Skip to main content
SpringerLink
Log in

Recovery of metals from electroactive components of spent Li-ion batteries after leaching with formic acid

  • Original Paper
  • Published:
Brazilian Journal of Chemical Engineering Aims and scope Submit manuscript

Abstract

In this study, the recovery of manganese, nickel, cobalt and lithium of electroactive components from spent lithium-ion batteries is described in detail. Experiments were performed in the presence of formic acid as leachant. Temperature, time, acid concentration and solid/liquid ratio were varied. Manganese, nickel and lithium were leached in high yields (> 99 wt.%) at ~ 80 °C for 3 h using 10 mol L−1 formic acid. This acid played the dual role of leachant and reductant for nickel and manganese. However, cobalt was only half leached under these conditions. The insoluble cobalt was rapidly dissolved after adding H2O2 to the leachant. Leached manganese, cobalt and nickel, in this order, were extracted from the leachates with di-2-ethylhexylphosphoric acid (D2EHPA) (25 °C, A/O = 1 v/v) after adjusting pH of the leachate using lithium carbonate. Stripping was run using 1 mol L−1 H2SO4. Lithium (99.5 wt.%) was recovered as formate, a high-value added byproduct, by careful evaporation of the aqueous final solution, thus reducing generation of final wastes.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

Code availability

Not applicable.

References

  • Aaltonen M, Peng C, Wilson BP, Lundström M (2017) Leaching of metals from spent lithium-ion batteries. Recycling. https://doi.org/10.3390/recycling2040020

    Article  Google Scholar 

  • Alfath M, Lee CW (2020) Recent advances in the catalyst design and mass transport control for the electrochemical reduction of carbon dioxide to formate. Catalysts. https://doi.org/10.3390/catal10080859

    Article  Google Scholar 

  • Almeida JR, Moura MN, Barrada RV, Barbieri EMS, Carneiro MTWD, Ferreira SAD, Lelis MFF, Freitas MBJG, Brandão GP (2019) Composition analysis of the cathode active material of spent Li-ion batteries leached in citric acid solution: a study to monitor and assist recycling processes. Sci Total Environ 685:589–595

    CAS  PubMed  Google Scholar 

  • Atia TA, Elia G, Hahn R, Altimari P, Pagnanelli F (2019) Closed-loop hydrometallurgical treatment of end-of-life lithium ion batteries: towards zero-waste process and metal recycling in advanced batteries. J Energy Chem 35:220–227

    Google Scholar 

  • Ayanda OS, Adekola FA, Baba AA, Ximba BJ, Fatoki OS (2013) Application of Cyanex® extractant in Cobalt/Nickel separation process by solvent extraction. Int J Phys Sci 8:89–97

    CAS  Google Scholar 

  • Barik SP, Prabaharan G, Kumar L (2017) Leaching and separation of Co and Mn from electrode materials of spent lithium-ion batteries using hydrochloric acid: Laboratory and pilot scale study. J Cleaner Prod 147:37–43

    CAS  Google Scholar 

  • Blomgren GE (2017) The development and future of lithium ion batteries. J Electrochem Soc 164:A5019–A5025

    CAS  Google Scholar 

  • Bukowsky H, Uhlemann E, Gloe K, Mühl P (1992) The separation of calcium and magnesium from lithium chloride by liquid-liquid extraction with di (2-ethylhexyl) phosphoric acid. Hydrometallurgy 28:323–329

    CAS  Google Scholar 

  • Cavell RG (1968) Chemistry of phosphorus fluorides. Part III. The reaction of thiophosphoryl-fluoride with dimethylamine and some properties of the dimethylaminothio-phosphoryl fluorides. Can J Chem 46:613–621

    CAS  Google Scholar 

  • Cerrillo-Gonzalez M, Villen-Guzman M, Vereda-Alonso C, Gomez-Lahoz C, Rodriguez-Maroto J, Paz-Garcia J (2020) Recovery of Li and Co from LiCoO2 via hydrometallurgical–electrodialytic treatment. Appl Sci. https://doi.org/10.3390/app10072367

    Article  Google Scholar 

  • Daniel DJ, Ramasamy DP (2014) Studies on semi-organic non linear optical single crystal: lithium formate monohydrate (HCO2Li⋅H2O). Opt Mater 36:971–976

    Google Scholar 

  • Dhiman S, Gupta B (2019) Partition studies on cobalt and recycling of valuable metals from waste Li-ion batteries via solvent extraction and chemical precipitation. J Cleaner Prod 225:820–832

