Preparation of low-expansion high-performance Si–C composites based on porous advantage of detoxified and purified waste cathode graphite blocks

Abstract

Waste graphitization cathode carbon blocks are a type of hazardous solid waste generated during the aluminum electrolysis process, and their proper disposal is a key step in the resource utilization of discarded graphite. This study utilizes the porous “defect advantage” of a cathode carbon block matrix to prepare silicon-doped and asphalt-coated detoxified and purified waste graphitization cathode carbon blocks for use as high-performance silicon/carbon composite anode materials. The results show that the uniformly silicon-doped silicon/carbon composite material features a unique amorphous carbon-encapsulated “locked silicon” structure, which effectively addresses issues such as cathode volume expansion, excessive growth of the solid electrolyte interphase (SEI) film, and poor electrical contact between active materials. Consequently, electrochemical performance is enhanced. After assembly in a half-cell, the PSCC/10%Si@C (purified waste graphitization cathode carbon/10%Si@C) material exhibits optimal electrochemical stability, with an initial charging specific capacity of 514.5 mAh/g at 0.1 C (1 C = 170 mA/g) and a capacity retention rate of 95.1% after 100 cycles. At a charge rate of 2.0 C, a specific capacity of 216.9 mAh/g is achieved. This technology provides a new pathway for the economical and high-value utilization of waste cathode carbon blocks and the development of low-cost, high-performance anode materials.

Keywords

waste graphitization cathode carbon blocks / defect advantage / silicon/carbon anode materials / hazardous waste resource utilization

References

[1] Yurkov AA. Refractories and carbon cathode materials for the aluminum industry. Refract. Ind. Ceram., 2006, 473139

[2] Ma LT, Qiu ZS, Tang YSet al.. The recycling of carbon-rich solid wastes from aluminum electrolytic cells: A review. Environ. Chem. Lett., 2024, 2252531

[3] L.M. Dong, F. Jiao, W. Liu, S.Y. Gu, C. Wang, and W.Q. Qin, Harmless recovery and utilization of electrolytic aluminum spent cathode carbon block: A comprehensive review, J. Cleaner Prod., 429(2023), art. No. 139326.

[4] Xiao J, Yuan J, Tian ZLet al.. Comparison of ultrasound-assisted and traditional caustic leaching of spent cathode carbon (SCC) from aluminum electrolysis. Ultrason. Sonochem., 2018, 40: 21

[5] Cai WC, Xia HY, Zhang Q, Jiang GY, Xu YJ. Defluorination of waste cathodic carbon through steam under conventional high-temperature roasting. JOM, 2023, 752400

[6] Zhang X, Xu L, Ren YY, Xie C, Wei Q, Shu JJ. Graphitization transformation of aluminum electrolytic spent carbon cathode. Ceram. Int., 2024, 501832118

[7] F.N. Han, L. Yu, X.Y. Mo, et al., Measurement and control of containing-fluorine particulate matter emission during spent pot lining combustion detoxification process, J. Hazard. Mater., 447(2023), art. No. 130748.

[8] Dzikunu P, Arthur EK, Gikunoo E, Bleppony E, Agyemang FO, Mensah-Darkwa K. Successive selective leaching procedures for valorization of spent pot lining carbon. Process. Saf. Environ. Prot., 2023, 169: 1

[9] H.S. Li, J.R. Wang, W.Y. Hou, et al., The study of carbon recovery from electrolysis aluminum carbon dust by froth flotation, Metals, 11(2021), No. 1, art. No. 145.

[10] Y.F. Wang, X.P. Chen, S.J. Zhang, and P.X. Yang, Recycling of spent pot lining first cut from aluminum smelters by utilizing the two-step decomposition characteristics of dolomite, Materials, 13(2020), No. 22, art. No. 5283.

[11] J. Yuan, H.J. Li, and S. Ding, Leaching kinetics of aluminum from alkali-fused spent cathode carbon using hydrochloric acid and sodium fluoride, Processes, 10(2022), No. 5, art. No. 849.

