Efficient hydrometallurgical recycling of lithium iron-phosphate batteries using acetic acid
DOI:
https://doi.org/10.15407/hftp16.04.463Keywords:
battery recycling, lithium iron phosphate, black mass, acetic acid leaching, hydrometallurgy, environmental friendlinessAbstract
The selectivity of metal extraction from multi-element waste using the hydrometallurgical process is an urgent task. To extract lithium selectively from a waste, the leaching reagent should ideally react only with lithium, while FePO4 and graphite should remain in a solid state. The use of H2O2 allows one to control the degree of oxidation of the solution by oxidizing Fe2+ to Fe3+, followed by light precipitation, thus effectively suppressing iron leaching. The paper presents a method for processing the “black mass”, after mechanical separation from the current collector, using a solution of acetic acid with addition of hydrogen peroxide. In contrast to the above studies, where the object of processing was exclusively the cathode mass of a lithium iron-phosphate battery, our team used "black mass" as a raw material, which is an intermediate product in the processing of LIB, and raw materials in the processes of hydrometallurgical leaching of metals.
The source of the “black mass” in our research was a lithium iron-phosphate battery HWE200A, LF54174200 3.2 V 200Ah (China). The phase composition, morphology, and particle size of the resulting compounds were analyzed by X-ray diffraction and scanning electron microscopy. Quantitative analysis of the concentration of lithium and iron, aluminum, and copper impurities in solutions was performed by Optical Emission Spectroscopy from inductively coupled plasma (ICP-OES) with an ICP spectrometer iCAP 6500 DUO (Thermo Electron Corp.)
Using XRD analysis, the phase composition and crystallographic parameters of the obtained compounds and available impurities were determined. According to the results of research by the proposed method of processing the “black mass” with selective extraction of lithium compounds from spent LFP batteries, the degree of lithium extraction from the “black mass” is achieved by about 98 % with two times treating in the mixture of 0.8 M Hac + 5 wt. % H2O2. The presence of lithium in the form of SEI layer on the surface of the anode material was noted, which accounted for about 14 % of the total amount of lithium in the “black mass”. It is proved that the addition of hydrogen peroxide to a solution of acetic acid promotes the oxidation of Fe2+ to Fe3+in the crystal structure of lithium iron phosphate, which leads to a decrease in the solubility of iron. It was determined that the total amount of impurities (Fe, Al and Cu) in solutions of lithium salts did not exceed 1 %, which was precipitated in the form of corresponding hydroxides. The purity of the obtained Li2CO3, FePO4 compounds and graphite is more than 99.9 wt. %, which meets the battery purity standard and allows them to be used for LiFePO4/C synthesis and reuse in LFP batteries.
References
1. Bank M.S., Swarzenski P.W., Duarte C.M., Rillig M.C., Koelmans A.A., Metian M., Wright S., Provencher J.F., Sanden M., Jordaan A., Wagner M., Thiel M., Ok Y.S., Global Plastic Pollution Observation System to Aid Policy. Environ. Sci. Technol. 2021. 55 (12): 7770. https://doi.org/10.1021/acs.est.1c00818
2. Rogelj J., Geden O., Cowie A., Reisinger A., Net-zero emissions targets are vague: three ways to fix. Nature. 2021. 591(7850): 365. https://doi.org/10.1038/d41586-021-00662-3
3. Rogelj J., den Elzen M., Hohne N., Fransen T., Fekete H., Winkler H., Schaeffer R., Sha F., Riahi K., Meinshausen M., Paris Agreement climate proposals need a boost to keep warming well below 2 degrees C. Nature. 2016. 534(7609): 631-9. https://doi.org/10.1038/nature18307
4. Wang F., Harindintwali J.D., Yuan Z., Wang M., Wang F., Li S., Yin Z., Huang L., Fu Y., Li L., Chang S.X., Zhang L., Rinklebe J., Yuan Z., Zhu Q., Xiang L., Tsang D.C.W., Xu L., Jiang X., Liu J., Wei N., Kastner M., Zou Y., Ok Y.S., Shen J., Peng D., Zhang W., Barcelo D., Zhou Y., Bai Z., Li B., Zhang B., Wei K., Cao H., Tan Z., Zhao L.B., He X., Zheng J., Bolan N., Liu X., Huang C., Dietmann S., Luo M., Sun N., Gong J., Gong Y., Brahushi F., Zhang T., Xiao C., Li X., Chen W., Jiao N., Lehmann J., Zhu Y.G., Jin H., Schaffer A., Tiedje J.M., Chen J.M. Technologies and perspectives for achieving carbon neutrality. Innovation (Camb). 2021. 2(4): 100180. https://doi.org/10.1016/j.xinn.2021.100180
5. Ukraine, Energy Strategy up to 2050. 2022. URL: https://mev.gov.ua/en/reforma/energy-strategy (access date: 16.05.2025).
6. Yang Y., Okonkwo E.G., Huang G., Xu S., Sun W., He Y. On the sustainability of lithium ion battery industry - A review and perspective. Energy Storage Mater. 2021. 36: 186. https://doi.org/10.1016/j.ensm.2020.12.019
7. Fergus J.W. Recent developments in cathode materials for lithium ion batteries. J. Power Sources. 2010. 195(4): 939. https://doi.org/10.1016/j.jpowsour.2009.08.089
8. China Industrial Association of Power Sources: China's top 20 power lithium-ion battery companies in terms of installed capacity in 2020. 2020. URL: https://mev.gov.ua/en/reforma/energy-strategy (access date: 16.05.2025).