    CAS  Google Scholar 

  • Ding Y, Cano ZP, Yu A, Lu J, Chen Z (2019) Automotive Li-ion batteries: current status and future perspectives. Electrochem Energy Rev 2:1–28

    CAS  Google Scholar 

  • Fernandes A, Afonso JC, Dutra AJB (2012) Hydrometallurgical route to recover nickel, cobalt and cadmium from spent Ni-Cd batteries. J Power Sources 220:286–291

    CAS  Google Scholar 

  • Fu Y, He Y, Chen H, Ye C, Lu Q, Li R, Xie W, Wang J (2019) Effective leaching and extraction of valuable metals from electrode material of spent lithium-ion batteries using mixed organic acids leachant. J Ind Eng Chem 79:154–162

    CAS  Google Scholar 

  • Gaines L (2018) Lithium-ion battery recycling processes: research towards a sustainable course. Sust Mater Technol 17:e00068

    CAS  Google Scholar 

  • Gao W, Zhang X, Hong ZH, Lin X, Cao H, Zhang Y, Sun Z (2017) Lithium carbonate recovery from cathode scrap of spent lithium-ion battery: a closed-loop process. Environ Sci Technol 51:1662–1669

    CAS  PubMed  Google Scholar 

  • Gao W, Liu C, Cao H, Zheng X, Lin X, Wang H, Zhang Y, Sun Z (2018) Comprehensive evaluation on effective leaching of critical metals from spent lithium-ion batteries. Waste Manag 75:477–485

    CAS  PubMed  Google Scholar 

  • Gouvea LR, Morais CA (2010) Development of a process for the separation of zinc and copper from sulfuric liquor obtained from the leaching of an industrial residue by solvent extraction. Miner Eng 23:492–497

    CAS  Google Scholar 

  • He LP, Sun SY, Song XF, Yu JG (2015) Recovery of cathode materials and Al from spent lithium-ion batteries by ultrasonic cleaning. Waste Manag 46:523–528

    CAS  PubMed  Google Scholar 

  • Hietala J, Vuori A, Johnsson P, Pollari I, Reutemann W, Kieczka H (2016) Formic acid. Ullmann’s encyclopaedia of industrial chemistry. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

    Google Scholar 

  • Ibiapina VF, Afonso JC, Gante V, Vianna CA, Mantovano JL (2018) Separation of zinc from manganese by solvent extraction from acidic leachates of spent zinc-MnO2 dry cells using neutral organophosphorus extractants. Quim Nova 41:770–777

    CAS  Google Scholar 

  • Janiszewska M, Markiewicz A, Regel-Ros M (2019) Hydrometallurgical separation of Co(II) from Ni(II) from model and real waste solutions. J Cleaner Prod 228:746–754

    CAS  Google Scholar 

  • Jo CH, Myung ST (2019) Efficient recycling of valuable resources from discarded lithium-ion batteries. J Power Sources 426:259–265

    CAS  Google Scholar 

  • Kumar N, Leung K, Siegel DJ (2014) crystal surface and state of charge dependencies of electrolyte decomposition on LiMn2O4 cathode. J Electrochem Soc 161:E3059–E3065

    CAS  Google Scholar 

  • Li L, Qu W, Zhang X, Lu J, Chen R, Wu F, Amine K (2015) Succinic acid-based leaching system: a sustainable process for recovery of valuable metals from spent Li-ion batteries. J Power Sources 282:544–551

    CAS  Google Scholar 

  • Liu P, Xiao L, Chen Y, Tang Y, Wu J, Chen H (2019a) 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 783:743–752

    CAS  Google Scholar 

  • Liu C, Lin J, Cao H, Zhang Y, Sun Z (2019b) Recycling of spent lithium-ion batteries in view of lithium recovery: a critical review. J Cleaner Prod 228:801–813

    CAS  Google Scholar 

  • Lurie J (1978) Handbook of Analytical Chemistry, 3rd edn. Mir, Moscow

    Google Scholar 

  • Lv W, Wang Z, Cao H, Zheng X, Jin W, Zhang Y, Sun Z (2018) A sustainable process for metal recycling from spent lithium-ion batteries using ammonium chloride. Waste Manag 79:545–553

    CAS  PubMed  Google Scholar 

  • Meng Q, Zhang Y, Dong P (2017) Use of glucose as reductant to recover Co from spent lithium ions Batteries. Waste Manag 64:214–218

    CAS  PubMed  Google Scholar 

  • Meng Q, Zhang Y, Dong P (2018a) Use of electrochemical cathode-reduction method for leaching of cobalt from spent lithium-ion batteries. J Clean Prod 180:64–70

