Preferentially selective extraction of lithium from spent LiCoO₂ cathodes by medium-temperature carbon reduction roasting

Abstract

Lithium recovery from spent lithium-ion batteries (LIBs) have attracted extensive attention due to the skyrocketing price of lithium. The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO₂ (LCO) cathodes to overcome the incomplete recovery and loss of lithium during the recycling process. The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li₂CO₃ under a suitable temperature to control the reduced state of the cobalt oxide. The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium. The results showed that 99.10% of the whole lithium could be recovered as Li₂CO₃ with a purity of 99.55%. This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.

Keywords

spent LiCoO₂ cathodes / medium-temperature carbon reduction / lithium extraction priority / crystal transformation / macroscopic transport resistance

References

[1] Y.C. Lyu, X. Wu, K. Wang, et al., An overview on the advances of LiCoO₂ cathodes for lithium-ion batteries, Adv. Energy Mater., 11(2021), No. 2, art. No. 2000982.

[2] Fujita T, Chen H, Wang KT, et al. Reduction, reuse and recycle of spent Li-ion batteries for automobiles: A review. Int. J. Miner. Metall. Mater., 2021, 28(2): 179.

[3] Lin J, Wu JW, Fan ES, et al. Environmental and economic assessment of structural repair technologies for spent lithiumion battery cathode materials. Int. J. Miner. Metall. Mater., 2022, 29(5): 942.

[4] Tang ZX, Ye HQ, Ma X, Han K. Effect of particle micro-structure on the electrochemical properties of LiNi_0.8Co_0.1Mn_0.1O₂ cathode material. Int. J. Miner. Metall. Mater., 2022, 29(8): 1618.

[5] Qu JP, Zhao YS, Ji YR, Zhu YR, Yi TF. Approaching high-performance lithium storage materials by constructing Li₂ZnTi₃O₈@LiAlO₂ composites. Int. J. Miner. Metall. Mater., 2023, 30(4): 611.

[6] Chen MY, Ma XT, Chen B, et al. Recycling end-of-life electric vehicle lithium-ion batteries. Joule, 2019, 3(11): 2622.

[7] J.X. Wang, Q. Zhang, J.Z. Sheng, et al., Direct and green repairing of degraded LiCoO₂ for reuse in lithium-ion batteries, Natl. Sci. Rev., 9(2022), No. 8, art. No. nwac097.

[8] Yang M, Bi RY, Wang JY, Yu RB, Wang D. Decoding lithium batteries through advanced in situ characterization techniques. Int. J. Miner. Metall. Mater., 2022, 29(5): 965.

[9] Liu CW, Lin J, Cao HB, Zhang Y, Sun Z. Recycling of spent lithium-ion batteries in view of lithium recovery: A critical review. J. Cleaner Prod., 2019, 228, 801.

[10] Guo XY, Cao X, Huang GY, Tian QH, Sun HY. Re-covery of lithium from the effluent obtained in the process of spent lithium-ion batteries recycling. J. Environ. Manage., 2017, 198, 84.

[11] Lin J, Li L, Fan ES, et al. Conversion mechanisms of selective extraction of lithium from spent lithium-ion batteries by sulfation roasting. ACS Appl. Mater. Interfaces, 2020, 12(16): 18482.

[12] Hou JH, Ma XT, Fu JZ, et al. A green closed-loop process for selective recycling of lithium from spent lithium-ion batteries. Green Chem., 2022, 24(18): 7049.

[13] Liu YB, Ma BZ, Lü YW, Wang CY, Chen YQ. A review of lithium extraction from natural resources. Int. J. Miner. Metall. Mater., 2023, 30(2): 209.

[14] Dang H, Chang ZD, Zhou HL, Ma SH, Li M, Xiang JL. Extraction of lithium from the simulated pyrometallurgical slag of spent lithium-ion batteries by binary eutectic molten carbonates. Int. J. Miner. Metall. Mater., 2022, 29(9): 1715.

[15] Wang JX, Liang Z, Zhao Y, et al. Direct conversion of degraded LiCoO₂ cathode materials into high-performance LiCoO₂: A closed-loop green recycling strategy for spent lithium-ion batteries. Energy Storage Mater., 2022, 45, 768.

[16] Lin TN, Wang Y, Jin S, et al. An enhanced strategy based on the pyrolysis of bean dregs for efficient selective recovery of lithium from spent lithium-ion batteries. Green Chem., 2022, 24(24): 9552.

