Targeted regeneration and upcycling of spent graphite by defect-driven tin nucleation

Abstract

The recycling of spent batteries has become increasingly important owing to their wide applications, abundant raw material supply, and sustainable development. Compared with the degraded cathode, spent anode graphite often has a relatively intact structure with few defects after long cycling. Yet, most spent graphite is simply burned or discarded due to its limited value and inferior performance on using conventional recycling methods that are complex, have low efficiency, and fail in performance restoration. Herein, we propose a fast, efficient, and “intelligent” strategy to regenerate and upcycle spent graphite based on defect-driven targeted remediation. Using Sn as a nanoscale healant, we used rapid heating (~50 ms) to enable dynamic Sn droplets to automatically nucleate around the surface defects on the graphite upon cooling owing to strong binding to the defects (~5.84 eV/atom), thus simultaneously achieving Sn dispersion and graphite remediation. As a result, the regenerated graphite showed enhanced capacity and cycle stability (458.9 mAh g^-1 at 0.2 A g^-1 after 100 cycles), superior to those of commercial graphite. Benefiting from the self-adaption of Sn dispersion, spent graphite with different degrees of defects can be regenerated to similar structures and performance. EverBatt analysis indicates that targeted regeneration and upcycling have significantly lower energy consumption (~99% reduction) and near-zero CO₂ emission, and yield much higher profit than hydrometallurgy, which opens a new avenue for direct upcycling of spend graphite in an efficient, green, and profitable manner for sustainable battery manufacture.

Keywords

battery recycling / spent graphite / targeted regeneration / upcycling graphite

References

[1] Goodenough JB. Electrochemical energy storage in a sustainable modern society. Energy Environ Sci. 2014; 7 (1): 14- 18.

[2] Fan E, Li L, Wang Z, et al. Sustainable recycling technology for Li-ion batteries and beyond: challenges and future prospects. Chem Rev. 2020; 120 (14): 7020- 7063.

[3] Ciez RE, Whitacre JF. Examining different recycling processes for lithium-ion batteries. Nat Sustain. 2019; 2 (2): 148- 156.

[4] Zhao Y, Kang Y, Fan M, et al. Precise separation of spent lithium-ion cells in water without discharging for recycling. Energy Storage Mater. 2022; 45: 1092- 1099.

[5] Baars J, Domenech T, Bleischwitz R, Melin HE, Heidrich O. Circular economy strategies for electric vehicle batteries reduce reliance on raw materials. Nat Sustain. 2021; 4 (1): 71- 79.

[6] Abdollahifar M, Doose S, Cavers H, Kwade A. Graphite recycling from end-of-life lithium-ion batteries: processes and applications. Adv Mater Technol. 2023; 8 (2): 2200368.

[7] Wang T, Song Z, Zhang Y, et al. Direct recycling of shorted solid-state electrolytes enabled by targeted recovery. Energy Stor Mater. 2022; 52: 365- 370.

[8] Barbhuiya NH, Kumar A, Singh A, et al. The future of flash graphene for the sustainable management of solid waste. ACS Nano. 2021; 15 (10): 15461- 15470.

[9] Wang J, 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- 776.

[10] Li L, Fan E, Guan Y, et al. Sustainable recovery of cathode materials from spent lithium-ion batteries using lactic acid leaching system. ACS Sustainable Chem Eng. 2017; 5 (6): 5224- 5233.

[11] Natarajan S, Aravindan V. An urgent call to spent LIB recycling: whys and wherefores for graphite recovery. Adv Energy Mater. 2020; 10 (37): 2002238.

[12] Dreimol CH, Guo H, Ritter M, et al. Sustainable wood electronics by iron-catalyzed laser-induced graphitization for large-scale applications. Nat Commun. 2022; 13: 3680.

[13] Saadi MASR, Advincula PA, Thakur MSH, et al. Sustainable valorization of asphaltenes via flash joule heating. Sci Adv. 2022; 8 (46): eadd3555.

[14] Liu J, Shi H, Hu X, et al. Critical strategies for recycling process of graphite from spent lithium-ion batteries: a review. Sci Total Environ. 2021; 816: 151621.