    CAS  Google Scholar 

  • Meng Q, Zhang Y, Dong P, Liang F (2018b) A novel process for leaching of metals from LiNi1/3Co1/3Mn1/3O2 material of spent lithium ion batteries: Process optimization and kinetics aspects. J Ind Eng Chem 61:133–141

    CAS  Google Scholar 

  • Meng Q, Zhang Y, Dong P (2018c) A combined process for cobalt recovering and cathode material regeneration from spent LiCoO2 batteries: process optimization and kinetics aspects. Waste Manag 71:372–380

    CAS  PubMed  Google Scholar 

  • Meng F, Liu Q, Kim R, Wang J, Liu G, Ghahreman A (2020) Selective recovery of valuable metals from industrial waste lithium-ion batteries using citric acid under reductive conditions: leaching optimization and kinetic analysis. Hydrometallurgy 191:105160

    CAS  Google Scholar 

  • Meshram P, Mishra A, Sahu R (2020) Environmental impact of spent lithium ion batteries and green recycling perspectives by organic acids: a review. Chemosphere. https://doi.org/10.1016/j.chemosphere.2019.125291

    Article  PubMed  Google Scholar 

  • Musariri B, Akdogan G, Dorfling C, Bradshaw S (2019) Evaluating organic acids as alternative leaching reagents for metal recovery from lithium ion batteries. Miner Eng 137:108–117

    CAS  Google Scholar 

  • Myung ST, Maglia F, Park KJ, Yoon CS, Lamp P, Kim SJ, Sun YK (2017) Nickel-rich layered cathode materials for automotive lithium-ion batteries: achievements and perspectives. ACS Energy Lett 2:196–223

    CAS  Google Scholar 

  • Nayaka GP, Pai KV, Manjanna J, Keny SJ (2016a) Use of mild organic acid reagents to recover the Co and Li from spent Li-ion batteries. Waste Manag 51:234–238

    CAS  PubMed  Google Scholar 

  • Nayaka GP, Pai KV, Santhosh G, Manjanna J (2016b) Dissolution of cathode active material of spent Li-ion batteries using tartaric acid and ascorbic acid mixture to recover Co. Hydrometallurgy 161:54–57

    CAS  Google Scholar 

  • Nayaka GP, Zhang Y, Dong P, Wang D, Pai KV, Manjanna J, Santhosh G, Duan J, Zhou Z, Xiao J (2018) Effective and environmentally friendly recycling process designed for LiCoO2 cathode powders of spent Li-ion batteries using mixture of mild organic acids. Waste Manag 78:51–57

    CAS  PubMed  Google Scholar 

  • Pinna EG, Ruiz MC, Ojeda MW, Rodriguez MH (2017) Cathodes of spent Li-ion batteries: dissolution with phosphoric acid and recovery of lithium and cobalt from leach liquors. Hydrometallurgy 167:66–71

    CAS  Google Scholar 

  • Rao PVS (1973) Kinetics of oxidation of formic acid by potassium permanganate. Z Phys Chemie Leipzig 2520:276–279

    Google Scholar 

  • Ritcey GM, Ashbrook AW (1984) Principles and applications to process metallurgy (part I). Elsevier, New York

    Google Scholar 

  • Sharma NN, Mehrotra MC (1955) Cerate oxidimetry: oxidation of glycerol, glycol and other organic compounds. Anal Chim Acta 13:419–423

    CAS  Google Scholar 

  • Shih YJ, Chien SK, Jhang SR, Lin YC (2019) Chemical leaching, precipitation and solvent extraction for sequential separation of valuable metals in cathode material of spent lithium ion batteries. J Taiwan Inst Chem E 100:151–159

    CAS  Google Scholar 

  • Silva RG, Afonso JC, Mahler CF (2018a) Lixiviação ácida de baterias íon-lítio. Quim Nova 41:581–586

    CAS  Google Scholar 

  • Silva WC, Corrêa RS, Silva CSM, Afonso JC, Silva RS, Vianna CA, Mantovano JL (2018b) Recovery of base metals, silicon and fluoride ions from mobile phone printed circuit boards after leaching with hydrogen fluoride and hydrogen peroxide mixtures. Waste Manag 78:781–788

    CAS  PubMed  Google Scholar 

  • Srámková B, Zýka J (1974) Oxidizing properties and analytical use of Co(III) solutions. Microchem J 19:295–305

    Google Scholar 

  • Vieceli N, Nogueira CA, Guimarães C, Pereira MC, Durão FO, Margarido F (2018) Hydrometallurgical recycling of lithium-ion batteries by reductive leaching with sodium metabisulphite. Waste Manag 71:350–361

