Progress on Regeneration and Reutilization of Anode Materials from Spent Lithium-ion Batteries

Abstract The vigorous development of the electric vehicle market produces a large number of spent power batteries. Considering the environmental pollution of hazardous wastes and the scarcity of some resources, the recycling of spent lithium-ion batteries (LIBs) has great economic value and practical significance. In recent years, many efforts have been made in the recovery of cathode materials (such as high-value metal cobalt, nickel, lithium, etc.). Unfortunately, the regeneration of the relatively lower value-added anode materials (mainly graphite) has not gained much attention. However, considering the wide application of carbon-based materials and the higher content of lithium in the anode than that in the environment, the recycling of anode materials has attracted increasing attention since 2016. Therefore, this review summarizes the latest research progress in the recovery of graphite anode materials of spent LIBs, analyzes the strengths and deficiencies of various recovery routes including direct physical recovery, heat treatment recovery, hydrometallurgy recovery, heat treatment-hydrometallurgy recovery, extraction and electrochemical methods from the perspectives of energy, environment and economy; moreover, the reuse of recycled anode materials in the fields of energy storage and preparation of functional materials are also recapitulated. Finally, challenges and future prospects of LIBs anode recycling are proposed, a low energy-consuming and environmentally-benign approach should be explored to enable the green recycling of spent LIBs.

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	Articles by authors
	Liu Dongxu
	Cai Muya
	Chen Xiang
	Xie Hongwei
	Ning Zhiqiang
	Yin Huayi

Keywords： lithium-ion batteries anode graphite regeneration reutilization

Received 2021-03-14;

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Liu Dongxu, Cai Muya, Chen Xiang, Xie Hongwei, Ning Zhiqiang, Yin Huayi.Progress on Regeneration and Reutilization of Anode Materials from Spent Lithium-ion Batteries[J] Chemcial Industry and Engineering, 2021,V38(6): 2-12

[1] Anonym. Global EV Outlook 2018[EB/OL]. 2021-03-15. https://www.iea.org/reports/global-ev-outlook-2018
[2] Anonym. Global EV Outlook 2019[EB/OL]. 2021-03-15. https://www.iea.org/reports/global-ev-outlook-2019
[3] Anonym. Global EV Outlook 2020[EB/OL]. 2021-03-15. https://www.iea.org/reports/global-ev-outlook-2020
[4] Zhang B, Xie H, Lu B, et al. A green electrochemical process to recover Co and Li from spent LiCoO₂-based batteries in molten salts[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(15):13391-13399
[5] Qu X, Xie H, Chen X, et al. Recovery of LiCoO₂ from spent lithium-ion batteries through a low-temperature ammonium chloride roasting approach:Thermodynamics and reaction mechanisms[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(16):6524-6532
[6] Zhao J, Zhang B, Xie H, et al. Hydrometallurgical recovery of spent cobalt-based lithium-ion battery cathodes using ethanol as the reducing agent[J]. Environmental Research, 2020, doi:10.1016/j.envres.2019.108803
[7] Li H, Xing S, 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
[8] Fan E, Li L, Zhang 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
[9] Zhang J, Hu J, Liu Y, et al. Sustainable and facile method for the selective recovery of lithium from cathode scrap of spent LiFePO₄ batteries[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(6):5626-5631
[10] Liu P, Xiao L, Chen Y, et al. Recovering valuable metals from LiNi_xCo_yMn_{1-x-yO₂ 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

[11] Tang Y, Qu X, Zhang B, et al. Recycling of spent lithium nickel cobalt manganese oxides via a low-temperature ammonium sulfation roasting approach[J]. Journal of Cleaner Production, 2021, doi:10.1016/j.jclepro.2020.123633

[12] 张英杰, 宁培超, 杨轩, 等. 废旧三元锂离子电池回收技术研究新进展[J]. 化工进展, 2020, 39(7):2828-2840 Zhang Yingjie, Ning Peichao, Yang Xuan, et al. Research progress on the recycling technology of spent ternary lithium ion battery[J]. Chemical Industry and Engineering Progress, 2020, 39(7):2828-2840(in Chinese)

[13] Harper G, Sommerville R, Kendrick E, et al. Recycling lithium-ion batteries from electric vehicles[J]. Nature, 2019, 575(7781):75-86

[14] Li L, Ge J, Chen R, et al. Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries[J]. Waste Management, 2010, 30(12):2615-2621

[15] Zheng Z, Chen M, Wang Q, et al. High performance cathode recovery from different electric vehicle recycling streams[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(11):13977-13982

[16] Kim D S, Sohn J S, Lee C K, et al. Simultaneous separation and renovation of lithium cobalt oxide from the cathode of spent lithium ion rechargeable batteries[J]. Journal of Power Sources, 2004, 132(1/2):145-149

[17] Ordoñez J, Gago E J, Girard A. Processes and technologies for the recycling and recovery of spent lithium-ion batteries[J]. Renewable and Sustainable Energy Reviews, 2016, 60:195-205