[15] Liu X, Yin L, Ren D, et al. In situ observation of thermaldriven degradation and safety concerns of lithiated graphite anode. Nat Commun. 2021; 12: 4235.

[16] Ding Y, Qiao ZA. Carbon surface chemistry: new insight into the old story. Adv Mater. 2022; 34 (42): 2206025.

[17] Wandt J, Jakes P, Granwehr J, Eichel R-A, Gasteiger HA. Quantitative and time-resolved detection of lithium plating on graphite anodes in lithium ion batteries. Mater Today. 2018; 21 (3): 231- 240.

[18] Yang J, Fan E, Lin J, et al. Recovery and reuse of anode graphite from spent lithium-ion batteries via citric acid leaching. ACS Appl Energy Mater. 2021; 4 (6): 6261- 6268.

[19] Xu C, Ma G, Yang W, et al. One-step reconstruction of acid treated spent graphite for high capacity and fast charging lithium-ion batteries. Electrochim Acta. 2022; 415: 140198.

[20] Zhang Z, Zhu X, Hou H, Tang L, Xiao J, Zhong Q. Regeneration and utilization of graphite from the spent lithium-ion batteries by modified low-temperature sulfuric acid roasting. Waste Manage. 2022; 150: 30- 38.

[21] Alcaraz L, Díaz-Guerra C, Calbet J, López ML, López FA. Obtaining and characterization of highly crystalline recycled graphites from different types of spent batteries. Materials. 2022; 15 (9): 3246.

[22] 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. ACS Sustainable Chem Eng. 2020; 8 (25): 9447- 9455.

[23] Gao Y, Zhang J, Jin H, et al. Regenerating spent graphite from scrapped lithium-ion battery by high-temperature treatment. Carbon. 2022; 189: 493- 502.

[24] Fan E, Lin J, Zhang X, et al. Anode materials sustainable recycling from spent lithium-ion batteries: an edge-selectively nitrogen-repaired graphene nanoplatelets. eTransportation. 2022; 14: 100205.

[25] Dong S, Song Y, Ye K, et al. Ultra-fast, low-cost, and green regeneration of graphite anode using flash joule heating method. EcoMat. 2022; 4 (5): e12212.

[26] Yuwen C, Liu B, Zhang H, et al. Efficient recovery and regeneration of waste graphite through microwave stripping from spent batteries anode for high-performance lithium-ion batteries. J Clean Prod. 2022; 333: 130197.

[27] Fan W, Zhang J, Ma R, Chen Y, Wang C. Regeneration of graphite anode from spent lithium-ion batteries via microwave calcination. J Electroanal Chem. 2022; 908: 116087.

[28] Chen Q, Huang L, Liu J, Luo Y, Chen Y. A new approach to regenerate high-performance graphite from spent lithium-ion batteries. Carbon. 2022; 189: 293- 304.

[29] Kim S, Bang J, Yoo J, et al. A comprehensive review on the pretreatment process in lithium-ion battery recycling. J Clean Prod. 2021; 294: 126329.

[30] Wang C, Liu M, Thijs M, Ooms FGB, Ganapathy S, Wagemaker M. High dielectric barium titanate porous scaffold for efficient Li metal cycling in anode-free cells. Nat Commun. 2021; 12: 6536.

[31] Zhang N, Deng W, Xu Z, Wang X. Upcycling of spent LiCoO₂ cathodes via nickel-and manganese-doping. Carbon Energy. 2023; 5 (1): e231.

[32] Chen W, Salvatierra RV, Li JT, et al. Flash recycling of graphite anodes. Adv Mater. 2023; 35 (8): 2207303.

[33] Yao Y, Huang Z, Hughes LA, et al. Extreme mixing in nanoscale transition metal alloys. Matter. 2021; 4 (7): 2340- 2353.

[34] Yao Y, Huang Z, Xie P, et al. High temperature shockwave stabilized single atoms. Nat Nanotechnol. 2019; 14 (9): 851- 857.

