Highly selective metal recovery from spent lithium-ion batteries through stoichiometric hydrogen ion replacement

doi:10.1007/s11705-020-2029-3

Front. Chem. Sci. Eng.

2021, Vol. 15

Issue (5) : 1243-1256 https://doi.org/10.1007/s11705-020-2029-3

RESEARCH ARTICLE

Highly selective metal recovery from spent lithium-ion batteries through stoichiometric hydrogen ion replacement

Weiguang Lv^1,², Xiaohong Zheng¹, Li Li³, Hongbin Cao¹, Yi Zhang¹, Renjie Chen³, Hancheng Ou⁴, Fei Kang¹, Zhi Sun^1,²(

)

¹. National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Innovation Academy for Green Manufacture, Chinese Academy of Sciences, Beijing 100190, China
². School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100190, China
³. School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China
⁴. Ganzhou Highpower Technology Co., Ltd., Ganzhou 341000, China

Download: PDF(6119 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Spent lithium-ion battery recycling has attracted significant attention because of its importance in regard to the environment and resource importance. Traditional hydrometallurgical methods usually leach all valuable metals and subsequently extract target meals to prepare corresponding materials. However, Li recovery in these processes requires lengthy operational procedures, and the recovery efficiency is low. In this research, we demonstrate a method to selectively recover lithium before the leaching of other elements by introducing a hydrothermal treatment. Approximately 90% of Li is leached from high-Ni layered oxide cathode powders, while consuming a nearly stoichiometric amount of hydrogen ions. With this selective recovery of Li, the transition metals remain as solid residue hydroxides or oxides. Furthermore, the extraction of Li is found to be highly dependent on the content of transition metals in the cathode materials. A high leaching selectivity of Li (>98%) and nearly 95% leaching efficiency of Li can be reached with LiNi_0.8Co_0.1Mn_0.1O₂. In this case, both the energy and material consumption during the proposed Li recovery is significantly decreased compared to traditional methods; furthermore, the proposed method makes full use of H⁺ to leach Li⁺. This research is expected to provide new understanding for selectively recovering metal from secondary resources.

Keywords recycling spent LIBs selective recovery hydrothermal treatment

Corresponding Author(s): Zhi Sun

Just Accepted Date: 03 March 2021 Online First Date: 28 April 2021 Issue Date: 30 August 2021

Cite this article:

Weiguang Lv,Xiaohong Zheng,Li Li, et al. Highly selective metal recovery from spent lithium-ion batteries through stoichiometric hydrogen ion replacement[J]. Front. Chem. Sci. Eng., 2021, 15(5): 1243-1256.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-2029-3
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I5/1243

Tab.1 Scrap compositions obtained from inductively coupled plasma optical emission spectrometer

Fig.1 Scheme showing the selective recovery approach.

Fig.2 Effects of (a) the initial H₂SO₄ concentration and (b) reaction temperature on the metal leaching efficiencies (L_M, M= Li, Ni, Co, Mn) and leaching selectivities (S_M, M= Li, Ni, Co, Mn) of different metals from NCM 1 under leaching conditons of 1.03 mol·L^–1 H₂SO₄, 200 °C, S/L= 200 g·L^–1, 500 r·min^–1 and 4 h (The theoretical value (grey cycle) is calculated by a one-to-one replacement of hydrogen ions with Li ions).

Fig.3 (a) Effects of leaching time on the metal leaching efficiencies and leaching selectivities of different metals from NCM 1 under leaching conditions of 1.03 mol·L^–1 H₂SO₄, 200 °C, S/L= 200 g·L^–1 and 500 r·min^–1; (b) effects of leaching time on the metal leaching efficiencies and leaching selectivities of different metals for NCM 2 under leaching conditions of 1.03 mol·L^–1 H₂SO₄, 200 °C, S/L= 200 g·L^–1 and 500 r·min^–1 (Because the residues in (b) are not cleaned with deionized water, the leaching efficiency of Li is lower than before).

