Journal of Materials Science

, Volume 53, Issue 19, pp 13790–13800 | Cite as

Improved extraction of cobalt and lithium by reductive acid from spent lithium-ion batteries via mechanical activation process

  • Yaoguang Guo
  • Yaguang Li
  • Xiaoyi Lou
  • Jie Guan
  • Yingshun Li
  • Xianmin Mai
  • Hu Liu
  • Cindy Xinxin Zhao
  • Ning Wang
  • Chao Yan
  • Guilan Gao
  • Hao Yuan
  • Jue Dai
  • Ruijng Su
  • Zhanhu Guo
Mechanochemical Synthesis


Cobalt (Co) and lithium (Li) were extracted from pure LiCoO2 powders and actual cathode material powders from the spent lithium-ion batteries (LIBs) after l-ascorbic acid dissolution via a mechanical activation process. The influences of activation time and rotation speed on the leaching were discussed. The mechanism of the improved leaching yield was proposed based on the characterization analysis including X-ray diffraction, scanning electron microscope, BET-specific surface area and particle size analyzer. The reduced particle size, increased specific surface area of activated samples, destroyed crystal structure and amorphous state of LiCoO2 contributed to the improved leaching efficiencies of Co and Li. With the activated process, about 99% Co and 100% Li were extracted from actual spent LIBs after 60-min grinding at 500 rpm with mild conditions. This effective process would be of great importance for recovering valuable metals from the spent LIBs at room temperature.



We gratefully appreciate the financial support from Shanghai “Chenguang” Program (15CG60), Shanghai Sailing Program (18YF1429900, 15YF1404300), Natural Science Foundation of China (51678353), Shanghai Natural Science Foundation (No. 15ZR1416800), Cultivate discipline fund of Shanghai Polytechnic University (XXKPY1601) and Eastern Scholar Professorship Grant. The authors also acknowledge the Graduate Student Funding Program of Shanghai Polytechnic University (A01GY16F030), Shanghai Polytechnic University Leap Program (EGD18XQD24), and project supported by Shanghai Cooperative Centre for WEEE Recycling (ZF1224).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2018_2229_MOESM1_ESM.docx (4 mb)
Supplementary material 1 (DOCX 4076 kb)