[17] Sun LY, Liu BR, Wu T, et al. Hydrometallurgical recycling of valuable metals from spent lithium-ion batteries by reductive leaching with stannous chloride. Int. J. Miner. Metall. Mater., 2021, 28(6): 991.

[18] Chen XP, Cao L, Kang DZ, Li JZ, Zhou T, Ma HR. Recovery of valuable metals from mixed types of spent lithium ion batteries. Part II: Selective extraction of lithium. Waste Manage., 2018, 80, 198.

[19] Chen XP, Kang DZ, Cao L, Li JZ, Zhou T, Ma HR. Separation and recovery of valuable metals from spent lithium ion batteries: Simultaneous recovery of Li and Co in a single step. Sep. Purif. Technol., 2019, 210, 690.

[20] Lv WG, Wang ZH, Zheng XH, et al. Selective recovery of lithium from spent lithium-ion batteries by coupling advanced oxidation processes and chemical leaching processes. ACS Sustainable Chem. Eng., 2020, 8(13): 5165.

[21] Guan J, Li YG, Guo YG, et al. Mechanochemical process enhanced cobalt and lithium recycling from wasted lithium-ion batteries. ACS Sustainable Chem. Eng., 2017, 5(1): 1026.

[22] Y.Z. Jiang, X.P. Chen, S.X. Yan, S.Z. Li, and T. Zhou, Pursuing green and efficient process towards recycling of different metals from spent lithium-ion batteries through Ferro-chemistry, Chem. Eng. J., 426(2021), art. No. 131637.

[23] X.P. Chen, D.Z. Kang, J.Z. Li, T. Zhou, and H.R. Ma, Gradient and facile extraction of valuable metals from spent lithium ion batteries for new cathode materials re-fabrication, J. Hazard. Mater., 389(2020), art. No. 121887.

[24] Y.F. Zheng, P.H. Shao, L.M. Yang, et al., Gas exchange-driven carbothermal reduction for simultaneous lithium extraction from anode and cathode scraps, Resour. Conserv. Recycl., 188(2023), art. No. 106696.

[25] Z.M. Yan, A. Sattar, and Z.S. Li, Priority Lithium recovery from spent Li-ion batteries via carbothermal reduction with water leaching, Resour. Conserv. Recycl., 192(2023), art. No. 106937.

[26] N. Wei, Y.Q. He, G.W. Zhang, et al., Recycling of valuable metals from spent lithium-ion batteries by self-supplied reductant roasting, J. Environ. Manage., 329(2023), art. No. 117107.

[27] R. Morina, D. Merli, P. Mustarelli, and C. Ferrara, Lithium and cobalt recovery from lithium-ion battery waste via functional ionic liquid extraction for effective battery recycling, ChemElectroChem, 10(2023), No. 1, art. No. e202201059.

[28] Zhang JL, Hu JT, Zhang WJ, Chen YQ, Wang CY. Efficient and economical recovery of lithium, cobalt, nickel, manganese from cathode scrap of spent lithium-ion batteries. J. Clean. Prod., 2018, 204, 437.

[29] Xiao JF, Li J, Xu ZM. Novel approach for in situ recovery of lithium carbonate from spent lithium ion batteries using vacuum metallurgy. Environ. Sci. Technol., 2017, 51(20): 11960.

[30] X.P. Chen, Y. Wang, S.Z. Li, Y.Z. Jiang, Y. Cao, and X. Ma, Selective recycling of valuable metals from waste LiCoO₂ cathode material of spent lithium-ion batteries through low-temperature thermochemistry, Chem. Eng. J., 434(2022), art. No. 134542.

[31] Zhou FY, Qu X, Wu YX, et al. Vacuum pyrolysis of pine sawdust to recover spent lithium ion batteries: The synergistic effect of carbothermic reduction and pyrolysis gas reduction. ACS Sustainable Chem. Eng., 2022, 10(3): 1287.

[32] Wang WQ, Zhang YC, Liu XG, Xu SM. A simplified process for recovery of Li and co from spent LiCoO₂ cathode using Al foil as the in situ reductant. ACS Sustainable Chem. Eng., 2019, 7(14): 12222.

[33] Xu P, Liu CW, Zhang XH, et al. Synergic mechanisms on carbon and sulfur during the selective recovery of valuable metals from spent lithium-ion batteries. ACS Sustainable Chem. Eng., 2021, 9(5): 2271.