Fig.4 E-pH diagrams for the (a) Ni-H₂O, (b) Co-H₂O, (c) Mn-H₂O and (d) Li-H₂O systems at different temperatures of 25, 100, 150 and 200 °C, respectively, (c(M²⁺/M⁺) = 0.1 mol·kg^–1, M= Li, Ni, Co, Mn). (e) Ni-H₂O system at 1, 0.1, 0.01, 0.0001 mol·kg^–1 Ni²⁺ at 25 °C and (f) Ni-H₂O system at 1, 0.1, 0.01, 0.0001 mol·kg^–1 Ni²⁺ at 200 °C (regenerated according to data from HSC Chemistry 6).

Fig.5 XRD patterns for the residues at different leaching times (other leaching conditions: raw materials, NCM 2; 1.03 mol·L^–1 H₂SO₄, 200 °C, S/L= 200 g·L^–1, 500 r·min^–1).

Fig.6 SEM images of the residues at different reaction times: (a) raw NCM 2 and (b) –10 min, (c) 0 min, (d) 30 min, (e) 60 min and (f) 240 min. EDS point results of (g) raw NCM 2, (h) 30 min and (i) 240 min particles (The figures are magnified 10000 times, and the inset figures are enlarged 5000 times. The –10 min residues are from the reaction in which the autoclave is heated to 150 °C at which point the heating is immediately stopped. Similarly, 0 min means the sample is heated to 200 °C with a holding time of 0 min).

Fig.7 EDS mapping results of the residue particles at leaching times of (a) 60 min and (b) 240 min.

Fig.8 Atomic ratio of the different transition metals from the XPS results (Mn 2p, Ni 2p and Co 2p) on the surface of the residues at different reaction times.

Fig.9 XPS spectra of (a) Mn 3s, (b) Ni 2p and (c) Co 2p for the residues at different reaction times.

Fig.10 (a) Leaching results for the different spent cathode materials through the hydrothermal treatment (1.03 mol·L^–1 H₂SO₄, 200 °C, S/L= 200 g·L^–1, 500 r·min^–1 and 4 h; 0.5 mol·L^–1 H₂SO₄ for leaching LMO; the molar ratios of H⁺ and Li⁺ are all close to 1:1 when disposing these cathode materials); (b) effects of the occupying fraction of Ni²⁺/Ni³⁺ and Co²⁺/Co³⁺ on the L_Li and S_Li.

Tab.2 Relevant data of the different cathode materials [48] ^a)

