithium-ion batteries: strategies for highly selective lithium recovery[J]. Chemical Engineering Journal, 2021: 133993.
72	LI H, XING S Z, LIU Y, et al. Recovery of lithium, iron, and phosphorus from spent LiFePO₄ batteries using stoichiometric sulfuric acid leaching system[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(9): 8017-8024.
73	LI L, GE J, CHEN R J, et al. Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries[J]. Waste Management, 2010, 30(12): 2615-2621.
74	LYU W, WANG Z H, ZHENG X H, et al. Selective recovery of lithium from spent lithium-ion batteries by coupling advanced oxidation processes and chemical leaching processes[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(13): 5165-5174.
75	MENG Q, ZHANG Y J, DONG P. Use of glucose as reductant to recover Co from spent lithium ions batteries[J]. Waste Management, 2017, 64: 214-218.
76	MESHRAM P, PANDEY B D, MANKHAND T R. Hydrometallurgical processing of spent lithium ion batteries (LIBs) in the presence of a reducing agent with emphasis on kinetics of leaching[J]. Chemical Engineering Journal, 2015, 281: 418-427.
77	LI L, BIAN Y F, ZHANG X X, et al. Process for recycling mixed-cathode materials from spent lithium-ion batteries and kinetics of leaching[J]. Waste Management, 2018, 71: 362-371.
78	GAO W F, ZHANG X H, ZHENG X H, et al. Lithium carbonate recovery from cathode scrap of spent lithium-ion battery: a closed-loop process[J]. Environmental Science & Technology, 2017, 51(3): 1662-1669.
79	TAKACOVA Z, HAVLIK T, KUKURUGYA F, et al. Cobalt and lithium recovery from active mass of spent Li-ion batteries: theoretical and experimental approach[J]. Hydrometallurgy, 2016, 163: 9-17.
80	CHEN X P, LUO C B, ZHANG J X, et al. Sustainable recovery of metals from spent lithium-ion batteries: a green process[J]. ACS Sustainable Chemistry & Engineering, 2015, 3(12): 3104-3113.
81	ZENG X L, LI J H, SHEN B Y. Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid[J]. Journal of Hazardous Materials, 2015, 295: 112-118.
82	LI L, LU J, REN Y, et al. Ascorbic-acid-assisted recovery of cobalt and lithium from spent Li-ion batteries[J]. Journal of Power Sources, 2012, 218: 21-27.
83	YANG Y X, MENG X Q, CAO H B, et al. Selective recovery of lithium from spent lithium iron phosphate batteries: a sustainable process[J]. Green Chemistry, 2018, 20(13): 3121-3133.
84	CHEN L L, CHAO Y H, LI X W, et al. Engineering a tandem leaching system for the highly selective recycling of valuable metals from spent Li-ion batteries[J]. Green Chemistry, 2021, 23(5): 2177-2184.
85	NIINAE M, KOMATSU N, NAKAHIRO Y, et al. Preferential leaching of cobalt, nickel and copper from cobalt-rich ferromanganese crusts with ammoniacal solutions using ammonium thiosulfate and ammonium sulfite as reducing agents[J]. Hydrometallurgy, 1996, 40(1/2): 111-121.
86	ZHENG X H, GAO W F, ZHANG X H, et al. Spent lithium-ion battery recycling—Reductive ammonia leaching of metals from cathode scrap by sodium sulphite[J]. Waste Management, 2017, 60: 680-688.
87	GUO Y G, LI Y G, LOU X Y, et al. Improved extraction of cobalt and lithium by reductive acid from spent lithium-ion batteries via mechanical activation process[J]. Journal of Materials Science, 2018, 53(19): 13790-13800.
88	WANG M M, TAN Q Y, LI J H. Unveiling the role and mechanism of mechanochemical activation on lithium cobalt oxide powders from spent lithium-ion batteries[J]. Environmental Science & Technology, 2018, 52(22): 13136-13143.
89	TAN Q Y, LI J H. Recycling metals from wastes: a novel application of mechanochemistry[J]. Environmental Science & Technology, 2015, 49(10): 5849-5861.
90	XIE J Y, HUANG K Y, NIE Z L, et al. An effective process for the recovery of valuable metals from cathode material of lithium-ion batteries by mechanochemical reduction[J]. Resources, Conservation and Recycling, 2021, 168: 105261.
91	LIU K, LIU L L, TAN Q Y, et al. Selective extraction of lithium from a spent lithium iron phosphate battery by mechanochemical solid-phase oxidation[J]. Green Chemistry, 2021, 23(3): 1344-1352.
92	LIU K, TAN Q Y, LIU L L, et al. Acid-free and selective extraction of lithium from spent lithium iron phosphate batteries via a mechanochemically induced isomorphic substitution[J]. Environmental Science & Technology, 2019, 53(16): 9781-9788.
93	WANG M M, TAN Q Y, LIU L L, et al. Selective regeneration of lithium from spent lithium-ion batteries using ionic substitution stimulated by mechanochemistry[J]. Journal of Cleaner Production, 2021, 279: 123612.
94	YU J Z, WANG X, ZHOU M Y, et al. A redox targeting-based material recycling strategy for spent lithium ion batteries[J]. Energy & Environmental Science, 2019, 12(9): 2672-2677.
95	LIU K, YANG S L, LAI F Y, et al. Innovative electrochemical strategy to recovery of cathode and efficient lithium leaching from spent lithium-ion batteries[J]. ACS Applied Energy Materials, 2020, 3(5): 4767-4776.
96	GMAR S, CHAGNES A. Recent advances on electrodialysis for the recovery of lithium from primary and secondary resources[J]. Hydrometallurgy, 2019, 189: 105124.
97	CHAN K H, MALIK M, AZIMI G. Separation of lithium, nickel, manganese, and cobalt from waste lithium-ion batteries using electrodialysis[J]. Resources, Conservation and Recycling, 2022, 178: 106076.
98	LYU W, RUAN D S, ZHENG X H, et al. One-step recovery of valuable metals from spent lithium-ion batteries and synthesis of persulfate through paired electrolysis[J]. Chemical Engineering Journal, 2021, 421: 129908.