9. China Industrial Association of Power Sources: LFP Battery is Returning, driving Chinese LFP Battery Manufacturers going Overseas. 2022. URL: https://isolarparts.com/blogs/nwes2/lfp-battery-is-returning-driving-chinese-lfp-battery-manufacturers-going-overseas; http://www.iccsino.com/news/show-htm-itemid-16446.html (access date: 16.05.2025).
10. Li J., Ma Z.-F. Past and Present of LiFePO4: From Fundamental Research to Industrial Applications. Chem. 2019. 5(1): 3. https://doi.org/10.1016/j.chempr.2018.12.012
11. Liu W., Liu H., Liu W., Cui Z. Life cycle assessment of power batteries used in electric bicycles in China. Renewable Sustainable Energy Rev. 2021. 139: 110596. https://doi.org/10.1016/j.rser.2020.110596
12. Wang W., Wu Y. An overview of recycling and treatment of spent LiFePO4 batteries in China. Resour. Conserv. Recycl. 2017. 127: 233. https://doi.org/10.1016/j.resconrec.2017.08.019
13. Wang M., Liu K., Dutta S., Alessi D.S., Rinklebe J., Ok Y.S., Tsang D.C.W. Recycling of lithium iron phosphate batteries: Status, technologies, challenges, and prospects. Renewable Sustainable Energy Rev. 2022. 163: 112515. https://doi.org/10.1016/j.rser.2022.112515
14. Huang B., Pan Z., Su X., An L. Recycling of lithium-ion batteries: Recent advances and perspectives. J. Power Sources. 2018. 399: 274. https://doi.org/10.1016/j.jpowsour.2018.07.116
15. Vasconcelos D.d.S., Ten?rio J.A.S., Botelho Junior A.B., Espinosa D.C.R. Circular Recycling Strategies for LFP Batteries: A Review Focusing on Hydrometallurgy Sustainable Processing. Metals. 2023. 13(3): 543. https://doi.org/10.3390/met13030543
16. Li H., Xing S., Liu Y., Li F., Guo H., Kuang G. Recovery of Lithium, Iron, and Phosphorus from Spent LiFePO4 Batteries Using Stoichiometric Sulfuric Acid Leaching System. ACS Sustainable Chem. Eng. 2017. 5(9): 8017. https://doi.org/10.1021/acssuschemeng.7b01594
17. Kumar J., Shen X., Li B., Liu H., Zhao J. Selective recovery of Li and FePO4 from spent LiFePO4 cathode scraps by organic acids and the properties of the regenerated LiFePO4. Waste Manage. 2020. 113: 32. https://doi.org/10.1016/j.wasman.2020.05.046
18. Ouaneche T., Stievano L., Rabuel F., Jamali A., Gu?ry C., Monconduit L., Sougrati M.T., Recham N. Revitamize LFP! Ascorbic Acid?Assisted Direct Regeneration of Spent LiFePO4 for Li?Ion Batteries. Batteries Supercaps. 2025. 8(8): e202400765. https://doi.org/10.1002/batt.202400765
19. Bhar M., Ghosh S., Krishnamurthy S., Kaliprasad Y., Martha S.K. A review on spent lithium-ion battery recycling: from collection to black mass recovery. RSC Sustainability. 2023. 1(5): 1150. https://doi.org/10.1039/D3SU00086A
20. Jing Q., Zhang J., Liu Y., Yang C., Ma B., Chen Y., Wang C. E-pH Diagrams for the Li-Fe-P-H2O System from 298 to 473 K: Thermodynamic Analysis and Application to the Wet Chemical Processes of the LiFePO4 Cathode Material. J. Phys. Chem. C. 2019. 123(23): 14207. https://doi.org/10.1021/acs.jpcc.9b02074
21. Yang Y., Meng X., Cao H., Lin X., Liu C., Sun Y., Zhang Y., Sun Z. Selective recovery of lithium from spent lithium iron phosphate batteries: a sustainable process. Green Chemistry. 2018. 20(13): 3121. https://doi.org/10.1039/C7GC03376A
22. Qiu T., Yang J.G., Bai X.J., Wang Y.L. The preparation of synthetic graphite materials with hierarchical pores from lignite by one-step impregnation and their characterization as dye absorbents. RSC Adv. 2019. 9(22): 12737. https://doi.org/10.1039/C9RA00343F
23. Wang Y.-M., Zhang C.-H. Study on Structural Evolution of Synthetic Graphite Derived from Lignite Prepared by High Temperature-High Pressure Method. Crystals. 2022. 12(4): 464. https://doi.org/10.3390/cryst12040464
24. Zhang S., Liu Q., Zhang H., Ma R., Li K., Wu Y., Teppen B.J. Structural order evaluation and structural evolution of coal derived natural graphite during graphitization. Carbon. 2020. 157: 714. https://doi.org/10.1016/j.carbon.2019.10.104
25. Shcherbatiuk I., Potapenko H., Panchenko D., Khomenko V., Patlun D., Halyuk B., Derkach R., Potapenko O., Barsukov V. Characteristics of graphite obtained by recycling lithium - iron phosphate batteries. J. Electrochem. Sci. Eng. 2024. 14(3): 2257. https://doi.org/10.5599/jese.2257
26. Shcherbatiuk I., Bazievskiy A., Panchenko D., Gorobets M., Potapenko O., Vavilon K., Potapenko H., Kirillov S., Zinin V., Dubinevych S., Golub O. Electrochemical Characteristics of LiFePO4, Recovered After Battery Degradation. Ukr. Chem. J. 2023. 88(12): 189. https://doi.org/10.33609/2708-129X.88.12.2022.189-198
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