1	E Fan, L Li, Z Wang, J Lin, Y Huang, Y Yao, R Chen, F Wu. Sustainable recycling technology for Li-ion batteries and beyond: challenges and future prospects. Chemical Reviews, 2020, 120(14): 7020–7063 https://doi.org/10.1021/acs.chemrev.9b00535
2	W G Lv, Z H Wang, H B Cao, Y Sun, Y Zhang, Z Sun. A critical review and analysis on the recycling of spent lithium-ion batteries. ACS Sustainable Chemistry & Engineering, 2018, 6(2): 1504–1521 https://doi.org/10.1021/acssuschemeng.7b03811
3	G Harper, R Sommerville, E Kendrick, L Driscoll, P Slater, R Stolkin, A Walton, P Christensen, O Heidrich, S Lambert, A Abbott, K Ryder, L Gaines, P Anderson. Recycling lithium-ion batteries from electric vehicles. Nature, 2019, 575(7781): 75–86 https://doi.org/10.1038/s41586-019-1682-5
4	J Xiao, J Li, Z Xu. Challenges to future development of spent lithium ion batteries recovery from environmental and technological perspectives. Environmental Science & Technology, 2020, 54(1): 9–25
5	X Zeng, S H Ali, J Tian, J Li. Mapping anthropogenic mineral generation in China and its implications for a circular economy. Nature Communications, 2020, 11(1): 1544 https://doi.org/10.1038/s41467-020-15246-4
6	H Dang, B F Wang, Z D Chang, X Wu, J G Feng, H L Zhou, W J Li, C Y Sun. Recycled lithium from simulated pyrometallurgical slag by chlorination roasting. ACS Sustainable Chemistry & Engineering, 2018, 6(10): 13160–13167 https://doi.org/10.1021/acssuschemeng.8b02713
7	Y Yang, S Lei, S Song, W Sun, L Wang. Stepwise recycling of valuable metals from Ni-rich cathode material of spent lithium-ion batteries. Waste Management (New York, N.Y.), 2020, 102: 131–138 https://doi.org/10.1016/j.wasman.2019.09.044
8	M Yu, Z H Zhang, F Xue, B Yang, G H Guo, J H Qiu. A more simple and efficient process for recovery of cobalt and lithium from spent lithium-ion batteries with citric acid. Separation and Purification Technology, 2019, 215: 398–402 https://doi.org/10.1016/j.seppur.2019.01.027
9	C S Dos Santos, J C Alves, S P Da Silva, L Evangelista Sita, P R C Da Silva, L C De Almeida, J Scarminio. A closed-loop process to recover Li and Co compounds and to resynthesize LiCoO2 from spent mobile phone batteries. Journal of Hazardous Materials, 2019, 362: 458–466 https://doi.org/10.1016/j.jhazmat.2018.09.039
10	X Chen, C Guo, H Ma, J Li, T Zhou, L Cao, D Kang. Organic reductants based leaching: a sustainable process for the recovery of valuable metals from spent lithium ion batteries. Waste Management (New York, N.Y.), 2018, 75: 459–468 https://doi.org/10.1016/j.wasman.2018.01.021
11	L Li, Y F Bian, X X Zhang, Q Xue, E S Fan, F Wu, R J Chen. Economical recycling process for spent lithium-ion batteries and macro- and micro-scale mechanistic study. Journal of Power Sources, 2018, 377: 70–79 https://doi.org/10.1016/j.jpowsour.2017.12.006
12	Y Yang, S Xu, Y He. Lithium recycling and cathode material regeneration from acid leach liquor of spent lithium-ion battery via facile co-extraction and co-precipitation processes. Waste Management (New York, N.Y.), 2017, 64: 219–227 https://doi.org/10.1016/j.wasman.2017.03.018
13	D Dutta, A Kumari, R Panda, S Jha, D Gupta, S Goel, M K Jha. Close loop separation process for the recovery of Co, Cu, Mn, Fe and Li from spent lithium-ion batteries. Separation and Purification Technology, 2018, 200: 327–334 https://doi.org/10.1016/j.seppur.2018.02.022
