Efficient extraction of metals from industrially produced pyrolytic black powder using citric acid: Process optimization and leaching mechanism

Shen-ao Zhang , Yong-wei Wang , Yu-e Tan , Li-jue Wang , Jun-wei Han

Journal of Central South University ›› 2025, Vol. 32 ›› Issue (9) : 3591 -3609.

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Journal of Central South University ›› 2025, Vol. 32 ›› Issue (9) :3591 -3609. DOI: 10.1007/s11771-025-6006-3
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Efficient extraction of metals from industrially produced pyrolytic black powder using citric acid: Process optimization and leaching mechanism

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Abstract

Full-component pyrolysis can process organic components and reduce cathode materials, making it a key focus in green recycling of lithium-ion batteries (LIBs). However, the leaching mechanism and kinetics of pyrolyzed black powder in organic acid systems remain unclear, with most research still at the laboratory stage. This study pioneers the exploration of the leaching behavior and reaction mechanism of valuable metal extraction from industrial-scale pyrolyzed black powder using citric acid. The effects of various leaching conditions on the extraction of metals were investigated by single factor experiments and response surface method. Under optimal conditions, the leaching efficiencies of Li, Ni, Co, and Mn all exceeded 97%. Kinetic analysis revealed that the leaching process was controlled by internal diffusion, with the apparent activation energies for Li, Ni, Co, and Mn being 17.89, 23.14, 20.27, and 15.21 kJ/mol, respectively. Additionally, residue characterization identified FePO4 formation as the primary inhibitor of iron dissolution.

Keywords

spent lithium-ion battery / pyrolysis / leaching kinetics / response surface methodology / citric acid

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Shen-ao Zhang, Yong-wei Wang, Yu-e Tan, Li-jue Wang, Jun-wei Han. Efficient extraction of metals from industrially produced pyrolytic black powder using citric acid: Process optimization and leaching mechanism. Journal of Central South University, 2025, 32(9): 3591-3609 DOI:10.1007/s11771-025-6006-3

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References

[1]

Gao W-h, Nie C-c, Li L, et al.. Sustainable and efficient deep eutectic solvents in recycling of spent lithium-ion batteries: Recent advances and perspectives. Journal of Cleaner Production, 2024, 464: 142735 J]

[2]

Zhang Y-c, Yu W-h, Xu S-m. Enhanced leaching of metals from spent lithium-ion batteries by catalytic carbothermic reduction. Rare Metals, 2023, 42(8): 2688-2699 J]

[3]

Men L-j, Feng S-y, Zhang J-f, et al.. A systematic review of efficient recycling for the cathode materials of spent lithium-ion batteries: Process intensification technologies beyond traditional methods. Green Chemistry, 2024, 26(31170-1193 J]

[4]

Abdalla A M, Abdullah M F, Dawood M K, et al.. Innovative lithium-ion battery recycling: Sustainable process for recovery of critical materials from lithium-ion batteries. Journal of Energy Storage, 2023, 67: 107551 J]

[5]

Cun Z-g, Xing P, Wang C-y, et al.. Stepwise recovery of critical metals from spent NCM lithium-ion battery via calcium hydroxide assisted pyrolysis and leaching. Resources, Conservation and Recycling, 2024, 202: 107390 J]

[6]

Zheng X-h, Zhu Z-w, Lin X, et al.. A minireview on metal recycling from spent lithium ion batteries. Engineering, 2018, 4(3): 361-370 J]

[7]

Chang D, Yang S-h, Shi P-f, et al.. Selective recovery of lithium and efficient leaching of transition metals from spent LiNixCoyMnzO2 batteries based on a synergistic roasting process. Chemical Engineering Journal, 2022, 449: 137752 J]

[8]

Ning Y-d, Zhang Y-j, Zhu B-y, et al.. Reducing the environmental impact of lithium-ion battery recycling through co-processing of NCM and LFP. Process Safety and Environmental Protection, 2024, 187: 810-819 J]

[9]

Chen L-l, Chao Y-h, Li X-w, et al.. Engineering a tandem leaching system for the highly selective recycling of valuable metals from spent Li-ion batteries. Green Chemistry, 2021, 23(52177-2184 J]

[10]

Zheng S-m, Xu S, Wang Z-h, et al.. Efficient leaching of valuable metals from spent lithium-ion batteries using green deep eutectic solvents: Process optimization, mechanistic analysis, and environmental impact assessment. Journal of Cleaner Production, 2024, 480: 144128 J]

[11]

Shi G-c, Zhang N, Cheng J, et al.. Full closed-loop green regeneration and recycling technology for spent ternary lithium batteries: Hydrogen reduction with sulfuric acid cycle-leaching process. Journal of Environmental Chemical Engineering, 2023, 11(6): 111207 J]

