Hydrothermal method for efficient impurity removal and calcination repair of spent graphite

Abstract Graphite materials occupy an important position in lithium-ion batteries (LIBs), and if spent graphite (SG) can be recycled and reused, the shortage of graphite resources will be alleviated, which is beneficial to the sustainable development of the new energy industry. For the restoration and regeneration process of SG, this study focuses on the application of different removal methods for different metal impurities. Efficient removal of Cu and Li under hydrothermal conditions, efficient removal of Co, Mn and Ni simultaneously under water bath conditions, and finally the effect of different temperature and time on the removal of organic impurities from the surface of SG was investigated. For the above obtained regenerated graphite (RG), it was characterized and analyzed by XRD and SEM. Finally, the graphite was prepared into button cells and tested for its electrochemical properties. The results show that the leaching rates of Cu, Li, Co, Mn and Ni exceed 96% under the suitable conditions. The capacity retention of RG was 97.99% at a current density of 0.1 C. This method achieved the restoration and regeneration of waste graphite.

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	HUA Weiming
	CHEN Xiangping
	JI Shaowen
	LI Futao

Keywords： lithium-ion batteries spent graphite hydrothermal method regenerated graphite electrochemical properties

Received 2023-03-31;

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HUA Weiming, CHEN Xiangping, JI Shaowen, LI Futao.Hydrothermal method for efficient impurity removal and calcination repair of spent graphite[J] Chemcial Industry and Engineering, 2025,V42(2): 97-106