14	S G Zhu, W Z He, G M Li, X Zhou, X J Zhang, J W Huang. Recovery of Co and Li from spent lithium-ion batteries by combination method of acid leaching and chemical precipitation. Transactions of Nonferrous Metals Society of China, 2012, 22(9): 2274–2281 https://doi.org/10.1016/S1003-6326(11)61460-X
15	L Shuya, C Yang, C Xuefeng, S Wei, W Yaqing, Y Yue. Separation of lithium and transition metals from leachate of spent lithium-ion batteries by solvent extraction method with Versatic 10. Separation and Purification Technology, 2020, 250: 117258 https://doi.org/10.1016/j.seppur.2020.117258
16	C W Liu, J Lin, H B Cao, Y Zhang, Z Sun. Recycling of spent lithium-ion batteries in view of lithium recovery: a critical review. Journal of Cleaner Production, 2019, 228: 801–813 https://doi.org/10.1016/j.jclepro.2019.04.304
17	J Lin, C W Liu, H B Cao, R J Chen, Y X Yang, L Li, Z Sun. Environmentally benign process for selective recovery of valuable metals from spent lithium-ion batteries by using conventional sulfation roasting. Green Chemistry, 2019, 21(21): 5904–5913 https://doi.org/10.1039/C9GC01350D
18	X D Zhang, D H Wang, H J Chen, L X Yang, Y S Yu, L Xu. Chemistry evolution of LiNi1/3Co1/3Mn1/3O2-NaHSO4 center dot H2O system during roasting. Solid State Ionics, 2019, 339: 114983 https://doi.org/10.1016/j.ssi.2019.05.018
19	C Peng, F P Liu, Z L Wang, B P Wilson, M Lundstrom. Selective extraction of lithium (Li) and preparation of battery grade lithium carbonate (Li2CO3) from spent Li-ion batteries in nitrate system. Journal of Power Sources, 2019, 415: 179–188 https://doi.org/10.1016/j.jpowsour.2019.01.072
20	W Q Wang, Y C Zhang, X G Liu, S M Xu. A simplified process for recovery of Li and Co from spent LiCoO2 cathode using Al foil as the in situ reductant. ACS Sustainable Chemistry & Engineering, 2019, 7(14): 12222–12230 https://doi.org/10.1021/acssuschemeng.9b01564
21	J F Xiao, J Li, Z M Xu. Novel approach for in situ recovery of lithium carbonate from spent lithium ion batteries using vacuum metallurgy. Environmental Science & Technology, 2017, 51(20): 11960–11966 https://doi.org/10.1021/acs.est.7b02561
22	J L Zhang, J T Hu, W J Zhang, Y Q Chen, C Y Wang. Efficient and economical recovery of lithium, cobalt, nickel, manganese from cathode scrap of spent lithium-ion batteries. Journal of Cleaner Production, 2018, 204: 437–446 https://doi.org/10.1016/j.jclepro.2018.09.033
23	Y Tang, H Xie, B Zhang, X Chen, Z Zhao, J Qu, P Xing, H Yin. Recovery and regeneration of LiCoO2-based spent lithium-ion batteries by a carbothermic reduction vacuum pyrolysis approach: controlling the recovery of CoO or Co. Waste Management (New York, N.Y.), 2019, 97: 140–148 https://doi.org/10.1016/j.wasman.2019.08.004
24	W Gao, X Zhang, X Zheng, X Lin, H Cao, Y Zhang, Z Sun. Lithium carbonate recovery from cathode scrap of spent lithium-ion battery: a closed-loop process. Environmental Science & Technology, 2017, 51(3): 1662–1669 https://doi.org/10.1021/acs.est.6b03320
25	Y X Yang, H L Yang, H B Cao, Z H Wang, C W Liu, Y Sun, H Zhao, Y Zhang, Z Sun. Direct preparation of efficient catalyst for oxygen evolution reaction and high-purity Li2CO3 from spent LiNi0.5Mn0.3Co0.2O2 batteries. Journal of Cleaner Production, 2019, 236: 117576 https://doi.org/10.1016/j.jclepro.2019.07.051
26	M M Wang, C C Zhang, F S Zhang. Recycling of spent lithium-ion battery with polyvinyl chloride by mechanochemical process. Waste Management (New York, N.Y.), 2017, 67: 232–239 https://doi.org/10.1016/j.wasman.2017.05.013
