使用硫酸和草酸选择性浸出废弃锂离子电池中的锂

余海军; 王东兴; 饶帅; 段丽娟; 邵彩茹; 涂小慧; 马致远; 曹洪杨; 刘志强

doi:10.1007/s12613-023-2741-3

Volume 31 Issue 4

Apr. 2024

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文章导航 > 矿物冶金与材料学报（英文） > 2024 > 31(4): 688-696

Haijun Yu, Dongxing Wang, Shuai Rao, Lijuan Duan, Cairu Shao, Xiaohui Tu, Zhiyuan Ma, Hongyang Cao, and Zhiqiang Liu, Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid, Int. J. Miner. Metall. Mater., 31(2024), No. 4, pp. 688-696. https://doi.org/10.1007/s12613-023-2741-3

Cite this article as:

Haijun Yu, Dongxing Wang, Shuai Rao, Lijuan Duan, Cairu Shao, Xiaohui Tu, Zhiyuan Ma, Hongyang Cao, and Zhiqiang Liu, Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid, Int. J. Miner. Metall. Mater., 31(2024), No. 4, pp. 688-696. https://doi.org/10.1007/s12613-023-2741-3

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研究论文

使用硫酸和草酸选择性浸出废弃锂离子电池中的锂

1)
暨南大学先进耐磨蚀及功能材料研究院，广州 510632，中国
2)
广东省科学院资源利用与稀土开发研究所，广州 510650，中国
3)
稀有金属分离与综合利用国家重点实验室，广州 510650，中国
4)
广东省稀土开发及应用研究重点实验室，广州 510650，中国

通讯作者:
王东兴 E-mail: 710797438@qq.com

涂小慧 E-mail: 3162510484@qq.com

文章亮点

(1) 利用硫酸和草酸协同从废弃锂电池中选择性浸锂。

(2) 系统地研究了浸出条件对选择性浸锂的影响规律。

(3) 揭示了硫酸-草酸体系选择性浸锂的机理。

中文摘要

近年来，随着锂离子电池的广泛应用，未来锂离子电池退役量将剧增。考虑到环境保护和资源循环利用，废弃锂离子电池的回收利用变得迫在眉睫。现有废弃锂离子电池湿法冶金回收工艺通常采用还原酸浸法将有价金属同时提取到浸出液中，后续再通过沉淀、萃取、反萃等工艺分离各有价金属。这类工艺流程较长，且锂在流程最末端回收，锂的损失率高。本文旨在开发一种新的选择性优先浸锂工艺，利用硫酸和草酸协同作用选择性浸出废弃锂电池中的锂，有利于锂的优先回收。在最佳浸出条件下（浸出时间1.5 h、浸出温度70°C、液固比4 mL/g、硫酸配比1.3、草酸配比1.3），锂的浸出率为89.6%，选择性浸出效果较好。经ICP成分分析、XRD物相分析和SEM显微分析推断出，在硫酸体系中的草酸起到了还原剂与沉淀剂的作用。草酸可降低锂离子电池正极材料中部分镍、钴、锰的价态从而破坏正极材料的层状结构，有利于锂的浸出；同时，草酸根与溶液中的镍、钴、锰结合形成草酸盐留在渣中，从而实现选择性浸锂。

关键词:

Research Article

Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid

+ Author Affiliations

1)
Institute of Advanced Wear & Corrosion Resistant and Functional Materials, Jinan University, Guangzhou 510632, China
2)
Institute of Resources Utilization and Rare Earth Development, Guangdong Academy of Sciences, Guangzhou 510650, China
3)
State Key Laboratory of Separation and Comprehensive Utilization of Rare Metals, Guangzhou 510650, China
4)
Guangdong Province Key Laboratory of Rare Earth Development and Application, Guangzhou 510650, China

All the authors have no financial or commercial conflicts.

Corresponding authors:
Dongxing Wang E-mail: 710797438@qq.com

Xiaohui Tu E-mail: 3162510484@qq.com
Received: 13 July 2023; Revised: 5 September 2023; Accepted: 8 September 2023; Available online: 9 September 2023

Abstract

Abstract

Traditional hydrometallurgical methods for recovering spent lithium-ion batteries (LIBs) involve acid leaching to simultaneously extract all valuable metals into the leachate. These methods usually are followed by a series of separation steps such as precipitation, extraction, and stripping to separate the individual valuable metals. In this study, we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic acids. Under optimal leaching conditions (leaching time of 1.5 h, leaching temperature of 70°C, liquid–solid ratio of 4 mL/g, oxalic acid ratio of 1.3, and sulfuric acid ratio of 1.3), the lithium leaching efficiency reached 89.6%, and the leaching efficiencies of Ni, Co, and Mn were 12.8%, 6.5%, and 21.7%. X-ray diffraction (XRD) and inductively coupled plasma optical emission spectrometer (ICP-OES) analyses showed that most of the Ni, Co, and Mn in the raw material remained as solid residue oxides and oxalates. This study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.
- selective leaching;
- oxalic acid;
- sulfuric acid;
- spent lithium-ion batteries

