A promising method for recovery of LiMn₂O₄ and graphite from waste lithium-ion batteries: Roasting enhanced flotation

Abstract

In this study, a roasting enhanced flotation process was proposed to recover LiMn₂O₄ and grapite from waste lithium-ion batteries (LIBs). The effects of roasting temperature and time on the surface modification was investigated, and a series of analytical technologies were used to reveal process mechanism. The results indicate that LiMn₂O₄ can be effectively separated from graphite via flotation after the roasting. The flotation grade of LiMn₂O₄ was significantly increased from 63.10% to 91.36% after roasting at 550 °C for 2 h. The TG-DTG analysis demonstrates that the difficulty in flotation separation of LiMn₂O₄ from graphite is caused by the organic binder and electrolytes coating on their surfaces. The XRD, SEM, XPS, and contact angle analyses confirm that the organic films on the surfaces of those materials can be effectively removed by roasting, after which the wettability of LiMn₂O₄ is regained and thus the surface wettability difference between the cathode and anode materials is increased significantly. The closed-circuit flotation test indicates that a LiMn₂O₄ sample with high grade of 99.81% is obtained, while the recovery of LiMn₂O₄ is as high as 99.40%. This study provides an economical and eco-friendly way to recycling waste LIBs.

Keywords

spent lithium-ion battery / resource recycling / roasting / surface modification / flotation

References

[1] BertuolD A, ToniassoC, JiménezB M, et al.. Application of spouted bed elutriation in the recycling of lithium ion batteries [J]. Journal of Power Sources, 2015, 275: 627-632

[2] ZengX, LiJ, LiuL. Solving spent lithiumion battery problems in China: Opportunities and challenges [J]. Renewable and Sustainable Energy Reviews, 2015, 52: 1759-1767

[3] TarasconJ M, ArmandM. Issues and challenges facing rechargeable lithium batteries [J]. Nature, 2001, 414(6861): 359-367

[4] NittaN, WuF, LeeJ T, et al.. Li-ion battery materials: Present and future [J]. Materials Today, 2015, 18(5): 252-264

[5] ZhangY, OuyangY, LiuL, et al.. Synthesis and characterization of Na_0.44MnO₂ nanorods/graphene composite as cathode materials for sodium-ion batteries [J]. Journal of Central South University, 2019, 26(6): 1510-1520

[6] TrägerT, FriedrichB, WeyheR. Recovery concept of value metals from automotive lithium-ion batteries [J]. Chemie Ingenieur Technik, 2015, 87(11): 1550-1557

[7] HarperG, SommervilleR, KendrickE, et al.. Recycling lithium-ion batteries from electric vehicles [J]. Nature, 2019, 575(7781): 75-86

[8] ZhouL, YangD, DuT, et al.. The current process for the recycling of spent lithium ion batteries [J]. Frontiers in Chemistry, 2020, 8: 578044

[9] LiH, YeH, SunM, et al.. Process for recycle of spent lithium iron phosphate battery via a selective leaching-precipitation method [J]. Journal of Central South University, 2020, 27(11): 3239-3248

[10] RuismäkiR, RinneT, DańczakA, et al.. Integrating flotation and pyrometallurgy for recovering graphite and valuable metals from battery scrap [J]. Metals, 2020, 10(5): 680

[11] HuangB, PanZ, SuX, et al.. Recycling of lithium-ion batteries: Recent advances and perspectives [J]. Journal of Power Sources, 2018, 399274-286

[12] FanX, SongC, LuX, et al.. Separation and recovery of valuable metals from spent lithium-ion batteries via concentrated sulfuric acid leaching and regeneration of LiNi_1/3Co_1/3Mn_1/3O₂ [J]. Journal of Alloys and Compounds, 2021, 863158775

[13] PengC, LiuF, WangZ, 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, 415179-188

[14] ChiuK, ChenW. Recovery and separation of valuable metals from cathode materials of spent lithiumion batteries (LIBs) by ion exchange [J]. Science of Advanced Materials, 2017, 9(12): 2155-2160

[15] ZengX, LiJ, SinghN. Recycling of spent lithium-ion battery: A critical review [J]. Critical Reviews in Environmental Science and Technology, 2014, 44(10): 1129-1165

[16] ZhangG, HeY, FengY, 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

[17] ZhangG, YuanX, HeY, et al.. High-efficiency liberation and flotation enhancement of electrode materials derived from spent lithium-ion during pyrolysis pretrement[J]. Journal of Central South University (Science and Technology), 2021, 52(4): 1058-1065(in Chinese)

[18] ZhangG, HeY, WangH, et al.. Application of mechanical crushing combined with pyrolysis-enhanced flotation technology to recover graphite and LiCoO₂ from spent lithium-ion batteries [J]. Journal of Cleaner Production, 2019, 231: 1418-1427