27	X Zheng, W Gao, X Zhang, M He, X Lin, H Cao, Y Zhang, Z Sun. Spent lithium-ion battery recycling—reductive ammonia leaching of metals from cathode scrap by sodium sulphite. Waste Management (New York, N.Y.), 2017, 60: 680–688 https://doi.org/10.1016/j.wasman.2016.12.007
28	S M Shin, N H Kim, J S Sohn, D H Yang, Y H Kim. Development of a metal recovery process from Li-ion battery wastes. Hydrometallurgy, 2005, 79(3-4): 172–181 https://doi.org/10.1016/j.hydromet.2005.06.004
29	B Swain, J Jeong, J C Lee, G H Lee, J S Sohn. Hydrometallurgical process for recovery of cobalt from waste cathodic active material generated during manufacturing of lithium ion batteries. Journal of Power Sources, 2007, 167(2): 536–544 https://doi.org/10.1016/j.jpowsour.2007.02.046
30	P Ning, Q Meng, P Dong, J Duan, M Xu, Y Lin, Y Zhang. Recycling of cathode material from spent lithium ion batteries using an ultrasound-assisted DL-malic acid leaching system. Waste Management (New York, N.Y.), 2020, 103: 52–60 https://doi.org/10.1016/j.wasman.2019.12.002
31	H Munir, R R Srivastava, H Kim, S Ilyas, M K Khosa, B Yameen. Leaching of exhausted LNCM cathode batteries in ascorbic acid lixiviant: a green recycling approach, reaction kinetics and process mechanism. Journal of Chemical Technology and Biotechnology (Oxford, Oxfordshire), 2020, 95(8): 2286–2294 https://doi.org/10.1002/jctb.6418
32	L Zhuang, C Sun, T Zhou, H Li, A Dai. Recovery of valuable metals from LiNi0.5Co0.2Mn0.3O2 cathode materials of spent Li-ion batteries using mild mixed acid as leachant. Waste Management (New York, N.Y.), 2019, 85: 175–185 https://doi.org/10.1016/j.wasman.2018.12.034
33	Q K Jing, J L Zhang, Y B Liu, C Yang, B Z Ma, Y Q Chen, C Y Wang. E-pH diagrams for the Li-Fe-P-H2O system from 298 to 473 K: thermodynamic analysis and application to the wet chemical processes of the LiFePO4 cathode material. Journal of Physical Chemistry C, 2019, 123(23): 14207–14215 https://doi.org/10.1021/acs.jpcc.9b02074
34	R Golmohammadzadeh, F Faraji, F Rashchi. Recovery of lithium and cobalt from spent lithium ion batteries (LIBs) using organic acids as leaching reagents: a review. Resources, Conservation and Recycling, 2018, 136: 418–435 https://doi.org/10.1016/j.resconrec.2018.04.024
35	M Esmaeili, S O Rastegar, R Beigzadeh, T Gu. Ultrasound-assisted leaching of spent lithium ion batteries by natural organic acids and H2O2. Chemosphere, 2020, 254: 126670 https://doi.org/10.1016/j.chemosphere.2020.126670
36	J De Oliveira Demarco, J Stefanello Cadore, F Da Silveira de Oliveira, E Hiromitsu Tanabe, D Assumpção Bertuol. Recovery of metals from spent lithium-ion batteries using organic acids. Hydrometallurgy, 2019, 190: 105169 https://doi.org/10.1016/j.hydromet.2019.105169
37	W Lv, Z Wang, H Cao, X Zheng, W Jin, Y Zhang, Z Sun. A sustainable process for metal recycling from spent lithium-ion batteries using ammonium chloride. Waste Managememt, 2018, 79: 545–553 https://doi.org/10.1016/j.wasman.2018.08.027
38	W Lee, S Muhammad, T Kim, H Kim, E Lee, M Jeong, S Son, J H Ryou, W S Yoon. New insight into Ni-rich layered structure for next-generation Li rechargeable batteries. Advanced Energy Materials, 2018, 8(4): 1701788 https://doi.org/10.1002/aenm.201701788
39	W Li, H Y Asl, Q Xie, A Manthiram. Collapse of LiNi1−x−yCoxMnyO2 lattice at deep charge irrespective of nickel content in lithium-ion batteries. Journal of the American Chemical Society, 2019, 141(13): 5097–5101 https://doi.org/10.1021/jacs.8b13798