  1. 1.
    Wang R, Lin Y, Wu S (2009) A novel recovery process of metal values from the cathode active materials of the lithium-ion secondary batteries. Hydrometallurgy 99:194–201CrossRefGoogle Scholar
  2. 2.
    Zhang T, He Y, Wang F, Ge L, Zhu X, Li H (2014) Chemical and process mineralogical characterizations of spent lithium-ion batteries: an approach by multi-analytical techniques. Waste Manag 34:1051–1058CrossRefGoogle Scholar
  3. 3.
    Zhang X, Xie Y, Cao H, Nawaz F, Zhang Y (2014) A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for lithium-ion batteries. Waste Manag 34:1715–1724CrossRefGoogle Scholar
  4. 4.
    Zeng X, Li J, Singh N (2013) Recycling of spent lithium-ion battery: a critical review. Crit Rev Environ Sci Technol 10:1129–1165Google Scholar
  5. 5.
    Dorella G, Mansur MB (2007) A study of the separation of cobalt from spent Li-ion battery residues. J Power Sources 170:210–215CrossRefGoogle Scholar
  6. 6.
    Rivera I, Roca A, Cruells M, Patiño F, Salinas E (2007) Study of silver precipitation in thiosulfate solutions using sodium dithionite. Application to an industrial effluent. Hydrometallurgy 89:89–98CrossRefGoogle Scholar
  7. 7.
    Scrosati B, Garche J (2010) Lithium batteries: status, prospects and future. J Power Sources 195:2419–2430CrossRefGoogle Scholar
  8. 8.
    Nayakaa GP, Paia KV, Santhoshb G, Manjannac J (2016) Recovery of cobalt as cobalt oxalate from spent lithium ion batteries by using glycine as leaching agent. J Environ Chem Eng 4:2378–2383CrossRefGoogle Scholar
  9. 9.
    Lee CK, Rhee KI (2002) Preparation of LiCoO2 from spent lithium-ion batteries. J Power Sources 109:17–21CrossRefGoogle Scholar
  10. 10.
    Shin SM, Kim NH, Sohn JS, Yang DH, Kim YH (2005) Development of a metal recovery process from Li-ion battery wastes. Hydrometallurgy 79:172–181CrossRefGoogle Scholar
  11. 11.
    Xu J, Thomas HR, Francis RW, Lum KR, Wang J, Bo Liang (2008) A review of processes and technologies for the recycling of lithium-ion secondary batteries. J Power Sources 177:512–527CrossRefGoogle Scholar
  12. 12.
    Chagnes A, Pospiech B (2013) A brief review on hydrometallurgical technologies for recycling spent lithium-ion batteries. J Chem Technol Biot 88:1191–1199CrossRefGoogle Scholar
  13. 13.
    Li L, Ge J, Chen R, Wu F, Chen S, Zhang X (2010) Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries. Waste Manag 30:2615–2621CrossRefGoogle Scholar
  14. 14.
    Mishra D, Kim DJ, Ralph DE, Ahn JG, Rhee YH (2008) Bioleaching of metals from spent lithium ion secondary batteries using Acidithiobacillus ferrooxidans. Waste Manag 28:333–338CrossRefGoogle Scholar
  15. 15.
    Kang J, Senanayake G, Sohn J, Shin SM (2010) Recovery of cobalt sulfate from spent lithium ion batteries by reductive leaching and solvent extraction with Cyanex 272. Hydrometallurgy 100:168–171CrossRefGoogle Scholar
  16. 16.
    Meshram P, Pandey BD, Mankhand TR (2015) Recovery of valuable metals from cathodic active material of spent lithium ion batteries: leaching and kinetic aspects. Waste Manag 45:306–313CrossRefGoogle Scholar
  17. 17.
    Meshram P, Pandey BD, Mankhand TR (2015) Hydrometallurgical processing of spent lithium ion batteries (LIBs) in the presence of a reducing agent with emphasis on kinetics of leaching. Chem Eng J 281:418–427CrossRefGoogle Scholar
  18. 18.
    Tanong K, Coudert L, Mercier G, Blais JF (2016) Recovery of metals from a mixture of various spent batteries by a hydrometallurgical process. J Environ Manag 181:95–107CrossRefGoogle Scholar
  19. 19.
    Contestabile M, Panero S, Scrosati B (2001) A laboratory-scale lithium-ion battery recycling process. J Power Sources 92:65–69CrossRefGoogle Scholar
  20. 20.
    Guo Y, Li F, Zhu H, Li G, Huang J, He W (2016) Leaching lithium from the anode electrode materials of spent lithium-ion batteries by hydrochloric acid (HCl). Waste Manag 51:227–233CrossRefGoogle Scholar
  21. 21.
    Sun L, Qiu K (2012) Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries. Waste Manag 32:1575CrossRefGoogle Scholar
  22. 22.
    Li L, Ge J, Wu F, Chen RJ, Chen S, Wu B (2010) Recovery of cobalt and lithium from spent lithium ion batteries using organic citric acid as leachant. J Hazard Mater 176:288CrossRefGoogle Scholar
  23. 23.
    Li L, Qu W, Zhang XX, Lu J, Chen RJ, Wu F, Khalil A (2015) Succinic acid-based leaching system: a sustainable process for recovery of valuable metals from spent Li-ion batteries. J Power Sources 282:544–551CrossRefGoogle Scholar
  24. 24.
    Zeng X, Li J, Shen B (2015) Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid. J Hazard Mater 295:112–118CrossRefGoogle Scholar
  25. 25.
    Nayaka GP, Pai KV, Santhosh G, Manjanna J (2016) Dissolution of cathode active material of spent Li-ion batteries using tartaric acid and ascorbic acid mixture to recover Co. Hydrometallurgy 161:54–57CrossRefGoogle Scholar
