Extraction of Nickel Cobalt and Manganese from Spent  NMC Cathodes by Malonic Acid Leaching

A.А. Yelagina; A.A. Starodubtseva; T.V. Kan; S.D. Malik; Y.S. Zhigalenok; F.I. Malchik

doi:10.18321/cpc23(4)513-522

Authors

A.А. Yelagina Al-Farabi Kazakh National University, Al-Farabi ave., 71, Almaty, Kazakhstan
A.A. Starodubtseva Al-Farabi Kazakh National University, Al-Farabi ave., 71, Almaty, Kazakhstan
T.V. Kan Al-Farabi Kazakh National University, Al-Farabi ave., 71, Almaty, Kazakhstan
S.D. Malik Al-Farabi Kazakh National University, Al-Farabi ave., 71, Almaty, Kazakhstan
Y.S. Zhigalenok Al-Farabi Kazakh National University, Al-Farabi ave., 71, Almaty, Kazakhstan
F.I. Malchik Al-Farabi Kazakh National University, Al-Farabi ave., 71, Almaty, Kazakhstan

DOI:

https://doi.org/10.18321/cpc23(4)513-522

Keywords:

spent lithium-ion batteries, NMC cathode material, hydrometallurgy, leaching, malonic acid, recycling, green chemistryplating

Abstract

This study investigates the feasibility of using malonic acid as a standalone leaching agent for the extraction of nickel, cobalt, and manganese from NMC-type cathode mass without the addition of external reducing agents. A systematic optimization of the leaching process parameters, including acid concentration, temperature, solid-to-liquid ratio, and contact time, was performed. It was established that the optimal process conditions are a malonic acid concentration of 2 M, a solid-to-liquid ratio of 20 g/L, a temperature of 60 °C, and a contact time of 80-90 min. Under these parameters, extraction rates of 98% for nickel, 97% for manganese, and 93% for cobalt are achieved. Increasing the temperature above 60 °C leads to efficiency decrease due to thermal decarboxylation of malonic acid. The addition of hydrogen peroxide under optimal conditions does not improve but rather decreases extraction efficiency. The high efficiency is attributed to the dual function of malonic acid, acting simultaneously as an agent for acidic breakdown of the oxide lattice and as a chelating ligand stabilizing metal ions in solution.

References

(1) J.C.-Y. Jung, P.-C. Sui, J. Zhang. A review of recycling spent lithium-ion battery cathode materials using hydrometallurgical treatments, J. Energy Storage, 35 (2021) 102217. Crossref

(2) X. Tang, P. Li, Z. Zhao, et al. Recovery of valuable metals and modification of cathode materials from spent lithium-ion batteries, J. Alloys Compd., 874 (2021) 159853. Crossref

(3) X. Xia, P. Li. A review of the life cycle assessment of electric vehicles: Considering the influence of batteries, Sci. Total Environ., 814 (2022) 152870. Crossref

(4) P. Li, X. Xia, J. Guo. A review of the life cycle carbon footprint of electric vehicle batteries, Sep. Purif. Technol., 296 (2022) 121389. Crossref

(5) S. Zhou, Y. Zhang, Q. Meng, et al. Recycling of LiCoO₂ cathode material from spent lithium ion batteries by ultrasonic enhanced leaching and one-step regeneration, J. Environ. Manage., 277 (2021) 111426. Crossref

(6) J. Lie, J.-C. Liu. Closed-vessel microwave leaching of valuable metals from spent lithium-ion batteries (LIBs) using dual-function leaching agent: Ascorbic acid, Sep. Purif. Technol., 266 (2021) 118458. Crossref

(7) P. Liu, L. Xiao, Y. Chen, et al. Recovering valuable metals from LiNixCoyMn1−x−yO₂ cathode materials of spent lithium ion batteries via a combination of reduction roasting and stepwise leaching, J. Alloys Compd., 783 (2019) 743–752. Crossref

(8) W. Yu, Y. Guo, S. Xu, et al. Comprehensive recycling of lithium-ion batteries: Fundamentals, pretreatment, and perspectives, Energy Storage Mater., 54 (2023) 172–220. Crossref

(9) P.M. Tembo, C. Dyer, V. Subramanian. Lithium-ion battery recycling – a review of the material supply and policy infrastructure, NPG Asia Mater., 16 (2024) 43. Crossref