[12]

Dong L-p, Li Y-j, Shi P, et al.. Low-viscosity acidic deep eutectic solvent for extraction of valuable metals from spent NCM. Journal of Power Sources, 2023, 582: 233564 J]

[13]

Wang Y, Xu Z-q, Zhang X, et al.. A green process to recover valuable metals from the spent ternary lithium-ion batteries. Separation and Purification Technology, 2022, 299: 121782 J]

[14]

Sonoc A C, Jeswiet J, Murayama N, et al.. A study of the application of Donnan dialysis to the recycling of lithium ion batteries. Hydrometallurgy, 2018, 175: 133-143 J]

[15]

Qi Y-p, Meng F-s, Yi X-x, et al.. A novel and efficient ammonia leaching method for recycling waste lithium ion batteries. Journal of Cleaner Production, 2020, 251: 119665 J]

[16]

Al-Asheh S, Aidan A, Allawi T, et al.. Treatment and recycling of spent lithium-based batteries: A review. Journal of Material Cycles and Waste Management, 2024, 26(176-95 J]

[17]

Tao R, Xing P, Li H-q, et al.. In situ reduction of cathode material by organics and anode graphite without additive to recycle spent electric vehicle LiMn2O4 batteries. Journal of Power Sources, 2022, 520: 230827 J]

[18]

Lombardo G, Ebin B, St J Foreman M R, et al.. Incineration of EV Lithium-ion batteries as a pretreatment for recycling—Determination of the potential formation of hazardous by-products and effects on metal compounds. Journal of Hazardous Materials, 2020, 393: 122372 J]

[19]

Yu W-h, Guo Y, Shang Z, et al.. A review on comprehensive recycling of spent power lithium-ion battery in China. eTransportation, 2022, 11: 100155 J]

[20]

Meshram P, Pandey B D, Mankhand T R. Recovery of valuable metals from cathodic active material of spent lithium ion batteries: Leaching and kinetic aspects. Waste Management, 2015, 45: 306-313 J]

[21]

Liu P-c, Xiao L, Tang Y-w, et al.. Study on the reduction roasting of spent LiNixCoyMnzO2 lithium-ion battery cathode materials. Journal of Thermal Analysis and Calorimetry, 2019, 136(31323-1332 J]

[22]

Zhao Y-z, Liu B-g, Zhang L-b, et al.. Microwave-absorbing properties of cathode material during reduction roasting for spent lithium-ion battery recycling. Journal of Hazardous Materials, 2020, 384: 121487 J]

[23]

Yuan Q, Zeng J, Sui Q-x, et al.. Thermodynamic and experimental analysis of lithium selectively recovery from spent lithium-ion batteries by in situ carbothermal reduction. Journal of Environmental Chemical Engineering, 2023, 11(5): 111029 J]

[24]

Zhang Y-c, Wang W-q, Fang Q, et al.. Improved recovery of valuable metals from spent lithium-ion batteries by efficient reduction roasting and facile acid leaching. Waste Management, 2020, 102: 847-855 J]

[25]

Diaz F, Wang Y, Moorthy T, et al.. Degradation mechanism of nickel-cobalt-aluminum (NCA) cathode material from spent lithium-ion batteries in microwave-assisted pyrolysis. Metals, 2018, 8(8565 J]

[26]

Jiang H-d, Li Z-h, Xie W-n, et al.. Study on the thermal reduction effect of organic components in spent ternary lithium battery cathode active materials. Waste Management, 2022, 148: 33-42 J]

[27]

Tao R, Xing P, Li H-q, et al.. Full-component pyrolysis coupled with reduction of cathode material for recovery of spent LiNixCoyMnzO2 lithium-ion batteries. ACS Sustainable Chemistry & Engineering, 2021, 9(186318-6328 J]

[28]

Tao R, Xing P, Li H-q, et al.. Kinetics study and recycling strategies in different stages of full-component pyrolysis of spent LiNixCoyMnzO2 lithium-ion batteries. Waste Management, 2023, 155: 8-18 J]

[29]

Luo Y, Ou L-m, Yin C-z. A green and efficient combination process for recycling spent lithium-ion batteries. Journal of Cleaner Production, 2023, 396: 136552 J]

[30]

Zhang J-z, Hu X-y, He T-t, et al.. Rapid extraction of valuable metals from spent LiNixCoyMn1−xyO2 cathodes based on synergistic effects between organic acids. Waste Management, 2023, 165: 19-26 J]

[31]

Kim J Y, Wu J-j, Kim E W, et al.. Recycling for recovery of critical metals from LiCoO2 cathode material through methanesulfonic acid-citric acid organic leaching system. Mining, Metallurgy & Exploration, 2023, 40(5): 1455-1467 J]

[32]