[1] CHENG Q, MARCHETTI B, CHEN X, et al. Separation, purification, regeneration and utilization of graphite recovered from spent lithium-ion batteries-A review[J]. Journal of Environmental Chemical Engineering, 2022, 10(2): 107312
[2] DU K, ANG E H, WU X, et al. Progresses in sustainable recycling technology of spent lithium-ion batteries[J]. Energy & Environmental Materials, 2022, 5(4): 1012-1036
[3] GREY C P, HALL D S. Prospects for lithium-ion batteries and beyond—A 2030 vision[J]. Nature Communications, 2020, 11: 6279
[4] LI N, SU D. In-situ structural characterizations of electrochemical intercalation of graphite compounds[J]. Carbon Energy, 2019, 1(2): 200-218
[5] YAN Z, JIN H, GUO J. Low-temperature synthesis of graphitic carbon-coated silicon anode materials[J]. Carbon Energy, 2019, 1(2): 246-252
[6] CHANDRAN V, GHOSH A, PATIL C K, et al. Comprehensive review on recycling of spent lithium-ion batteries[J]. Materials Today: Proceedings, 2021, 47: 167-180
[7] ZHOU L, YANG D, DU T, et al. The current process for the recycling of spent lithium ion batteries[J]. Frontiers in Chemistry, 2020, 8: 578044
[8] ABDOLLAHIFAR M, DOOSE S, CAVERS H, et al. Graphite recycling from end-of-life lithium-ion batteries: Processes and applications[J]. Advanced Materials Technologies, 2022, 8(2): 2200368
[9] NATARAJAN S, DIVYA M L, ARAVINDAN V. Should we recycle the graphite from spent lithium-ion batteries? The untold story of graphite with the importance of recycling[J]. Journal of Energy Chemistry, 2022, 71: 351-369
[10] NIU B, XIAO J, XU Z. Advances and challenges in anode graphite recycling from spent lithium-ion batteries[J]. Journal of Hazardous Materials, 2022, 439: 129678
[11] ZHU X, XIAO J, MAO Q, et al. A promising regeneration of waste carbon residue from spent Lithium-ion batteries via low-temperature fluorination roasting and water leaching[J]. Chemical Engineering Journal, 2022, 430: 132703
[12] ZHANG Y, ZHANG J, WU L, et al. Extraction of lithium and aluminium from bauxite mine tailings by mixed acid treatment without roasting[J]. Journal of Hazardous Materials, 2021, 404(Pt B): 124044
[13] JIANG Y, CHEN X, YAN S, et al. Pursuing green and efficient process towards recycling of different metals from spent lithium-ion batteries through Ferro-chemistry[J]. Chemical Engineering Journal, 2021, 426: 131637
[14] 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
[15] NATARAJAN S, ARAVINDAN V. An urgent call to spent LIB recycling: Whys and wherefores for graphite recovery[J]. Advanced Energy Materials, 2020, 10(37): 2002238.1-2002238.8
[16] YANG J, FAN E, LIN J, et al. Recovery and reuse of anode graphite from spent lithium-ion batteries via citric acid leaching[J]. ACS Applied Energy Materials, 2021, 4(6): 6261-6268
[17] WU J, ZHENG M, LIU T, et al. Direct recovery: A sustainable recycling technology for spent lithium-ion battery[J]. Energy Storage Materials, 2023, 54: 120-134
[18] YAN C, YUAN H, PARK H S, et al. Perspective on the critical role of interface for advanced batteries[J]. Journal of Energy Chemistry, 2020, 47: 217-220
[19] YU J, LIN M, TAN Q, et al. High-value utilization of graphite electrodes in spent lithium-ion batteries: From 3D waste graphite to 2D graphene oxide[J]. Journal of Hazardous Materials, 2021, 401: 123715
[20] XU Q, WANG Q, CHEN D, et al. Silicon/graphite composite anode with constrained swelling and a stable solid electrolyte interphase enabled by spent graphite[J]. Green Chemistry, 2021, 23(12): 4531-4539
[21] VADIVEL S, TEJANGKURA W, SAWANGPHRUK M. Graphite/graphene composites from the recovered spent Zn/carbon primary cell for the high-performance anode of lithium-ion batteries[J]. ACS Omega, 2020, 5(25): 15240-15246
[22] ZAKI A H, MOTAGALY A T A, KHALED R, et al. Economic and facile approach for synthesis of graphene-titanate nanocomposite for water reclamation[J]. Journal of Contaminant Hydrology, 2022, 250: 104052
[23] CHEN S, LI Z, BELVER C, et al. Comparison of the behavior of ZVI/carbon composites from both commercial origin and from spent Li-ion batteries and mill scale for the removal of ibuprofen in water[J]. Journal of Environmental Management, 2020, 264: 110480
[24] GAO Y, ZHU W, WANG C, et al. Enhancement of oxygen reduction on a newly fabricated cathode and its application in the electro-Fenton process[J]. Electrochimica Acta, 2020, 330: 135206
[25] CAO Z, ZHENG X, CAO H, et al. Efficient reuse of anode scrap from lithium-ion batteries as cathode for pollutant degradation in electro-Fenton process: Role of different recovery processes[J]. Chemical Engineering Journal, 2017, 337: 256-264
[26] ZHANG J, LEI Y, LIN Z, et al. A novel approach to recovery of lithium element and production of holey graphene based on the lithiated graphite of spent lithium ion batteries[J]. Chemical Engineering Journal, 2022, 436: 135011
[27] HE K, ZHANG Z, ZHANG F. Synthesis of graphene and recovery of lithium from lithiated graphite of spent Li-ion battery[J]. Waste Management, 2021, 124: 283-292
[28] MENG Y, LIANG H, ZHAO C, et al. Concurrent recycling chemistry for cathode/anode in spent graphite/LiFePO₄ batteries: Designing a unique cation/anion-co-workable dual-ion battery[J]. Journal of Energy Chemistry, 2022, 64: 166-171
[29] YANG J, ZHAO X, LI W, et al. Advanced cathode for dual-ion batteries: Waste-to-wealth reuse of spent graphite from lithium-ion batteries[J]. eScience, 2022, 2(1): 95-101
[30] YU H, DAI H, ZHU Y, et al. Mechanistic insights into the lattice reconfiguration of the anode graphite recycled from spent high-power lithium-ion batteries[J]. Journal of Power Sources, 2021, 481: 229159
[31] 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
[32] 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
[33] DA H, GAN M, JIANG D, et al. Epitaxial regeneration of spent graphite anode material by an eco-friendly in-depth purification route[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(48): 16192-16202
[34] CHENG Q, YUGE R, NAKAHARA K, et al. KOH etched graphite for fast chargeable lithium-ion batteries[J]. Journal of Power Sources, 2015, 284: 258-263
[35] NSHIZIRUNGU T, AGARWAL A, JO Y T, et al. Chlorinated polyvinyl chloride (CPVC) assisted leaching of lithium and cobalt from spent lithium-ion battery in subcritical water[J]. Journal of Hazardous Materials, 2020, 393: 122367
[36] NSHIZIRUNGU T, RANA M, JO Y T, et al. Rapid leaching and recovery of valuable metals from spent Lithium ion batteries (LIBs) via environmentally benign subcritical nickel-containing water over chlorinated polyvinyl chloride[J]. Journal of Hazardous Materials, 2020, 396(prepublish): 122667
[37] LIU Z, YIN Z, XIONG S, et al. Leaching and kinetic modeling of calcareous bornite in ammonia ammonium sulfate solution with sodium persulfate[J]. Hydrometallurgy, 2014, 144: 86-90
[38] POPESCU I A, VARGA T, EGEDY A, et al. Kinetic models based on analysis of the dissolution of copper, zinc and brass from WEEE in a sodium persulfate environment[J]. Computers & Chemical Engineering, 2015, 83: 214-220
[39] KULOVA TATIANA L, SKUNDIN ALEXANDER M. Electrode/electrolyte interphases of sodium-ion batteries[J]. Energies, 2022, 15(22): 8615
[40] PARIMALAM B S, MACINTOSH A D, KADAM R, et al. Decomposition reactions of anode solid electrolyte interphase (SEI) components with LiPF₆[J]. The Journal of Physical Chemistry C, 2017, 121(41): 22733-22738
[41] KVHN S P, EDSTRÖM K, WINTER M, et al. Face to face at the cathode electrolyte interphase: From interface features to interphase formation and dynamics[J]. Advanced Materials Interfaces, 2022, 9(8): 2102078
[42] LIU W, LIU P, MITLIN D. Review of emerging concepts in SEI analysis and artificial SEI membranes for lithium, sodium, and potassium metal battery anodes[J]. Advanced Energy Materials, 2020, 10(43): 2002297
[43] NATARAJAN S, BORICHA A B, BAJAJ H C. Recovery of value-added products from cathode and anode material of spent lithium-ion batteries[J]. Waste Management, 2018, 77: 455-465
[44] LI J, HE Y, FU Y, et al. Hydrometallurgical enhanced liberation and recovery of anode material from spent lithium-ion batteries[J]. Waste Management, 2021, 126: 517-526