Study of Copper Separation from Ternary Black Powder Leaching Solution Using P204 (D2EHPA) Multistage-Extraction

Abstract:

Nickel and cobalt recovered from ternary leaching solutions have high market value and stability. In addition to preventing environmental damage, this recovery process is also very useful in the application of power energy storage and electric vehicles. Solvent extraction is an effective and selective method for separating elements in ternary leaching solutions. This research focuses on the separation stage of feed solution impurities, especially Cu, by optimizing the extraction process using multi-stage extraction. This method, which is adapted to a laboratory scale, mixes the feed solution with saponified P204 (prepared with NaOH) and then stirred until phase separation into a loaded organic phase and raffinate occurs. The use of P204 with 3-stage extractions with O/A= 1.5/1 and pH= 4.5 succeeded in separating 99.96% extraction of Cu with a primary yield of Cu value of 99.999%. This solvent extraction also successfully separated 99.23% of Mn, Ca=95.62%, and other impurity metals such as Fe, Zn, Li, and Si reaching a final concentration in the raffinate solution of only 10^-3 g/L. The results of this research are very useful in the subsequent extraction process in the form of separating the valuable elements nickel and cobalt. This method can potentially overcome environmental problems resulting from the disposal of NCM battery waste in the metallurgical field.

• Periodical: Key Engineering Materials (Volume 1014)
• Pages: 69-76
• DOI: https://doi.org/10.4028/p-qY0TYS
• Online since: June 2025
• Authors: E Dian Ta Jaya*, Sheng Xi Wu, Yu Hua Li, Dun Pei Wei, Ya Qian Zhu
• Keywords: Environment, Metallurgy, Multistage Extraction, NCM, P204, Solvent Extraction

References

[1] T. Zhang et al., "Efficient leaching of valuable metals from NCM cathode materials by green deep eutectic solvent," J Clean Prod, vol. 438, p.140636, Jan. 2024.

DOI: 10.1016/J.JCLEPRO.2024.140636

[2] J. Qing et al., "Novel approach to recycling of valuable metals from spent lithium-ion batteries using hydrometallurgy, focused on preferential extraction of lithium," J Clean Prod, vol. 431, p.139645, Dec. 2023.

DOI: 10.1016/J.JCLEPRO.2023.139645

[3] J. Patel, R. Patel, R. Saxena, and A. Nair, "Thermal analysis of high specific energy NCM-21700 Li-ion battery cell under hybrid battery thermal management system for EV applications," J Energy Storage, vol. 88, p.111567, May 2024.

DOI: 10.1016/J.EST.2024.111567

[4] K. Mao et al., "Fracture mechanisms of NCM polycrystalline particles in lithium-ion batteries: A review," J Energy Storage, vol. 84, p.110807, Apr. 2024.

DOI: 10.1016/J.EST.2024.110807

[5] P. Jenis et al., "Recent progress and hurdles in cathode recycling for Li-ion batteries," Circular Economy, vol. 3, no. 2, p.100087, Jun. 2024.

DOI: 10.1016/J.CEC.2024.100087

[6] X. He, Y. Wen, X. Wang, Y. Cui, L. Li, and H. Ma, "Leaching NCM cathode materials of spent lithium-ion batteries with phosphate acid-based deep eutectic solvent," Waste Management, vol. 157, p.8–16, Feb. 2023.

DOI: 10.1016/J.WASMAN.2022.11.044

[7] Q. Cheng, Z. Wang, Y. Wang, J. T. Li, and H. Fu, "Recent advances in preferentially selective Li recovery from spent lithium-ion batteries: A review," J Environ Chem Eng, vol. 12, no. 3, p.112903, Jun. 2024.

DOI: 10.1016/J.JECE.2024.112903

[8] L. Dong, Y. Li, P. Shi, Z. Ren, and Z. Zhou, "Low-viscosity acidic deep eutectic solvent for extraction of valuable metals from spent NCM," J Power Sources, vol. 582, p.233564, Oct. 2023.

DOI: 10.1016/J.JPOWSOUR.2023.233564

[9] J. Wu et al., "Recent advancements in hydrometallurgical recycling technologies of spent lithium-ion battery cathode materials," Rare Metals 2023 43:3, vol. 43, no. 3, p.879–899, Dec. 2023.

DOI: 10.1007/S12598-023-02437-3

[10] W. S. Chen and H. J. Ho, "Recovery of Valuable Metals from Lithium-Ion Batteries NMC Cathode Waste Materials by Hydrometallurgical Methods," Metals 2018, Vol. 8, Page 321, vol. 8, no. 5, p.321, May 2018.

DOI: 10.3390/MET8050321

[11] S. Yang et al., "New strategy of electrochemical precipitation to metals separation in spent NCM cathode materials for direct regeneration," Electrochim Acta, vol. 431, p.141144, Nov. 2022.

DOI: 10.1016/J.ELECTACTA.2022.141144

[12] J. Cheng, C. Zheng, K. Xu, Y. Zhu, Y. Song, and C. Jing, "Sequential separation of critical metals from lithium-ion batteries based on deep eutectic solvent and electrodeposition," J Hazard Mater, vol. 465, p.133157, Mar. 2024.