[12] Robshaw TJ, Bonser K, Coxhill G, Dawson R, Ogden MD. Development of a combined leaching and ion-exchange system for valorisation of spent potlining waste. Waste Biomass Valorization, 2020, 11105467

[13] J. Yuan, J. Xiao, Z.L. Tian, et al., Optimization of purification treatment of spent cathode carbon from aluminum electrolysis using response surface methodology (RSM), Asia Pac. J. Chem. Eng., 13(2018), No. 1, art. No. e2164.

[14] Li H, Wu XF, Jiang LBet al.. Progress in study on the incineration technology of municipal sewage sludge. Environ. Eng., 2014, 32688

[15] Q.P. Zhao, Y.R. Wang, H. Dong, et al., Preparation of anode materials for lithium-ion batteries by spent carbon anode from electrolytic aluminum, J. Environ. Chem. Eng., 9(2021), No. 5, art. No. 105932.

[16] Yang K, Zhao ZJ, Xin X, Tian ZL, Peng K, Lai YQ. Graphitic carbon materials extracted from spent carbon cathode of aluminium reduction cell as anodes for lithium ion batteries: Converting the hazardous wastes into value-added materials. J. Taiwan Inst. Chem. Eng., 2019, 104: 201

[17] K. Yang, P.Y. Gong, Z.L. Tian, K. Peng, and Y.Q. Lai, Carbon recovered from spent carbon cathode of aluminum reduction cell towards its valorisation as negative electrodes for lithium ion batteries, Diamond Relat. Mater., 109(2020), art. No. 108062.

[18] Wu YS, Wang YH, Lee YH. Performance enhancement of spherical natural graphite by phenol resin in lithium ion batteries. J. Alloy. Compd., 2006, 4261–2218

[19] Wang XY, Wen ZY, Lin B, Lin J, Wu XW, Xu XG. Preparation and electrochemical characterization of tin/graphite/silver composite as anode materials for lithium-ion batteries. J. Power Sources, 2008, 1842508

[20] Wang YK, Yang LC, Hu RZ, Ouyang LZ, Zhu M. Facile synthesis of Fe₂O₃–graphite composite with stable electrochemical performance as anode material for lithium ion batteries. Electrochim. Acta, 2014, 125: 421

[21] Zhang D, Zhang CY, Zheng Xet al.. Facile synthesis of the Mn₃O₄ polyhedron grown on N-doped honeycomb carbon as high-performance negative material for lithium-ion batteries. Int. J. Miner. Metall. Mater., 2023, 3061152

[22] Gallego NC, Contescu CI, Meyer HMet al.. Advanced surface and microstructural characterization of natural graphite anodes for lithium ion batteries. Carbon, 2014, 72: 393

[23] Abdelkader-Fernández VK, Morales-Lara F, Melguizo M, García-Gallarín Cet al.. Degree of functionalization and stability of fluorine groups fixed to carbon nanotubes and graphite nanoplates by CF₄ microwave plasma. Appl. Surf. Sci., 2015, 357: 1410

[24] Cheng Q, Zhang Y. Multi-channel graphite for high-rate lithium ion battery. J. Electrochem. Soc., 2018, 1655A1104

[25] Mundszinger M, Farsi S, Rapp M, Golla-Schindler U, Kaiser U, Wachtler M. Morphology and texture of spheroidized natural and synthetic graphites. Carbon, 2017, 111: 764

[26] Pei ZZ, Li ZG, Zheng XL. Porous materials for lithiumion batteries. J. Nanosci. Nanotechnol., 2016, 1699028

[27] Li M, Hou XH, Sha YJet al.. Facile spray-drying/pyrolysis synthesis of core–shell structure graphite/silicon-porous carbon composite as a superior anode for Li-ion batteries. J. Power Sources, 2014, 248: 721

[28] Wang B, Li XL, Zhang XF, Luo B, Zhang YB, Zhi LJ. Contact-engineered and void-involved silicon/carbon nanohybrids as lithium-ion-battery anodes. Adv. Mater., 2013, 25263560

[29] M. Ko, S. Chae, J. Ma, et al., Scalable synthesis of silicon-nano-layer-embedded graphite for high-energy lithium-ion batteries, Nat. Energy, 1(2016), art. No. 16113.

