Recycling Cathode-Active Materials from Lithium-Ion Batteries with Supercritical Fluids
Review of Current and Alternative Methods
DOI:
https://doi.org/10.58445/rars.1840Keywords:
recycling, supercritical fluid extraction, cobalt, lithium-ion batteryAbstract
Lithium-ion batteries (LIBs) are widely used in the electric vehicle and smartphone industries, hailed as an alternative to fossil fuels. However, the mining of lithium and cobalt, the most common metals used in LIBs, is associated with miner exploitation and environmental damage. Therefore, an efficient recycling initiative must be implemented in order to ethically continue the production of LIBs.
In this Review, we examine the current industrial recycling procedures (pyrometallurgy and hydrometallurgy) by their yield and externalities. Despite their high recovery rates, we find that both methods are associated with wasteful usage of energy and materials. Then, we analyze a third method of metal recovery involving supercritical fluid (SCF) extraction. The impact of certain additives (hydrogen peroxide, ethanol, polymers) and operating conditions (temperature, pressure, reaction time) are summarized. We find that SCF extraction is effective and practical on a small scale while using moderate amounts of energy and materials. Lastly, we propose future experiments to further optimize the effects of additives and operating conditions of SCF extraction.
References
J. B. Goodenough, M. S. Whittingham, and A. Yoshino, “The Nobel Prize in Chemistry 2019”.
“Milestones in the History of U.S. Foreign Relations - Office of the Historian.” Accessed: Oct. 17, 2024. [Online]. Available: https://history.state.gov/milestones/1969-1976/oil-embargo
J.-M. Tarascon and M. Armand, “Issues and challenges facing rechargeable lithium batteries,” Nature, vol. 414, no. 6861, pp. 359–367, Nov. 2001, doi: 10.1038/35104644.
M. M. Thackeray, W. I. F. David, P. G. Bruce, and J. B. Goodenough, “Lithium insertion into manganese spinels,” Materials Research Bulletin, vol. 18, no. 4, p. 461, 1983.
K. A. Vishnumurthy and K. H. Girish, “A comprehensive review of battery technology for E-mobility,” Journal of the Indian Chemical Society, vol. 98, no. 10, p. 100173, Oct. 2021, doi: 10.1016/j.jics.2021.100173.
“Trends in electric cars – Global EV Outlook 2024 – Analysis - IEA.” Accessed: Oct. 17, 2024. [Online]. Available: https://www.iea.org/reports/global-ev-outlook-2024/trends-in-electric-cars
M. Huang, “Press Center - Global Quarterly Smartphone Production Jumps 12.1% in 4Q23; Annual Total Drops 2.1% Down to 1.166 Billion Units, Says TrendForce | TrendForce - Market research, price trend of DRAM, NAND Flash, LEDs, TFT-LCD and green energy, PV,” TrendForce. Accessed: Oct. 17, 2024. [Online]. Available: https://www.trendforce.com/presscenter/news/20240311-12070.html
B. Diouf and R. Pode, “Potential of lithium-ion batteries in renewable energy,” Renewable Energy, vol. 76, pp. 375–380, Apr. 2015, doi: 10.1016/j.renene.2014.11.058.
A. Väyrynen and J. Salminen, “Lithium ion battery production,” The Journal of Chemical Thermodynamics, vol. 46, pp. 80–85, Mar. 2012, doi: 10.1016/j.jct.2011.09.005.
“Li‐ion batteries: basics, progress, and challenges - Deng - 2015 - Energy Science & Engineering - Wiley Online Library.” Accessed: Oct. 17, 2024. [Online]. Available: https://scijournals.onlinelibrary.wiley.com/doi/full/10.1002/ese3.95
“Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: A comprehensive review - ScienceDirect.” Accessed: Oct. 17, 2024. [Online]. Available: https://www.sciencedirect.com/science/article/pii/S0304386X14002278
“Lithium recovery from brines: A vital raw material for green energies with a potential environmental impact in its mining and processing - ScienceDirect.” Accessed: Oct. 17, 2024. [Online]. Available: https://www.sciencedirect.com/science/article/pii/S0048969718318746
C. Banza Lubaba Nkulu et al., “Sustainability of artisanal mining of cobalt in DR Congo,” Nat Sustain, vol. 1, no. 9, pp. 495–504, Sep. 2018, doi: 10.1038/s41893-018-0139-4.
M. Malpede, “The Dark Side of Batteries: Education and Cobalt Mining in the Democratic Republic of the Congo,” Apr. 16, 2021, Social Science Research Network, Rochester, NY: 3680730. doi: 10.2139/ssrn.3680730.
W. Lv, Z. Wang, H. Cao, Y. Sun, Y. Zhang, and Z. Sun, “A Critical Review and Analysis on the Recycling of Spent Lithium-Ion Batteries,” ACS Sustainable Chem. Eng., vol. 6, no. 2, pp. 1504–1521, Feb. 2018, doi: 10.1021/acssuschemeng.7b03811.