DOI: 10.1016/J.JHAZMAT.2023.133157

[13] Z. Chi et al., "Direct regeneration method of spent LiNi1/3Co1/3Mn1/3O2 cathode materials via surface lithium residues," Green Chemistry, vol. 23, no. 22, p.9099–9108, Nov. 2021.

DOI: 10.1039/D1GC03526F

[14] R. Sepúlveda et al., "Solvent Extraction of Metal Ions from Synthetic Copper Leaching Solution Using R4NCy," Metals 2022, Vol. 12, Page 1053, vol. 12, no. 6, p.1053, Jun. 2022.

DOI: 10.3390/MET12061053

[15] D. Darvishi, D. F. Haghshenas, E. K. Alamdari, S. K. Sadrnezhaad, and M. Halali, "Synergistic effect of Cyanex 272 and Cyanex 302 on separation of cobalt and nickel by D2EHPA," Hydrometallurgy, vol. 77, no. 3–4, p.227–238, Jun. 2005.

DOI: 10.1016/J.HYDROMET.2005.02.002

[16] N. Peeters, K. Binnemans, and S. Riaño, "Recovery of cobalt from lithium-ion battery cathode material by combining solvoleaching and solvent extraction," Green Chemistry, vol. 24, no. 7, p.2839–2852, Apr. 2022.

DOI: 10.1039/D1GC03776E

[17] P. Meshram, S. Virolainen, Abhilash, and T. Sainio, "Solvent Extraction for Separation of 99.9% Pure Cobalt and Recovery of Li, Ni, Fe, Cu, Al from Spent LIBs," Metals (Basel), vol. 12, no. 6, p.1056, Jun. 2022.

DOI: 10.3390/met12061056

[18] T. Liu, J. Chen, H. Li, and K. Li, "An integrated process for the separation and recovery of valuable metals from the spent LiNi0.5Co0.2Mn0.3O2 cathode materials," Sep Purif Technol, vol. 245, p.116869, Aug. 2020.

DOI: 10.1016/J.SEPPUR.2020.116869

[19] S. H. Joo, D. J. Shin, C. H. Oh, J. P. Wang, G. Senanayake, and S. M. Shin, "Selective extraction and separation of nickel from cobalt, manganese and lithium in pre-treated leach liquors of ternary cathode material of spent lithium-ion batteries using synergism caused by Versatic 10 acid and LIX 84-I," Hydrometallurgy, vol. 159, p.65–74, Jan. 2016.

DOI: 10.1016/J.HYDROMET.2015.10.012

[20] D. yan Liu, S. neng Sun, and D. yang Li, "A feasible process for recycling valuable metals from LiNi0.5Co0.2Mn0.3O2 cathode materials of spent Li-ion batteries," Environ Technol, vol. 45, no. 16, p.3189–3201, Jul. 2024.

DOI: 10.1080/09593330.2023.2212845

[21] C. Li et al., "Separation and recovery of nickel cobalt manganese lithium from waste ternary lithium-ion batteries," Sep Purif Technol, vol. 306, p.122559, Feb. 2023.

DOI: 10.1016/J.SEPPUR.2022.122559

[22] Y. Yang, S. Xu, and Y. He, "Lithium recycling and cathode material regeneration from acid leach liquor of spent lithium-ion battery via facile co-extraction and co-precipitation processes," Waste Management, vol. 64, p.219–227, Jun. 2017.

DOI: 10.1016/J.WASMAN.2017.03.018

[23] L. Shuya, C. Yang, C. Xuefeng, S. Wei, W. Yaqing, and Y. Yue, "Separation of lithium and transition metals from leachate of spent lithium-ion batteries by solvent extraction method with Versatic 10," Sep Purif Technol, vol. 250, p.117258, Nov. 2020.

DOI: 10.1016/J.SEPPUR.2020.117258

[24] X. Jing, Z. Sun, D. Zhao, X. Tang, W. Lv, and Y. Shi, "Co-extraction of Mn2+, Co2+, and a part of Ni2+ from sulfuric acid solution containing Li+ using the new ionic liquids," J Mol Liq, vol. 363, p.119842, Oct. 2022.

DOI: 10.1016/J.MOLLIQ.2022.119842

[25] K. Zhang, H. Liang, X. Zhong, H. Cao, R. Wang, and Z. Liu, "Recovery of metals from sulfate leach solutions of spent ternary lithium-ion batteries by precipitation with phosphate and solvent extraction with P507," Hydrometallurgy, vol. 210, p.105861, Apr. 2022.

DOI: 10.1016/J.HYDROMET.2022.105861

[26] P. K. Choubey, O. S. Dinkar, R. Panda, A. Kumari, M. K. Jha, and D. D. Pathak, "Selective extraction and separation of Li, Co and Mn from leach liquor of discarded lithium ion batteries (LIBs)," Waste Management, vol. 121, p.452–457, Feb. 2021.

DOI: 10.1016/J.WASMAN.2020.10.002

[27] J. Zhang, B. Zhao, and B. Schreiner, "Separation hydrometallurgy of rare earth elements," Separation Hydrometallurgy of Rare Earth Elements, p.1–259, Feb. 2016.

DOI: 10.1007/978-3-319-28235-0_6