[30] Zheng ZH, Xie MZ, Yu GQet al.. Preparation of lithiumion battery anode materials from graphitized spent carbon cathode derived from aluminum electrolysis. Int. J. Miner. Metall. Mater., 2024, 31112466

[31] Zhuang XY, Zhang Y, He LXet al.. Strategy to form homogeneously macroporous Si as enhanced anode material of Li-ion batteries. J. Alloy. Compd., 2018, 731: 1

[32] Yu J, Wei YB, Meng BCet al.. Homogeneous distributed natural pyrite-derived composite induced by modified graphite as high-performance lithium-ion batteries anode. Int. J. Miner. Metall. Mater., 2023, 3071353

[33] G.Q. Yu, M.Z. Xie, Z.H. Zheng, Z.G. Wu, H.L. Zhao, and F.Q. Liu, Efficiently regenerating spent lithium battery graphite anode materials through heat treatment processes for impurity dissipation and crystal structure repair, Resour. Conserv. Recycl., 199(2023), art. No. 107267.

[34] Sourice J, Bordes A, Boulineau Aet al.. Core–shell amorphous silicon–carbon nanoparticles for high performance anodes in lithium ion batteries. J. Power Sources, 2016, 328: 527

[35] D.S. Ruan, L. Wu, F.M. Wang, et al., A low-cost silicon–graphite anode made from recycled graphite of spent lithium-ion batteries, J. Electroanal. Chem., 884(2021), art. No. 115073.

[36] Xu Q, Wang QW, Chen DQet al.. Silicon/graphite composite anode with constrained swelling and a stable solid electrolyte interphase enabled by spent graphite. Green Chem., 2021, 23124531

[37] Tian HJ, Tan XJ, Xin FX, Wang CS, Han WQ. Micro-sized nano-porous Si/C anodes for lithium ion batteries. Nano Energy, 2015, 11: 490

[38] Wong DP, Tseng HP, Chen YT, Hwang BJ, Chen LC, Chen KH. A stable silicon/graphene composite using solvent exchange method as anode material for lithium ion batteries. Carbon, 2013, 63: 397

[39] Yao Y, Liu N, McDowell MT, Pasta M, Cui Y. Improving the cycling stability of silicon nanowire anodes with conducting polymer coatings. Energy Environ. Sci., 2012, 577927

[40] Lu ZH, Shen J, Zhang Xet al.. From waste to wealth: Coal tar residue derived carbon materials as low-cost anodes for potassium-ion batteries. Int. J. Miner. Metall. Mater., 2025, 322464

[41] C.F. Xu, T.T. Xia, C. Wang, et al, Stable and fast Si–M–C ternary anodes enabled by interfacial engineering, J. Power Sources, 530(2022), art. No. 231290.

[42] Zhang A, Fang Z, Tang Y, Zhou Y, Wu P, Yu GH. Inorganic gel-derived metallic frameworks enabling high-performance silicon anodes. Nano Lett., 2019, 1996292

[43] Tang JL, Dysart AD, Kim DH, Saraswat R, Shaver GM, Pol VG. Fabrication of carbon/silicon composite as lithium-ion anode with enhanced cycling stability. Electrochim. Acta, 2017, 247: 626

[44] Y. Gao, J.L. Zhang, Y.Q. Chen, and C.Y. Wang, High value-added regeneration of anode materials from retired lithium-ion batteries: Structural design and synthesis process, Fuel Process. Technol., 250(2023), art. No. 107909.

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