[18] Natarajan S, Aravindan V. An urgent call to spent LIB recycling:Whys and wherefores for graphite recovery[J]. Advanced Energy Materials, 2020, doi:10.1002/aenm.202002238

[19] Hou H, Qiu X, Wei W, et al. Carbon anode materials for advanced sodium-ion batteries[J]. Advanced Energy Materials, 2017, doi:10.1002/aenm.201602898

[20] 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

[21] Dimovski S, Nikitin A, Ye H, et al. Synthesis of graphite by chlorination of iron carbide at moderate temperatures[J]. Journal of Materials Chemistry, 2004, 14(2):238-243

[22] Moradi B, Botte G G. Recycling of graphite anodes for the next generation of lithium ion batteries[J]. Journal of Applied Electrochemistry, 2016, 46(2):123-148

[23] Zeng X, Li J, Singh N. Recycling of spent lithium-ion battery:A critical review[J]. Critical Reviews in Environmental Science and Technology, 2014, 44(10):1129-1165

[24] Guo Y, Li F, Zhu H, 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

[25] Anonym. About Graphite[EB/OL]. 2021-03-15. https://www.masongraphite.com/about-graphite

[26] Lv W, Wang Z, Cao H, et al. A critical review and analysis on the recycling of spent lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(2):1504-1521

[27] 张梦龙, 何几文, 田欢, 等. 废旧锂离子电池中有价金属的回收研究进展[J]. 化学工业与工程, 2019, 36(4):23-30 Zhang Menglong, He Jiwen, Tian Huan, et al. Research progress on recovery of valuable metals from spent lithium ion batteries[J]. Chemical Industry and Engineering, 2019, 36(4):23-30(in Chinese)

[28] Fan E, Li L, Wang Z, et al. Sustainable recycling technology for Li-ion batteries and beyond:Challenges and future prospects[J]. Chemical Reviews, 2020, 120(14):7020-7063

[29] Zhang X, Li L, Fan E, et al. Toward sustainable and systematic recycling of spent rechargeable batteries[J]. Chemical Society Reviews, 2018, 47(19):7239-7302

[30] 周旭, 朱曙光, 次西拉姆, 等. 废锂离子电池负极材料的机械分离与回收[J]. 中国有色金属学报, 2011, 21(12):3082-3086 Zhou Xu, Zhu Shuguang, Ci Xilamu, et al. Mechanical separation and recovery process of anode materials from spent lithium-ion batteries[J]. The Chinese Journal of Nonferrous Metals, 2011, 21(12):3082-3086(in Chinese)

[31] 文瑞明, 胡拥军, 齐风佩, 等. 锂离子电池负极材料浮选回收研究[J]. 电池工业, 2013, 18(Z1):18-20,37 Wen Ruiming, Hu Yongjun, Qi Fengpei, et al. Study on flotation recovery of Li-ion battery cathode material[J]. Chinese Battery Industry, 2013, 18(Z1):18-20,37(in Chinese)

[32] He Y, Zhang T, Wang F, et al. Recovery of LiCoO₂ and graphite from spent lithium-ion batteries by Fenton reagent-assisted flotation[J]. Journal of Cleaner Production, 2017, 143:319-325

[33] Yu J, He Y, Ge Z, et al. A promising physical method for recovery of LiCoO₂ and graphite from spent lithium-ion batteries:Grinding flotation[J]. Separation and Purification Technology, 2018, 190:45-52

[34] Zhang G, He Y, Feng Y, et al. Pyrolysis-ultrasonic-assisted flotation technology for recovering graphite and LiCoO₂ from spent lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(8):10896-10904

[35] Sabisch J E C, Anapolsky A, Liu G, et al. Evaluation of using pre-lithiated graphite from recycled Li-ion batteries for new LiB anodes[J]. Resources, Conservation and Recycling, 2018, 129:129-134

[36] Wang H, Huang Y, Huang C, et al. Reclaiming graphite from spent lithium ion batteries ecologically and economically[J]. Electrochimica Acta, 2019, 313:423-431

[37] Ye C, Tu W, Yin L, et al. Converting detrimental HF in electrolytes into a highly fluorinated interphase on cathodes[J]. Journal of Materials Chemistry A, 2018, 6(36):17642-17652

[38] Liao X, Sun P, Xu M, et al. Application of tris(trimethylsilyl) borate to suppress self-discharge of layered nickel cobalt manganese oxide for high energy battery[J]. Applied Energy, 2016, 175:505-511

[39] Ma Z, Zhuang Y, Deng Y, et al. From spent graphite to amorphous sp2+sp3 carbon-coated sp2 graphite for high-performance lithium ion batteries[J]. Journal of Power Sources, 2018, 376:91-99

[40] Zhang J, Li X, Song D, et al. Effective regeneration of anode material recycled from scrapped Li-ion batteries[J]. Journal of Power Sources, 2018, 390:38-44

[41] Yi C, Yang Y, Zhang T, et al. A green and facile approach for regeneration of graphite from spent lithium ion battery[J]. Journal of Cleaner Production, 2020, 277:123585