[34] Nuraeni BA, Avarmaa K, Prentice LH, Rankin WJ, Rhamdhani MA. Recovery of cobalt and lithium by carbothermic reduction of LiCoO₂ cathode material: A kinetic study. Metall. Mater. Trans. B, 2023, 54(2): 602.

[35] Wang MM, Liu K, Xu ZB, et al. Selective extraction of critical metals from spent lithium-ion batteries. Environ. Sci. Technol., 2023, 57(9): 3940.

[36] Tang YQ, Xie HW, Zhang BL, 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. Waste Manage., 2019, 97, 140.

[37] S. Park, S. Jung, D. Kwon, M. Beak, E.E. Kwon, and K. Kwon, Carbothermic reduction of spent Lithium-Ion batteries using CO₂ as reaction medium, Chem. Eng. J., 435(2022), art. No. 135165.

[38] Mao JK, Li J, Xu ZM. Coupling reactions and collapsing model in the roasting process of recycling metals from LiCoO₂ batteries. J. Cleaner Prod., 2018, 205, 923.

[39] Li J, Wang GX, Xu ZM. 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. Hazard. Mater., 2016, 302, 97.

[40] Petranikova M, Miškufová A, Havlík T, Forsén O, Pehkonen A. Cobalt recovery from spent portable lithium accumulators after thermal treatment. Acta Metall. Slovaca, 2011, 17(2): 106.

[41] Yang Y, Sun W, Bu YJ, Zhang CY, Song SL, Hu YH. Recovering valuable metals from spent lithium ion battery via a combination of reduction thermal treatment and facile acid leaching. ACS Sustainable Chem. Eng., 2018, 6(8): 10445.

[42] Vieceli N, Casasola R, Lombardo G, Ebin B, Petranikova M. Hydrometallurgical recycling of EV lithium-ion batteries: Effects of incineration on the leaching efficiency of metals using sulfuric acid. Waste Manage., 2021, 125, 192.

[43] R. Hossain, U. Kumar, and V. Sahajwalla, Selective thermal transformation of value added cobalt from spent lithium-ion batteries, J. Cleaner Prod., 293(2021), art. No. 126140.

[44] Lombardo G, Ebin B, Foreman MRSJ, Steenari BM, Petranikova M. Chemical transformations in Li-ion battery electrode materials by carbothermic reduction. ACS Sustainable Chem. Eng., 2019, 7(16): 13668.

[45] Lu YC, Mansour AN, Yabuuchi N, Shao-Horn Y. Probing the origin of enhanced stability of “AlPO₄” nanoparticle coated LiCoO₂ during cycling to high voltages: Combined XRD and XPS studies. Chem. Mater., 2009, 21(19): 4408.

[46] Liu PC, Xiao L, Chen YF, Tang YW, Wu J, Chen H. Recovering valuable metals from LiNi_xCo_y, Mn_1−yO₂ cathode materials of spent lithium ion batteries via a combination of reduction roasting and stepwise leaching. J. Alloys Compd., 2019, 783, 743.

[47] G. Lombardo, B. Ebin, M.R.S.J. Foreman, B.M. Steenari, and M. Petranikova, Incineration of EV lithium-ion batteries as a pretreatment for recycling - Determination of the potential formation of hazardous by-products and effects on metal compounds, J. Hazard Mater., 393(2020), art. No. 122372.

[48] 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.

[49] Lee S, Jin W, Kim SH, et al. Oxygen vacancy diffusion and condensation in lithium-ion battery cathode materials. Angew. Chem. Int. Ed., 2019, 58(31): 10478.

[50] M.L. Wang, C. Liu, H. Shi, T.Y. Long, C.Y. Zhang, and B. Liu, Facile synthesis of chitosan-derived Maillard reaction productions coated CuFeO₂ with abundant oxygen vacancies for higher Fenton-like catalytic performance, Chemosphere, 283(2021), art. No. 131191.

[51] Kim DS, Sohn JS, Lee CK, Lee JH, Han KS, Lee YI. Simultaneous separation and renovation of lithium cobalt oxide from the cathode of spent lithium ion rechargeable batteries. J. Power Sources, 2004, 132(1–2): 145.

[52] B. Makuza, D.W. Yu, Z. Huang, Q.H. Tian, and X.Y. Guo, Dry grinding-carbonated ultrasound-assisted water leaching of carbothermally reduced lithium-ion battery black mass towards enhanced selective extraction of lithium and recovery of high-value metals, Resour. Conserv. Recycl., 174(2021;), art. No. 105784.