[19] ZhangT, HeY, WangF, et al.. Surface analysis of cobalt-enriched crushed products of spent lithiumion batteries by X-ray photoelectron spectroscopy [J]. Separation and Purification Technology, 2014, 138: 21-27

[20] LiangZ, CaiC, PengG, et al.. Hydrometallurgical recovery of spent lithium ion batteries: Environmental strategies and sustainability evaluation [J]. ACS Sustainable Chemistry & Engineering, 2021, 9(17): 5750-5767

[21] YaoY, ZhuM, ZhaoZ, et al.. Hydrometallurgical processes for recycling spent lithium-ion batteries: A critical review [J]. ACS Sustainable Chemistry & Engineering, 2018, 6(11): 13611-13627

[22] ZhangG, YuanX, HeY, et al.. Organics removal combined with in situ thermal-reduction for enhancing the liberation and metallurgy efficiency of LiCoO₂ derived from spent lithium-ion batteries [J]. Waste Management, 2020, 115: 113-120

[23] ZhongX, LiuW, HanJ, et al.. Pyrolysis and physical separation for the recovery of spent LiFePO₄ batteries [J]. Waste Management, 2019, 89: 83-93

[24] XiaoJ, LiJ, XuZ. 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

[25] LiJ, WangG, XuZ. 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

[26] ZhangG, DuZ, HeY, et al.. A sustainable process for the recovery of anode and cathode materials derived from spent lithium-ion batteries [J]. Sustainability, 2019, 11(8): 2363

[27] ZhangT, HeY, WangF, et al.. Chemical and process mineralogical characterizations of spent lithiumion batteries: An approach by multi-analytical techniques [J]. Waste Management, 2014, 3461051-1058

[28] ZhangG, HeY, WangH, et al.. Removal of organics by pyrolysis for enhancing liberation and flotation behavior of electrode materials derived from spent lithium-ion batteries [J]. ACS Sustainable Chemistry & Engineering, 2020, 8(5): 2205-2214

[29] Al-ThyabatS, NakamuraT, ShibataE, et al.. Adaptation of minerals processing operations for lithium-ion (LiBs) and nickel metal hydride (NiMH) batteries recycling: Critical review [J]. Minerals Engineering, 2013, 45: 4-17

[30] YuJ, HeY, GeZ, 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

[31] HeY, ZhangT, WangF, 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

[32] YuJ, HeY, LiH, et al.. Effect of the secondary product of semi-solid phase Fenton on the flotability of electrode material from spent lithium-ion battery [J]. Powder Technology, 2017, 315: 139-146

[33] YuJ, HeY, QuL, et al.. Exploring the critical role of grinding modification on the flotation recovery of electrode materials from spent lithium ion batteries [J]. Journal of Cleaner Production, 2020, 274: 123066

[34] LiuJ, WangH, HuT, et al.. Recovery of LiCoO₂ and graphite from spent lithium-ion batteries by cryogenic grinding and froth flotation [J]. Minerals Engineering, 2020, 148106223

[35] ChoiS S, KimY K. Microstructural analysis of poly (vinylidene fluoride) using benzene derivative pyrolysis products [J]. Journal of Analytical and Applied Pyrolysis, 2012, 9616-23

[36] HaoJ, WangH, ChenS, et al.. Pyrolysis characteristics of the mixture of printed circuit board scraps and coal powder [J]. Waste Management, 2014, 34(10): 1763-1769

[37] LiuW, XuJ, HanJ, et al.. Kinetic and mechanism studies on pyrolysis of printed circuit boards in the absence and presence of copper [J]. ACS Sustainable Chemistry & Engineering, 2019, 7(2): 1879-1889

[38] YangY, HuangG, XuS, et al.. Thermal treatment process for the recovery of valuable metals from spent lithium-ion batteries [J]. Hydrometallurgy, 2016, 165: 390-396

[39] ZhangG, HeY, FengY, et al.. Enhancement in liberation of electrode materials derived from spent lithium-ion battery by pyrolysis [J]. Journal of Cleaner Production, 2018, 199: 62-68

[40] ZhongX, HanJ, ChenL, et al.. Binding mechanisms of PVDF in lithium ion batteries [J]. Applied Surface Science, 2021, 553: 149564

[41] ChenY, LiuN, HuF, et al.. Thermal treatment and ammoniacal leaching for the recovery of valuable metals from spent lithium-ion batteries [J]. Waste Management, 2018, 75469-476

[42] WangF, ZhangT, HeY, et al.. Recovery of valuable materials from spent lithium-ion batteries by mechanical separation and thermal treatment [J]. Journal of Cleaner Production, 2018, 185: 646-652

[43] ZhongX, LiuW, HanJ, et al.. Pretreatment for the recovery of spent lithium ion batteries: Theoretical and practical aspects [J]. Journal of Cleaner Production, 2020, 263: 121439

[44] ZhongX, LiuW, HanJ, et al.. Pneumatic separation for crushed spent lithium-ion batteries [J]. Waste Management, 2020, 118331-340