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］

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

废锂离子电池正极材料中锂元素选择性回收的研究进展

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 9

References 98

Related Articles 15

Recommended Articles

Metrics

Comments

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

[1]	ZHANG Mingyan, LIU Yan, ZHANG Xueting, LIU Yake, LI Congju, ZHANG Xiuling. Research progress of non-noble metal bifunctional catalysts in zinc-air batteries [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 276-286.
[2]	HU Xi, WANG Mingshan, LI Enzhi, HUANG Siming, CHEN Junchen, GUO Bingshu, YU Bo, MA Zhiyuan, LI Xing. Research progress on preparation and sodium storage properties of tungsten disulfide composites [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 344-355.
[3]	ZHANG Jie, BAI Zhongbo, FENG Baoxin, PENG Xiaolin, REN Weiwei, ZHANG Jingli, LIU Eryong. Effect of PEG and its compound additives on post-treatment of electrolytic copper foils [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 374-381.
[4]	LI Jitong, WANG Gang, XIONG Yaxuan, XU Qian. Energy and exergy analysis of single-effect absorption refrigeration system with different refrigerants [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 104-112.
[5]	MA Yi, CAO Shiwei, WANG Jiajun, LIN Liqun, XING Yan, CAO Tengliang, LU Feng, ZHAO Zhenlun, ZHANG Zhijun. Research progress in recovery of spent cathode materials for lithium-ion batteries using deep eutectic solvents [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 219-232.
[6]	ZHU Chuanqiang, RU Jinbo, SUN Tingting, XIE Xingwang, LI Changming, GAO Shiqiu. Characteristics of selective non-catalytic reduction of NO _x with solid polymer denitration agent [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4939-4946.
[7]	MAO Shanjun, WANG Zhe, WANG Yong. Group recognition hydrogenation: From concept to application [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3917-3922.
[8]	WANG Baoying, WANG Huangying, YAN Junying, WANG Yaoming, XU Tongwen. Research progress of polymer inclusion membrane in metal separation and recovery [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3990-4004.
[9]	XIANG Yang, HUANG Xun, WEI Zidong. Recent progresses in the activity and selectivity improvement of electrocatalytic organic synthesis [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4005-4014.
[10]	WANG Yaogang, HAN Zishan, GAO Jiachen, WANG Xinyu, LI Siqi, YANG Quanhong, WENG Zhe. Strategies for regulating product selectivity of copper-based catalysts in electrochemical CO₂ reduction [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4043-4057.
[11]	LIU Yi, FANG Qiang, ZHONG Dazhong, ZHAO Qiang, LI Jinping. Cu facets regulation of Ag/Cu coupled catalysts for electrocatalytic reduction of carbon dioxide [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4136-4142.
[12]	LYU Jie, HUANG Chong, FENG Ziping, HU Yafei, SONG Wenji. Performance and control system of gas engine heat pump based on waste heat recovery [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4182-4192.
[13]	HU Yafei, FENG Ziping, TIAN Jiayao, SONG Wenji. Waste heat recovery performance of an air-source gas engine-driven heat pump system in multi-heating operation modes [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4204-4211.
[14]	ZHANG Yajuan, XU Hui, HU Bei, SHI Xingwei. Preparation of NiCoP/rGO/NF electrocatalyst by eletroless plating for efficient hydrogen evolution reaction [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4275-4282.
[15]	WANG Xiaohan, ZHOU Yasong, YU Zhiqing, WEI Qiang, SUN Jinxiao, JIANG Peng. Synthesis and hydrocracking performance of Y molecular sieves with different crystal sizes [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4283-4295.