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References

[1]	X.W. Duan, W.K. Zhu, Z.K. Ruan, M. Xie, J. Chen, and X.H. Ren, Recycling of lithium batteries—A review, Energies, 15(2022), No. 5, art. No. 1611. doi: 10.3390/en15051611
[2]	T. Or, S.W.D. Gourley, K. Kaliyappan, A.P. Yu, and Z.W. Chen, Recycling of mixed cathode lithium-ion batteries for electric vehicles: Current status and future outlook, Carbon Energy, 2(2020), No. 1, p. 6. doi: 10.1002/cey2.29
[3]	J.N. Meegoda, S. Malladi, and I.C. Zayas, End-of-life management of electric vehicle lithium-ion batteries in the United States, Clean Technol., 4(2022), No. 4, p. 1162. doi: 10.3390/cleantechnol4040071
[4]	S. Natarajan and V. Aravindan, Burgeoning prospects of spent lithium-ion batteries in multifarious applications, Adv. Energy Mater., 8(2018), No. 33, art. No. 1802303. doi: 10.1002/aenm.201802303
[5]	S.H. Joo, D.J. Shin, C. Oh, J.P. Wang, G. Senanayake, and S.M. Shin, 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, Hydrometallurgy, 159(2016), p. 65. doi: 10.1016/j.hydromet.2015.10.012
[6]	E. Gratz, Q.N. Sa, D. Apelian, and Y. Wang, A closed loop process for recycling spent lithium ion batteries, J. Power Sources, 262(2014), p. 255. doi: 10.1016/j.jpowsour.2014.03.126
[7]	L. Yang, G.X. Xi, and Y.B. Xi, Recovery of Co, Mn, Ni, and Li from spent lithium ion batteries for the preparation of LiNi_xCo_yMn_zO₂ cathode materials, Ceram. Int., 41(2015), No. 9, p. 11498. doi: 10.1016/j.ceramint.2015.05.115
[8]	N. Bahaloo-Horeh, S.M. Mousavi, and M. Baniasadi, Use of adapted metal tolerant Aspergillus niger to enhance bioleaching efficiency of valuable metals from spent lithium-ion mobile phone batteries, J. Cleaner Prod., 197(2018), p. 1546. doi: 10.1016/j.jclepro.2018.06.299
[9]	A. Heydarian, S.M. Mousavi, F. Vakilchap, and M. Baniasadi, Application of a mixed culture of adapted acidophilic bacteria in two-step bioleaching of spent lithium-ion laptop batteries, J. Power Sources, 378(2018), p. 19. doi: 10.1016/j.jpowsour.2017.12.009
[10]	Y.Y. Xin, X.M. Guo, S. Chen, J. Wang, F. Wu, and B.P. Xin, Bioleaching of valuable metals Li, Co, Ni and Mn from spent electric vehicle Li-ion batteries for the purpose of recovery, J. Cleaner Prod., 116(2016), p. 249. doi: 10.1016/j.jclepro.2016.01.001
[11]	M. Assefi, S. Maroufi, Y. Yamauchi, and V. Sahajwalla, Pyrometallurgical recycling of Li-ion, Ni–Cd and Ni–MH batteries: A minireview, Curr. Opin. Green Sustain. Chem., 24(2020), p. 26. doi: 10.1016/j.cogsc.2020.01.005
[12]	B. Makuza, Q.H. Tian, X.Y. Guo, K. Chattopadhyay, and D.W. Yu, Pyrometallurgical options for recycling spent lithium-ion batteries: A comprehensive review, J. Power Sources, 491(2021), art. No. 229622. doi: 10.1016/j.jpowsour.2021.229622
[13]	S. Windisch-Kern, A. Holzer, C. Ponak, and H. Raupenstrauch, Pyrometallurgical lithium-ion-battery recycling: Approach to limiting lithium slagging with the InduRed reactor concept, Processes, 9(2021), No. 1, art. No. 84. doi: 10.3390/pr9010084
[14]	L. Yun, D. Linh, L. Shui, et al., Metallurgical and mechanical methods for recycling of lithium-ion battery pack for electric vehicles, Resour. Conserv. Recycl., 136(2018), p. 198. doi: 10.1016/j.resconrec.2018.04.025
[15]	C. Ekberg and M. Petranikova, Chapter 7 - Lithium batteries recycling, [in] A. Chagnes and J. Światowska, eds., Lithium Process Chemistry : Resources , Extraction , Batteries and Recycling, Elsevier, Amsterdam, 2015, p. 233.