[42] Natarajan S, Shanthana Lakshmi D, Bajaj H C, et al. Recovery and utilization of graphite and polymer materials from spent lithium-ion batteries for synthesizing polymer-graphite nanocomposite thin films[J]. Journal of Environmental Chemical Engineering, 2015, 3(4):2538-2545

[43] 杨生龙, 杨凯雲, 范小萍, 等. 废旧锂离子电池负极片的硫酸浸出回收研究[J]. 电源技术, 2020, 44(3):364-366,376 Yang Shenglong, Yang Kaiyun, Fan Xiaoping, et al. Recycling of negative electrode sheets of spent lithium ion batteries by sulfuric acid leaching[J]. Chinese Journal of Power Sources, 2020, 44(3):364-366,376(in Chinese)

[44] Ma X, Chen M, Chen B, et al. High-performance graphite recovered from spent lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(24):19732-19738

[45] Yang Y, Song S, Lei S, et al. A process for combination of recycling lithium and regenerating graphite from spent lithium-ion battery[J]. Waste Management, 2019, 85:529-537

[46] Gao Y, Wang C, Zhang J, et al. Graphite recycling from the spent lithium-ion batteries by sulfuric acid curing-leaching combined with high-temperature calcination[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(25):9447-9455

[47] Rothermel S, Evertz M, Kasnatscheew J, et al. Graphite recycling from spent lithium-ion batteries[J]. ChemSusChem, 2016, 9(24):3473-3484

[48] Cao N, Zhang Y, Chen L, et al. An innovative approach to recover anode from spent lithium-ion battery[J]. Journal of Power Sources, 2021, doi:10.1016/j.jpowsour.2020.229163

[49] Aravindan V, Jayaraman S, Tedjar F, et al. From electrodes to electrodes:Building high-performance Li-ion capacitors and batteries from spent lithium-ion battery carbonaceous materials[J]. ChemElectroChem, 2019, 6(5):1407-1412

[50] Divya M L, Natarajan S, Lee Y S, et al. Achieving high-energy dual carbon Li-ion capacitors with unique low- and high-temperature performance from spent Li-ion batteries[J]. Journal of Materials Chemistry A, 2020, 8(9):4950-4959

[51] Liang H, Hou B, Li W, et al. Staging Na/K-ion de-/intercalation of graphite retrieved from spent Li-ion batteries:In operando X-ray diffraction studies and an advanced anode material for Na/K-ion batteries[J]. Energy & Environmental Science, 2019, 12(12):3575-3584

[52] Liu K, Yang S, Luo L, et al. From spent graphite to recycle graphite anode for high-performance lithium ion batteries and sodium ion batteries[J]. Electrochimica Acta, 2020, doi:10.1016/j.electacta.2020.136856

[53] Pham H D, Horn M, Fernando J F S, et al. Spent graphite from end-of-life Li-ion batteries as a potential electrode for aluminium ion battery[J]. Sustainable Materials and Technologies, 2020, doi:10.1016/j.susmat.2020.e00230

[54] Zhang W, Liu Z, Xia J, et al. Preparing graphene from anode graphite of spent lithium-ion batteries[J]. Frontiers of Environmental Science & Engineering, 2017, 11(5):1-8

[55] Natarajan S, Rao Ede S, Bajaj H C, et al. Environmental benign synthesis of reduced graphene oxide (rGO) from spent lithium-ion batteries (LIBs) graphite and its application in supercapacitor[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2018, 543:98-108

[56] Natarajan S, Bajaj H C, Aravindan V. Template-free synthesis of carbon hollow spheres and reduced graphene oxide from spent lithium-ion batteries towards efficient gas storage[J]. Journal of Materials Chemistry A, 2019, 7(7):3244-3252

[57] Chen X, Zhu Y, Peng W, et al. Direct exfoliation of the anode graphite of used Li-ion batteries into few-layer graphene sheets:A green and high yield route to high-quality graphene preparation[J]. Journal of Materials Chemistry A, 2017, 5(12):5880-5885

[58] Zhang Y, Song N, He J, et al. Lithiation-aided conversion of end-of-life lithium-ion battery anodes to high-quality graphene and graphene oxide[J]. Nano Letters, 2019, 19(1):512-519

[59] Zhang Y, Guo X, Wu F, et al. Mesocarbon microbead carbon-supported magnesium hydroxide nanoparticles:Turning spent Li-ion battery anode into a highly efficient phosphate adsorbent for wastewater treatment[J]. ACS Applied Materials & Interfaces, 2016, 8(33):21315-21325

[60] Zhang Y, Guo X, Yao Y, et al. Synthesis of Mg-decorated carbon nanocomposites from MesoCarbon MicroBeads (MCMB) graphite:Application for wastewater treatment[J]. ACS Omega, 2016, 1(3):417-423

[61] Zhao T, Yao Y, Wang M, et al. Preparation of MnO₂-modified graphite sorbents from spent Li-ion batteries for the treatment of water contaminated by lead, cadmium, and silver[J]. ACS Applied Materials & Interfaces, 2017, 9(30):25369-25376}