40	Q Y Su, Y J Li, L Li, W Li, G L Cao, L L Xue, J G Li, X L Cao. Synthesis and electrochemical properties of LiNi1/3Co1/3Mn1/3O2 via an original wet-chemical route for high voltage Li-ion batteries. Materials Letters, 2017, 198: 180–183 https://doi.org/10.1016/j.matlet.2017.03.130
41	K S Lee, S T Myung, Y K Sun. Microwave synthesis of spherical Li[Ni0.4Co0.2Mn0.4]O2 powders as a positive electrode material for lithium batteries. Chemistry of Materials, 2007, 19(11): 2727–2729 https://doi.org/10.1021/cm070502c
42	A Rafique, A Massa, M Fontana, S Bianco, A Chiodoni, C F Pirri, S Hernandez, A Lamberti. Highly uniform anodically deposited film of MnO2 nanoflakes on carbon fibers for flexible and wearable fiber-shaped supercapacitors. ACS Applied Materials & Interfaces, 2017, 9(34): 28386–28393 https://doi.org/10.1021/acsami.7b06311
43	Q Xu, X Li, H M Kheimeh Sari, W Li, W Liu, Y Hao, J Qin, B Cao, W Xiao, Y Xu, et al. Surface engineering of LiNi0.8Mn0.1Co0.1O2 towards boosting lithium storage: bimetallic oxides versus monometallic oxides. Nano Energy, 2020, 77: 105034 https://doi.org/10.1016/j.nanoen.2020.105034
44	D Huang, J Yu, Z Zhang, C Engtrakul, A Burrell, M Zhou, H Luo, R C Tenent. Enhancing the electrocatalysis of LiNi0.5Co0.2Mn0.3O2 by introducing lithium deficiency for oxygen evolution reaction. ACS Applied Materials & Interfaces, 2020, 12(9): 10496–10502 https://doi.org/10.1021/acsami.9b22438
45	H Yang, K Wu, G Hu, Z Peng, Y Cao, K Du. Design and synthesis of double-functional polymer composite layer coating to enhance the electrochemical performance of the Ni-rich cathode at the upper cutoff voltage. ACS Applied Materials & Interfaces, 2019, 11(8): 8556–8566 https://doi.org/10.1021/acsami.8b21621
46	D Ensling, G Cherkashinin, S Schmid, S Bhuvaneswari, A Thissen, W Jaegermann. Nonrigid band behavior of the electronic structure of LiCoO2 thin film during electrochemical Li deintercalation. Chemistry of Materials, 2014, 26(13): 3948–3956 https://doi.org/10.1021/cm501480b
47	N Weidler, S Paulus, J Schuch, J Klett, S Hoch, P Stenner, A Maljusch, J Brotz, C Wittich, B Kaiser, W Jaegermann. CoOx thin film deposited by CVD as efficient water oxidation catalyst: change of oxidation state in XPS and its correlation to electrochemical activity. Physical Chemistry Chemical Physics, 2016, 18(16): 10708–10718 https://doi.org/10.1039/C5CP05691H
48	H Sun, K J Zhao. Electronic structure and comparative properties of LiNixMnyCozO2 cathode materials. Journal of Physical Chemistry C, 2017, 121(11): 6002–6010 https://doi.org/10.1021/acs.jpcc.7b00810

[1]	Remus I. Iacobescu, Valérie Cappuyns, Tinne Geens, Lubica Kriskova, Silviana Onisei, Peter T. Jones, Yiannis Pontikes. The influence of curing conditions on the mechanical properties and leaching of inorganic polymers made of fayalitic slag[J]. Front. Chem. Sci. Eng., 2017, 11(3): 317-327.
[2]	Xiaokai SONG,Zhongyi JIANG,Lin LI,Hong WU. Immobilization of β-glucuronidase in lysozyme-induced biosilica particles to improve its stability[J]. Front. Chem. Sci. Eng., 2014, 8(3): 353-361.
[3]	QIAO Congzhen, LI Chengyue. Continuous reaction performances of benzene alkylation with long chain olefins catalyzed by ionic liquid[J]. Front. Chem. Sci. Eng., 2008, 2(1): 69-73.

Viewed

Full text

Abstract

Cited

Shared

Discussed