[35] Yao Y, Huang Z, Xie P, et al. Carbothermal shock synthesis of high-entropy-alloy nanoparticles. Science. 2018; 359 (6383): 1489- 1494.

[36] Xing Z, Gao N, Qi Y, Ji X, Liu H. Influence of enhanced carbon crystallinity of nanoporous graphite on the cathode performance of microbial fuel cells. Carbon. 2017; 115: 271- 278.

[37] Bychko I, Abakumov A, Didenko O, Chen M, Tang J, Strizhak P. Differences in the structure and functionalities of graphene oxide and reduced graphene oxide obtained from graphite with various degrees of graphitization. J Phys Chem Solids. 2022; 164: 110614.

[38] Wang X, Chen J, Dong C, Wang D, Mao Z. Hard carbon derived from graphite anode by mechanochemistry and the enhanced lithium-ion storage performance. ChemElectroChem. 2022; 9 (5): e202101613.

[39] Or T, Gourley SWD, Kaliyappan K, Yu A, Chen Z. Recycling of mixed cathode lithium-ion batteries for electric vehicles: current status and future outlook. Carbon Energy. 2020; 2 (1): 6- 43.

[40] Yi C, Ge P, Wu X, Sun W, Yang Y. Tailoring carbon chains for repairing graphite from spent lithium-ion battery toward closed-circuit recycling. J Energy Chem. 2022; 72: 97- 107.

[41] Liu B, Huang P, Liu M, Xie Z. Utilization of impurities and carbon defects in natural microcrystalline graphite to prepare silicon-graphite composite anode for highperformance lithium-ion batteries. J Mater Sci. 2021; 56 (31): 17682- 17693.

[42] Yao Y, Huang Z, Li T, et al. High-throughput, combinatorial synthesis of multimetallic nanoclusters. Proc Natl Acad Sci U S A. 2020; 117 (12): 6316- 6322.

[43] Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett. 1996; 77 (18): 3865- 3868.

[44] Segall MD, Lindan PJD, Probert MJ, et al. First-principles simulation: ideas, illustrations and the CASTEP code. J Phys Condens Matter. 2002; 14 (11): 2717- 2744.

[45] Banhart F, Kotakoski J, Krasheninnikov AV. Structural defects in graphene. ACS Nano. 2011; 5 (1): 26- 41.

[46] Gao W, Mueller JE, Anton J, Jiang Q, Jacob T. Nickel cluster growth on defect sites of graphene: a computational study. Angew Chem Int Ed. 2013; 52 (52): 14237- 14241.

[47] Han Y-C, Liu M-L, Sun L, et al. A general strategy for overcoming the trade-off between ultrasmall size and high loading of MOF-derived metal nanoparticles by millisecond pyrolysis. Nano Energy. 2022; 97: 107125.

[48] Ying H, Han W-Q. Metallic Sn-based anode materials: application in high-performance lithium-ion and sodium-ion batteries. Adv Sci. 2017; 4 (11): 1700298.

[49] Yu L, Zeng K, Li C, et al. High-entropy alloy catalysts: from bulk to nano toward highly efficient carbon and nitrogen catalysis. Carbon Energy. 2022; 4 (5): 731- 761.

[50] Cheng Y, Huang J, Qi H, et al. Controlling the Sn-C bonds content in SnO₂@ CNTs composite to form in situ pulverized structure for enhanced electrochemical kinetics. Nanoscale. 2017; 9 (47): 18681- 18689.

[51] Liang S, Cheng Y-J, Zhu J, Xia Y, Müller-Buschbaum P. A chronicle review of nonsilicon (Sn, Sb, Ge)-based lithium/sodium-ion battery alloying anodes. Small Methods. 2020; 4 (8): 2000218.

[52] Li W, Sun X, Yu Y. Si-, Ge-, Sn-based anode materials for lithium-ion batteries: from structure design to electrochemical performance. Small Methods. 2017; 1 (3): 1600037.

[53] Luo J, Zhang J, Guo Z, et al. Recycle spent graphite to defectengineered, high-power graphite anode. Nano Res. 2023; 16 (4): 4240- 4245.