Yan S-x, Sun C-h, Zhou T, et al.. Ultrasonic-assisted leaching of valuable metals from spent lithium-ion batteries using organic additives. Separation and Purification Technology, 2021, 257: 117930 J]

[33]

Sidiq A L, Floweri O, Karunawan J, et al.. NCM cathode active materials reproduced from end-of-life Li-ion batteries using a simple and green hydrometallurgical recycling process. Materials Research Bulletin, 2022, 153: 111901 J]

[34]

Zhuang L-q, Sun C-h, Zhou T, et al.. Recovery of valuable metals from LiNi0.5Co0.2Mn0.3O2 cathode materials of spent Li-ion batteries using mild mixed acid as leachant. Waste Management, 2019, 85: 175-185 J]

[35]

Kumar J, Shen X, Li B, et al.. Selective recovery of Li and FePO4 from spent LiFePO4 cathode scraps by organic acids and the properties of the regenerated LiFePO4. Waste Management, 2020, 113: 32-40 J]

[36]

Manzi J, Curcio M, Brutti S. Structural and morphological tuning of LiCoPO4 materials synthesized by solvo-thermal methods for Li-cell applications. Nanomaterials, 2015, 5(4): 2212-2230 J]

[37]

Pagnanelli F, Altimari P, Colasanti M, et al.. Recycling Li-ion batteries via the re-synthesis route: Improving the process sustainability by using lithium iron phosphate (LFP) scraps as reducing agents in the leaching operation. Metals, 2024, 14(11): 1275 J]

[38]

Martins L S, Rovani S, Botelho A B, et al.. Sustainable approach for critical metals recovery through hydrometallurgical processing of spent batteries using organic acids. Industrial & Engineering Chemistry Research, 2023, 62(4418672-18682 J]

[39]

Golmohammadzadeh R, Faraji F, Rashchi F. Recovery of lithium and cobalt from spent lithium ion batteries (LIBs) using organic acids as leaching reagents: A review. Resources, Conservation and Recycling, 2018, 136: 418-435 J]

[40]

Deng H-y, Hong R-z, Wang B, et al.. Ultrasonic enhanced preferential leaching process of Li from waste lithium-ion batteries using oxalic acid focused on optimization and mechanism. Separation and Purification Technology, 2025, 364: 132327 J]

[41]

Makuza B, Yu D-w, Huang Z, et al.. Dry grinding-carbonated ultrasound-assisted water leaching of carbothermally reduced lithium-ion battery black mass towards enhanced selective extraction of lithium and recovery of high-value metals. Resources, Conservation and Recycling, 2021, 174: 105784 J]

[42]

Chen H, Liao L-y, Ding Y-x, et al.. Feasible route for the regeneration of cathode materials from spent lithium-ion batteries via reduction leaching and in-site precipitation. Journal of Power Sources, 2024, 598: 234155 J]

[43]

Yang C, Wang Q, Xu L, et al.. Cleaner separation and recovery of valuable metals from spent ternary cathode via carbon dioxide synergetic tHermite reduction strategy. Journal of Environmental Management, 2024, 366: 121853 J]

[44]

Ma Y-y, Zhou X-y, Tang J-j, et al.. One-step selective recovery and cyclic utilization of valuable metals from spent lithium-ion batteries via low-temperature chlorination pyrolysis. Resources, Conservation and Recycling, 2021, 175: 105840 J]

[45]

Divya M L, Natarajan S, Aravindan V. Graphene from spent lithium-ion batteries. Batteries & Supercaps, 2022, 5(6e202200046 J]

[46]

Zhao L-n, Tian L-y, Li J-y, et al.. Recent progress in the recycling of spent graphite anodes: Failure mechanisms, repair techniques, and prospects. Energy Storage Materials, 2024, 71: 103640 J]

[47]

Wang Y-w, Wang L-j, Zhang S, et al.. Green strategy for recovering cathode materials from end-of-life lithium-ion batteries using grape pomace. Separation and Purification Technology, 2025, 354: 129184 J]

[48]

Chabhadiya K, Srivastava R R, Pathak P. Two-step leaching process and kinetics for an eco-friendly recycling of critical metals from spent Li-ion batteries. Journal of Environmental Chemical Engineering, 2021, 9(3105232 J]

[49]

Wang Y-w, Chang X-j, Cheng Y-h, et al.. Selective leaching of nickel and cobalt from sintered nickel alloy by oxygen pressure acid leaching process. Journal of Central South University, 2023, 30(124004-4020 J]

[50]

Li H-y, Li S-w, Peng J-h, et al.. Ultrasound augmented leaching of nickel sulfate in sulfuric acid and hydrogen peroxide media. Ultrasonics Sonochemistry, 2018, 40: 1021-1030 J]

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