    CAS  PubMed  Google Scholar 

  • Waldeland E, Malinen E (2011) Review of the dose-to-water energy dependence of alanine and lithium formate EPR dosimeters and LiF TL-dosimeters: comparison with Monte Carlo simulations. Radiat Meas 46:945–951

    CAS  Google Scholar 

  • Wang D, Wang X, Yang X, Yu R, Ge L, Shu H (2015) Polyaniline modification and performance enhancement of lithium-rich cathode material based on layered-spinel hybrid structure. J Power Sources 293:89–94

    CAS  Google Scholar 

  • Wang D, Zhang X, Chen H, Sun J (2018) Separation of Li and Co from the active mass of spent Li-ion batteries by selective sulfating roasting with sodium bisulfate and water leaching. Miner Eng 126:28–35

    CAS  Google Scholar 

  • Wang S, Wang C, Lai F, Yan F, Zhang Z (2020) Reduction-ammoniacal leaching to recycle lithium, cobalt, and nickel from spent lithium-ion batteries with a hydrothermal method: effect of reductants and ammonium salts. Waste Manag 102:122–130

    CAS  PubMed  Google Scholar 

  • Wood DL, Quassb JD, Lia J, Ahmedc S, Ventolab D, Danie C (2018) Technical and economic analysis of solvent-based lithium-ion electrode drying with water and NMP. Dry Technol 36:234–244

    CAS  Google Scholar 

  • Yang L, Yang L, Xu G, Feng Q, Li Y, Zhao E, Ma J, Fan S, Li X (2019) Separation and recovery of carbon powder in anodes from spent lithium-ion batteries to synthesize graphene. Sci Rep. https://doi.org/10.1038/s41598-019-46393-4

    Article  PubMed  PubMed Central  Google Scholar 

  • Yang X, Dong P, Hao T, Zhang Y, Meng Q, Li Q, Zhou S (2020a) A combined method of leaching and co-precipitation for recycling spent LiNi0.6Co0.2Mn0.2O2 cathode materials: process optimization and performance aspects. JOM 72:3843–3852

    CAS  Google Scholar 

  • Yang Y, Lei S, Song S, Sun W, Wang L (2020b) Stepwise recycling of valuable metals from Ni-rich cathode material of spent lithium-ion batteries. Waste Manag 102:131–138

    CAS  PubMed  Google Scholar 

  • Zhang Y, Meng Q, Dong P, Duan J, Lin Y (2018) Use of grape seed as reductant for leaching of cobalt from spent lithium-ion batteries. J Ind Eng Chem 66:86–93

    CAS  Google Scholar 

  • Zheng X, Gao W, Zhang X, He M, Lin X, Cao H, Zhang Y, Sun Z (2017) Spent lithium-ion battery recycling. Reductive ammonia leaching of metals from cathode scrap by sodium sulphite. Waste Manag 60:680–688

    CAS  PubMed  Google Scholar 

  • Zheng Y, Song W, Mo WT, Zhoub L, Liu JW (2018) Lithium fluoride recovery from cathode material of spent lithium-ion battery. RSC Adv 8:8990–8998

    CAS  Google Scholar 

  • Zhou S, Zhang Y, Meng Q, Dong P, Li Q (2021) Recycling of LiCoO2 cathode material from spent lithium ion batteries by ultrasonic enhanced leaching and one-step regeneration. J. Environ Manag 277:111426

    CAS  Google Scholar 

Download references

Acknowledgements

The authors thank the National Council for Scientific and Technological Development–Brazil (CNPq) for financial support. G. T. C. Zeba acknowledges the Coordination for the Improvement of Higher Education Personnel–Brazil (CAPES) for a fellowship.

Funding

Not applicable (cited in the acknowledgement section).

Author information

Authors and Affiliations

  1. Analytical Chemistry Department, Institute of Chemistry, Federal University of Rio de Janeiro, Ilha do Fundão, Rio de Janeiro, 21941-909, Brazil

    Guido Tande Crespo Zeba, Jéssica Frontino Paulino & Júlio Carlos Afonso

Authors
  1. Guido Tande Crespo Zeba
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jéssica Frontino Paulino
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Júlio Carlos Afonso
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Júlio Carlos Afonso.

Ethics declarations

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zeba, G.T.C., Paulino, J.F. & Afonso, J.C. Recovery of metals from electroactive components of spent Li-ion batteries after leaching with formic acid. Braz. J. Chem. Eng. 39, 147–158 (2022). https://doi.org/10.1007/s43153-021-00095-5

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s43153-021-00095-5

Keywords

Search

Navigation