(10) J. Piątek, S. Afyon, T. M. Budnyak, et al. Sustainable Li-Ion Batteries: Chemistry and Recycling, Adv. Energy Mater., 11 (2021) 2003456. Crossref

(11) R. Sommerville, J. Shaw-Stewart, V. Goodship, et al. A review of physical processes used in the safe recycling of lithium ion batteries, Sustain. Mater. Technol., 25 (2020) e00197. Crossref

(12) E. Fan, L. Li, Z. Wang, et al. Sustainable Recycling Technology for Li-Ion Batteries and Beyond: Challenges and Future Prospects, Chem. Rev., 120 (2020) 7020–7063. Crossref

(13) D. Patil, S. Chikkamath, S. Keny, et al. Rapid dissolution and recovery of Li and Co from spent LiCoO₂ using mild organic acids under microwave irradiation, J. Environ. Manage., 256 (2020) 109935. Crossref

(14) J.-W. Choi, J. Kim, S.-K. Kim, et al. Simple, green organic acid-based hydrometallurgy for waste-to-energy storage devices: Recovery of NiMnCoC₂O₄ as an electrode material for pseudocapacitor from spent LiNiMnCoO₂ batteries, J. Hazard. Mater., 424 (2022) 127481. Crossref

(15) L. Li, E. Fan, Y. Guan, et al. Sustainable Recovery of Cathode Materials from Spent Lithium-Ion Batteries Using Lactic Acid Leaching System, ACS Sustain. Chem. Eng., 5 (2017) 5224–5233. Crossref

(16) X. Chen, C. Luo, J. Zhang, et al. Sustainable Recovery of Metals from Spent Lithium-Ion Batteries: A Green Process, ACS Sustain. Chem. Eng., 3 (2015) 3104–3113. Crossref

(17) J.-S. Sohn, S.-M. Shin, D.-H. Yang, et al. Comparison of Two Acidic Leaching Processes for Selecting the Effective Recycle Process of Spent Lithium ion Battery, Geosystem Eng., 9 (2006) 1–6. Crossref

(18) L.-P. He, S.-Y. Sun, Y.-Y. Mu, et al. Recovery of Lithium, Nickel, Cobalt, and Manganese from Spent Lithium-Ion Batteries Using l-Tartaric Acid as a Leachant, ACS Sustain. Chem. Eng., 5 (2017) 714–721. Crossref

(19) E. Fan, J. Li, L. Li, et al. Leaching Mechanisms of Recycling Valuable Metals from Spent Lithium-Ion Batteries by a Malonic Acid-Based Leaching System, ACS Appl. Energy Mater., 3 (2020) 8532–8542. Crossref

(20) L. Sohbatzadeh, S. Shafaei Tonkaboni, M. Noaparast, et al. A Comparative Study of Malonic and l-Glutamic Acids for Metal Leaching from Spent Lithium-Ion Batteries: Kinetic and Optimization Analysis, Minerals, 13 (2023) 1104. Crossref

(21) P. Li, X. Xue, J. Huang, et al. Optimization of Synergistic Leaching of Valuable Metals from Spent Lithium-Ion Batteries by the Sulfuric Acid–Malonic Acid System Using Response Surface Methodology, ACS Appl. Mater. Interfaces, 14 (2022) 11359–11374. Crossref

(22) K. Davis, G. P. Demopoulos. Hydrometallurgical recycling technologies for NMC Li-ion battery cathodes: current industrial practice and new R&D trends, RSC Sustain., 1 (2023) 1932–1951. Crossref

(23) S. Badre-Eddine, L. Muhr, A. Chagnes. Innovative Integration of Citric Acid Leaching and Electrodialysis for Selective Lithium Recovery from NMC Cathode Material, Metals (Basel)., 15 (2025) 598. Crossref

(24) G. A. Hall. The Kinetics of the Decomposition of Malonic Acid in Aqueous Solution, J. Am. Chem. Soc., 71 (1949) 2691–2693. Crossref

(25) N. Gunawardena, T. Brill. Spectroscopy of Hydrothermal Reactions 15. The pH and Counterion Effects on the Decarboxylation Kinetics of the Malonate System, J. Phys. Chem. A, 105 (2001) 1876–1883. Crossref