[54] Khosla N, Narayan J, Narayan R, Sun X-G, Paranthaman MP. Microstructure and defect engineering of graphite anodes by pulsed laser annealing for enhanced performance of lithiumion batteries. Carbon. 2023; 205: 214- 225.

[55] Zhang Y, Tao L, Xie C, et al. Defect engineering on electrode materials for rechargeable batteries. Adv Mater. 2020; 32 (7): 1905923.

[56] Zheng F, Yang Y, Chen Q. High lithium anodic performance of highly nitrogen-doped porous carbon prepared from a metal-organic framework. Nat Commun. 2014; 5: 5261.

[57] Dong J, Xue Y, Zhang C, et al. Improved Li⁺ storage through homogeneous N-doping within highly branched tubular graphitic foam. Adv Mater. 2017; 29 (6): 1603692.

[58] Kim J, Nithya Jeghan SM, Lee G. Superior fast-charging capability of graphite anode via facile surface treatment for lithium-ion batteries. Microporous Mesoporous Mater. 2020; 305: 110325.

[59] Wang C, Li Y, Chui Y-S, Wu Q-H, Chen X, Zhang W. Three-dimensional Sn-graphene anode for highperformance lithium-ion batteries. Nanoscale. 2013; 5 (21): 10599- 10604.

[60] Wang M, Wang J, Xiao J, et al. Introducing a pseudocapacitive lithium storage mechanism into graphite by defect engineering for fast-charging lithium-ion batteries. ACS Appl Mater Interfaces. 2022; 14 (14): 16279- 16288.

[61] Han M, Liu G, Jiang J, et al. Realizing spherical lithium deposition by in situ formation of a Li₂S/Li-Sn alloy mixed layer on carbon paper for stable and safe Li metal anodes. ACS Appl Mater Interfaces. 2021; 13 (41): 48828- 48837.

[62] Lu J, Liu S, Liu J, et al. Millisecond conversion of photovoltaic silicon waste to binder-free high silicon content nanowires electrodes. Adv Energy Mater. 2021; 11 (40): 2102103.

[63] Zhao L-F, Hu Z, Lai W-H, et al. Hard carbon anodes: fundamental understanding and commercial perspectives for Na-Ion batteries beyond Li-ion and K-ion counterparts. Adv Energy Mater. 2021; 11 (1): 2002704.

[64] Liu Y, Xue JS, Zheng T, Dahn JR. Mechanism of lithium insertion in hard carbons prepared by pyrolysis of epoxy resins. Carbon. 1996; 34 (2): 193- 200.

[65] Qin J, He C, Zhao N, et al. Graphene networks anchored with Sn@ graphene as lithium ion battery anode. ACS Nano. 2014; 8 (2): 1728- 1738.

[66] Derrien G, Hassoun J, Panero S, Scrosati B. Nanostructured Sn-C composite as an advanced anode material in high-performance lithium-ion batteries. Adv Mater. 2007; 19 (17): 2336- 2340.

[67] Qing J, Lekakh S, Xu M, Field D. Formation of complex nuclei in graphite nodules of cast iron. Carbon. 2021; 171: 276- 288.

[68] Zhang H, Ji Y, Yao Y, et al. Transient and dry recycling of battery materials with negligible carbon footprint and roll-toroll scalability. Energy Environ Sci. 2023; 16 (6): 2561- 2571.

[69] Wang J, Ma J, Jia K, et al. Efficient extraction of lithium from anode for direct regeneration of cathode materials of spent Li-ion batteries. ACS Energy Lett. 2022; 7 (8): 2816- 2824.

[70] Lu J, Zhao Y, Kang Y, et al. Surplus energy utilization of spent lithium-ion batteries for high-profit organolithiums. Carbon Energy. 2023; 5 (6): 1- 10.

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

[72] Thompson DL, Hartley JM, Lambert SM, et al. The importance of design in lithium ion battery recycling—a critical review. Green Chem. 2020; 22 (22): 7585- 7603.

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