L. Li et al., “Recovery of valuable metals from spent lithium-ion batteries by ultrasonic-assisted leaching process,” Journal of Power Sources, vol. 262, pp. 380–385, Sep. 2014, doi: 10.1016/j.jpowsour.2014.04.013.
Y. Xu et al., “A simple solvent method for the recovery of LixCoO2 and its applications in alkaline rechargeable batteries,” Journal of Power Sources, vol. 252, pp. 286–291, Apr. 2014, doi: 10.1016/j.jpowsour.2013.11.052.
J. Mao, J. Li, and Z. Xu, “Coupling reactions and collapsing model in the roasting process of recycling metals from LiCoO2 batteries,” Journal of Cleaner Production, vol. 205, pp. 923–929, Dec. 2018, doi: 10.1016/j.jclepro.2018.09.098.
“Environmentally-friendly Oxygen-free Roasting/Wet Magnetic Separation Technology for in situ Recycling Cobalt, Lithium Carbonate and Graphite from Spent LiCoO2/graphite Lithium Batteries | Request PDF.” Accessed: Oct. 17, 2024. [Online]. Available: https://www.researchgate.net/publication/282388687_Environmentally-friendly_Oxygen-free_RoastingWet_Magnetic_Separation_Technology_for_in_situ_Recycling_Cobalt_Lithium_Carbonate_and_Graphite_from_Spent_LiCoO2graphite_Lithium_Batteries
G. Ren et al., “Recovery of valuable metals from spent lithium ion batteries by smelting reduction process based on FeO–SiO2–Al2O3 slag system,” Transactions of Nonferrous Metals Society of China, vol. 27, no. 2, pp. 450–456, Feb. 2017, doi: 10.1016/S1003-6326(17)60051-7.
“Recycling of cathode from spent lithium iron phosphate batteries - ScienceDirect.” Accessed: Oct. 17, 2024. [Online]. Available: https://www.sciencedirect.com/science/article/pii/S0304389420310578
“Hydrofluoric Acid: Burns and Systemic Toxicity, Protective Measures, Immediate and Hospital Medical Treatment - PMC.” Accessed: Oct. 17, 2024. [Online]. Available: https://pmc.ncbi.nlm.nih.gov/articles/PMC6290397/
O. US EPA, “Learn about Dioxin.” Accessed: Oct. 17, 2024. [Online]. Available: https://www.epa.gov/dioxin/learn-about-dioxin
“Sulfur Dioxide | Medical Management Guidelines | Toxic Substance Portal | ATSDR.” Accessed: Oct. 17, 2024. [Online]. Available: https://wwwn.cdc.gov/TSP/MMG/MMGDetails.aspx?mmgid=249&toxid=46
D. A. Ferreira, L. M. Z. Prados, D. Majuste, and M. B. Mansur, “Hydrometallurgical separation of aluminium, cobalt, copper and lithium from spent Li-ion batteries,” Journal of Power Sources, vol. 187, no. 1, pp. 238–246, Feb. 2009, doi: 10.1016/j.jpowsour.2008.10.077.
Z. Takacova, T. Havlik, F. Kukurugya, and D. Orac, “Cobalt and lithium recovery from active mass of spent Li-ion batteries: Theoretical and experimental approach,” Hydrometallurgy, vol. 163, pp. 9–17, Aug. 2016, doi: 10.1016/j.hydromet.2016.03.007.
“Analysis of a hydrometallurgical route to recover base metals from spent rechargeable batteries by liquid–liquid extraction with Cyanex 272 - ScienceDirect.” Accessed: Oct. 17, 2024. [Online]. Available: https://www.sciencedirect.com/science/article/pii/S0378775306000437
J. Kang, G. Senanayake, J. Sohn, and S. M. Shin, “Recovery of cobalt sulfate from spent lithium ion batteries by reductive leaching and solvent extraction with Cyanex 272,” Hydrometallurgy, vol. 100, no. 3, pp. 168–171, Jan. 2010, doi: 10.1016/j.hydromet.2009.10.010.
J. Zhao et al., “Hydrometallurgical recovery of spent cobalt-based lithium-ion battery cathodes using ethanol as the reducing agent,” Environmental Research, vol. 181, p. 108803, Feb. 2020, doi: 10.1016/j.envres.2019.108803.
L. Li, J. Ge, F. Wu, R. Chen, S. Chen, and B. Wu, “Recovery of cobalt and lithium from spent lithium ion batteries using organic citric acid as leachant,” Journal of Hazardous Materials, vol. 176, no. 1, pp. 288–293, Apr. 2010, doi: 10.1016/j.jhazmat.2009.11.026.
L. Li, J. Ge, R. Chen, F. Wu, S. Chen, and X. Zhang, “Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries,” Waste Management, vol. 30, no. 12, pp. 2615–2621, Dec. 2010, doi: 10.1016/j.wasman.2010.08.008.
S. Donegan, “Direct solvent extraction of nickel at Bulong operations,” Minerals Engineering, vol. 19, no. 12, pp. 1234–1245, Sep. 2006, doi: 10.1016/j.mineng.2006.03.003.