[16]	Z. Sun, H. Cao, Y. Xiao, et al., Toward sustainability for recovery of critical metals from electronic waste: The hydrochemistry processes, ACS Sustainable Chem. Eng., 5(2017), No. 1, p. 21. doi: 10.1021/acssuschemeng.6b00841
[17]	D.X. Wang, W. Li, S. Rao, et al., Oxygen-free calcination for enhanced leaching of valuable metals from spent lithium-ion batteries without a reductant, Sep. Purif. Technol., 259(2021), art. No. 118212. doi: 10.1016/j.seppur.2020.118212
[18]	D.D. Chen, S. Rao, D.X. Wang, H.Y. Cao, W.M. Xie, and Z.Q. Liu, Synergistic leaching of valuable metals from spent Li-ion batteries using sulfuric acid-L-ascorbic acid system, Chem. Eng. J., 388(2020), art. No. 124321. doi: 10.1016/j.cej.2020.124321
[19]	S. Gu, L. Zhang, B.T. Fu, X.P. Wang, and J.W. Ahn, Feasible route for the recovery of strategic metals from mixed lithium-ion batteries cathode materials by precipitation and carbonation, Chem. Eng. J., 420(2021), art. No. 127561. doi: 10.1016/j.cej.2020.127561
[20]	L.C. Zhang, L.J. Li, H.M. Rui, et al., Lithium recovery from effluent of spent lithium battery recycling process using solvent extraction, J. Hazard. Mater., 398(2020), art. No. 122840. doi: 10.1016/j.jhazmat.2020.122840
[21]	H. Ku, Y. Jung, M. Jo, et al., Recycling of spent lithium-ion battery cathode materials by ammoniacal leaching, J. Hazard. Mater., 313(2016), p. 138. doi: 10.1016/j.jhazmat.2016.03.062
[22]	Y. Guo, F. Li, H.C. Zhu, G.M. Li, J.W. Huang, and W.Z. He, Leaching lithium from the anode electrode materials of spent lithium-ion batteries by hydrochloric acid (HCl), Waste Manage., 51(2016), p. 227. doi: 10.1016/j.wasman.2015.11.036
[23]	Yuliusman, R. Fajaryanto, A. Nurqomariah, and Silvia, Acid leaching and kinetics study of cobalt recovery from spent lithium-ion batteries with nitric acid, E3S Web Conf., 67(2018), art. No. 03025. doi: 10.1051/e3sconf/20186703025
[24]	P. Meshram, B.D. Pandey, and T.R. Mankhand, Hydrometallurgical processing of spent lithium ion batteries (LIBs) in the presence of a reducing agent with emphasis on kinetics of leaching, Chem. Eng. J., 281(2015), p. 418. doi: 10.1016/j.cej.2015.06.071
[25]	X.P. Chen, H.R. Ma, C.B. Luo, and T. Zhou, Recovery of valuable metals from waste cathode materials of spent lithium-ion batteries using mild phosphoric acid, J. Hazard. Mater., 326(2017), p. 77. doi: 10.1016/j.jhazmat.2016.12.021
[26]	B. Wang, X.Y. Lin, Y.Y. Tang, Q. Wang, M.K.H. Leung, and X.Y. Lu, Recycling LiCoO₂ with methanesulfonic acid for regeneration of lithium-ion battery electrode materials, J. Power Sources, 436(2019), art. No. 226828. doi: 10.1016/j.jpowsour.2019.226828
[27]	B. Musariri, G. Akdogan, C. Dorfling, and S. Bradshaw, Evaluating organic acids as alternative leaching reagents for metal recovery from lithium ion batteries, Miner. Eng., 137(2019), p. 108. doi: 10.1016/j.mineng.2019.03.027
[28]	L. Yao, H.S. Yao, G.X. Xi, and Y. Feng, Recycling and synthesis of LiNi_1/3Co_1/3Mn_1/3O₂ from waste lithium ion batteries using D,L-malic acid, RSC Adv., 6(2016), No. 22, p. 17947. doi: 10.1039/C5RA25079J
[29]	Yuliusman, Silvia, A. Nurqomariah, and R. Fajaryanto, Recovery of cobalt and nickel from spent lithium ion batteries with citric acid using leaching process: Kinetics study, E3S Web Conf., 67(2018), art. No. 03008. doi: 10.1051/e3sconf/20186703008
[30]	S.X. Yan, C.H. Sun, T. Zhou, R.C. Gao, and H.S. Xie, Ultrasonic-assisted leaching of valuable metals from spent lithium-ion batteries using organic additives, Sep. Purif. Technol., 257(2021), art. No. 117930. doi: 10.1016/j.seppur.2020.117930
[31]	R. Gao and J.F. Wang, Recovery of cobalt from the LiNi_1/3Co_1/3Mn_1/3O₂ cathode of waste lithium-ion batteries, Chin. J. Environ. Eng., 14(2020), No. 2, p. 506.
[32]	X.P. Chen, Y.B. Chen, T. Zhou, D.P. Liu, H. Hu, and S.Y. Fan, Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries, Waste Manage., 38(2015), p. 349. doi: 10.1016/j.wasman.2014.12.023
[33]	O.K. Park, Y. Cho, S.H. Lee, H.C. Yoo, H.K. Song, and J. Cho, Who will drive electric vehicles, olivine or spinel?, Energy Environ. Sci., 4(2011), No. 5, art. No. 1621. doi: 10.1039/c0ee00559b
[34]	C. Peng, F.P. Liu, Z.L. Wang, B.P. Wilson, and M. Lundström, Selective extraction of lithium (Li) and preparation of battery grade lithium carbonate (Li₂CO₃) from spent Li-ion batteries in nitrate system, J. Power Sources, 415(2019), p. 179. doi: 10.1016/j.jpowsour.2019.01.072
[35]	L.L. Chen, Y.H. Chao, X.W. Li, et al., Engineering a tandem leaching system for the highly selective recycling of valuable metals from spent Li-ion batteries, Green Chem., 23(2021), No. 5, p. 2177. doi: 10.1039/D0GC03820B
[36]	J.T. Hu, J.L. Zhang, H.X. Li, Y.Q. Chen, and C.Y. Wang, A promising approach for the recovery of high value-added metals from spent lithium-ion batteries, J. Power Sources, 351(2017), p. 192. doi: 10.1016/j.jpowsour.2017.03.093
[37]	D.Y. Wu, D.X. Wang, Z.Q. Liu, S. Rao, and K.F. Zhang, Selective recovery of lithium from spent lithium iron phosphate batteries using oxidation pressure sulfuric acid leaching system, Trans. Nonferrous Met. Soc. China, 32(2022), No. 6, p. 2071. doi: 10.1016/S1003-6326(22)65931-4
[38]	C.Y. Yang, J.W. Wang, P. Yang, et al., Recovery of valuable metals from spent LiNi_0.8Co_0.1Mn_0.1O₂ cathode materials using compound leaching agents of sulfuric acid and oxalic acid, Sustainability, 14(2022), No. 21, art. No. 14169. doi: 10.3390/su142114169
[39]	J. Chen, T.C. Liu, H.L. Li, et al. , A Kind of Ternary Lithium Battery Cathode Material Recycling Method, Chinese Patent, CN112063847A, 2020.
[40]	Z.P. Qiu, Y.J. Zhang, P. Dong, S.B. Xia, and Y. Yao, A facile method for synthesis of LiNi_0.8Co_0.15Al_0.05O₂ cathode material, Solid State Ion., 307(2017), p. 73. doi: 10.1016/j.ssi.2017.04.011
[41]	D. Wang, Z.X. Wang, X.H. Li, et al., Effect of surface fluorine substitution on high voltage electrochemical performances of layered LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials, Appl. Surf. Sci., 371(2016), p. 172. doi: 10.1016/j.apsusc.2016.02.224
[42]	Y.Z. Duan, J.M. Guo, M.W. Xiang, et al., Single crystalline polyhedral LiNi_xMn_{2− x}O₄ as high-performance cathodes for ultralong cycling lithium-ion batteries, Solid State Ionics, 326(2018), p. 100. doi: 10.1016/j.ssi.2018.09.014
[43]	T. Chen, X. Li, H. Wang, et al., The effect of gradient boracic polyanion-doping on structure, morphology, and cycling performance of Ni-rich LiNi_0.8Co_0.15Al_0.05O₂ cathode material, J. Power Sources, 374(2018), p. 1. doi: 10.1016/j.jpowsour.2017.11.020
[44]	Y.Y. Wang, T.Y. Wang, L.J. Wu, et al., Recovery of valuable metals from spent ternary Li-ion batteries: Dissolution with amidosulfonic acid and D, Hydrometallurgy, 190(2019), art. No. 105162. doi: 10.1016/j.hydromet.2019.105162