S. Kurşunoglu, “EXTRACTION OF NICKEL FROM A MIXED NICKEL-COBALT HYDROXIDE PRECIPITATE,” Bilimsel Madencilik Dergisi, pp. 45–52, Mar. 2019, doi: 10.30797/madencilik.537644.
C. Cheng and M. D. Urbani, “The recovery of nickel and cobalt from leach solutions by solvent extraction: Process overview, recent research and development,” Proceedings of ISEC 2005, pp. 503–526, Jan. 2005.
S. Nowak and M. Winter, “The Role of Sub- and Supercritical CO2 as ‘Processing Solvent’ for the Recycling and Sample Preparation of Lithium Ion Battery Electrolytes,” Molecules, vol. 22, no. 3, p. 403, Mar. 2017, doi: 10.3390/molecules22030403.
P. Cattaneo, F. D’Aprile, V. Kapelyushko, P. Mustarelli, and E. Quartarone, “Supercritical CO2 technology for the treatment of end-of-life lithium-ion batteries,” RSC Sustain., vol. 2, no. 6, pp. 1692–1707, Jun. 2024, doi: 10.1039/D4SU00044G.
K. Li and Z. Xu, “A review of current progress of supercritical fluid technologies for e-waste treatment,” Journal of Cleaner Production, vol. 227, pp. 794–809, Aug. 2019, doi: 10.1016/j.jclepro.2019.04.104.
I. De Marco, S. Riemma, and R. Iannone, “Life cycle assessment of supercritical CO2 extraction of caffeine from coffee beans,” The Journal of Supercritical Fluids, vol. 133, pp. 393–400, Mar. 2018, doi: 10.1016/j.supflu.2017.11.005.
G. V. Amaral et al., “Dairy processing using supercritical carbon dioxide technology: Theoretical fundamentals, quality and safety aspects,” Trends in Food Science & Technology, vol. 64, pp. 94–101, Jun. 2017, doi: 10.1016/j.tifs.2017.04.004.
A. A. F. Zielinski, A. del P. Sanchez-Camargo, L. Benvenutti, D. M. Ferro, J. L. Dias, and S. R. S. Ferreira, “High-pressure fluid technologies: Recent approaches to the production of natural pigments for food and pharmaceutical applications,” Trends in Food Science & Technology, vol. 118, pp. 850–869, Dec. 2021, doi: 10.1016/j.tifs.2021.11.008.
“Water under Supercritical Conditions: Hydrogen Bonds, Polarity, and Vibrational Frequency Fluctuations from Ab Initio Simulations with a Dispersion Corrected Density Functional | ACS Omega.” Accessed: Oct. 17, 2024. [Online]. Available: https://pubs.acs.org/doi/10.1021/acsomega.7b02036
S. D. Cramer and B. S. Covino, Eds., “Electrochemical Series,” ASM International, 2005, pp. 665–671. doi: 10.31399/asm.hb.v13b.a0006542.
“Recycling of lithium, cobalt, nickel, and manganese from end-of-life lithium-ion battery of an electric vehicle using supercritical carbon dioxide - ScienceDirect.” Accessed: Oct. 17, 2024. [Online]. Available: https://www.sciencedirect.com/science/article/pii/S092134492200461X
D. A. Bertuol, C. M. Machado, M. L. Silva, C. O. Calgaro, G. L. Dotto, and E. H. Tanabe, “Recovery of cobalt from spent lithium-ion batteries using supercritical carbon dioxide extraction,” Waste Management, vol. 51, pp. 245–251, May 2016, doi: 10.1016/j.wasman.2016.03.009.
“Lithium and cobalt extraction from LiCoO2 assisted by p(VBPDA-co-FDA) copolymers in supercritical CO2 - ScienceDirect.” Accessed: Oct. 17, 2024. [Online]. Available: https://www.sciencedirect.com/science/article/pii/S0956053X24001673
J. Wu et al., “Kinetic Study of Polyvinyl Chloride Pyrolysis with Characterization of Dehydrochlorinated PVC,” ACS Sustainable Chem. Eng., vol. 12, no. 19, pp. 7402–7413, May 2024, doi: 10.1021/acssuschemeng.4c00564.
K. Liu and F.-S. Zhang, “Innovative leaching of cobalt and lithium from spent lithium-ion batteries and simultaneous dechlorination of polyvinyl chloride in subcritical water,” Journal of Hazardous Materials, vol. 316, pp. 19–25, Oct. 2016, doi: 10.1016/j.jhazmat.2016.04.080.
T. V. Barros et al., “Recovery of lithium and cobalt from lithium cobalt oxide and lithium nickel manganese cobalt oxide batteries using supercritical water,” Environmental Pollution, vol. 359, p. 124570, Oct. 2024, doi: 10.1016/j.envpol.2024.124570.
Downloads
Posted
Categories
License
Copyright (c) 2024 Daniel Ren
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.