  26. 26.
    Tromans D, Meech J (2001) Enhanced dissolution of minerals: stored energy, amorphism and mechanical activation. Miner Eng 14:1359–1377CrossRefGoogle Scholar
  27. 27.
    Tan Q, Li J (2015) Recycling metals from wastes: a novel application of mechanochemistry. Environ Sci Technol 49:5849–5861CrossRefGoogle Scholar
  28. 28.
    Yuan W, Li J, Zhang Q, Saito F (2012) Innovated application of mechanical activation to separate lead from scrap cathode ray tube funnel glass. Environ Sci Technol 46:4109–4114CrossRefGoogle Scholar
  29. 29.
    Zhang Q, Aoyagi T, Nagata C, Saito F (1999) Room temperature extraction of indium from ITO scrap by a mechanochemical treatment. Shigen-to-Sozai 115:185–188CrossRefGoogle Scholar
  30. 30.
    Murakami Y, Shindo D, Zhang Q, Saito F (2002) Microstructural investigation on the mechanism to extract indium from wasted materials. Adv Mater Sci Eng 332:64–69Google Scholar
  31. 31.
    Wang X, Zhao CX, Xu G, Chen ZK, Zhu F (2012) Degradation mechanisms in organic solar cells: localized moisture encroachment and cathode reaction. Sol Energ Mater Sol Cells 104:1–6CrossRefGoogle Scholar
  32. 32.
    Zhao CX, Deng LL, Ma MY, Kish JR, Xu G (2013) Multiple-interface tracking of degradation process in organic photovoltaics. AIP Adv 3:102121CrossRefGoogle Scholar
  33. 33.
    Hattori S, Murayama N, Shibata J (2013) Leaching and separation of rare earth elements from 800 waste fluorescent powder. Kagaku Kogaku Ronbunshu 39:472–478CrossRefGoogle Scholar
  34. 34.
    Li L, Lu J, Ren Y, Zhang XX, Chen RJ, Wu F, Khalil A (2012) Ascorbic-acid-assisted recovery of cobalt and lithium from spent Li-ion batteries. J Power Sources 218:21–27CrossRefGoogle Scholar
  35. 35.
    Xu X, Zhang H, Lou H, Ma C, Li Y, Guo Z, Gu H (2018) Chitosan-coated-magnetite with covalently grafted polystyrene based carbon nanocomposites for hexavalent chromium adsorption. Eng Sci.
  36. 36.
    Balaz P, Kammel R (1996) Application of attritors in hydrometallurgy of complex sulfidic ores. Metall 50:345–347Google Scholar
  37. 37.
    Pourghahramani P, Forssberg E (2007) Effects of mechanical activation on the reduction behavior of hematite concentrate. Intern J Mineral Process 82:96–105CrossRefGoogle Scholar
  38. 38.
    Habashi F (2000) Extractive metallurgy of activated minerals. Elsevier Science B.V., AmsterdamGoogle Scholar
  39. 39.
    Kim DS, Sohn JS, Lee CK, Lee JH, Han KS, Lee YI (2004) Simultaneous separation and renovation of lithium cobalt oxide from the cathode of spent lithium ion rechargeable batteries. J Power Sources 132:145–149CrossRefGoogle Scholar
  40. 40.
    Baláž P (2008) Mechanochemistry in nanoscience and minerals engineering. Springer, Berlin, pp 257–296Google Scholar
  41. 41.
    Galakhov VR, Kurmaev EZ, Uhlenbrock S, Neumann M, Kellerman DG, Gorshkov VS (1996) Degree of covalency of LiCoO2: X-ray emission and photoelectron study. Solid State Commun 99:221–224CrossRefGoogle Scholar
  42. 42.
    Deng L, Wang K, Zhao CX, Yan H, Britten JF, Xu G (2011) Phase and texture of solution-processed copper phthalocyanine thin films investigated by two-dimensional grazing incidence X-ray diffraction. Crystals 1:112–119CrossRefGoogle Scholar
  43. 43.
    Zhao CX, Xiao S, Xu G (2015) Density of organic thin films in organic photovoltaics. J Appl Phys 118:044510CrossRefGoogle Scholar
  44. 44.
    Song G, Yuan W, Zhu X, Wang X, Zhang C, Li J, Bai J, Wang J (2017) Improvement in rare earth element recovery from waste trichromatic phosphors by mechanical activation. J Clean Prod 151:361–370CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Environmental and Materials EngineeringShanghai Polytechnic UniversityShanghaiPeople’s Republic of China
  2. 2.Shanghai Waigaoqiao Bonded Area Environmental Services Co., Ltd.ShanghaiPeople’s Republic of China
  3. 3.Key Laboratory of Control of Quality and Safety for Aquatic Products, Ministry of Agriculture, East China Sea Fisheries Research InstituteChinese Academy of Fishery SciencesShanghaiPeople’s Republic of China
  4. 4.Shanghai Pudong Shuguang Research Center for High Environmental Treatment TechnologiesShanghaiPeople’s Republic of China
  5. 5.Shanghai Xin Jinqiao Environmental Protection Co., Ltd.ShanghaiPeople’s Republic of China
  6. 6.School of Urban Planning and ArchitectureSouthwest Minzu UniversityChengduPeople’s Republic of China
  7. 7.National Engineering Research Center for Advanced Polymer Processing TechnologyZhengzhou UniversityZhengzhouPeople’s Republic of China
  8. 8.Integrated Composites Laboratory (ICL), Department of Chemical and Bimolecular EngineeringUniversity of TennesseeKnoxvilleUSA
  9. 9.State Key Laboratory of Marine Resource Utilization in South China SeaHainan UniversityHaikouPeople’s Republic of China
  10. 10.School of Material Science and EngineeringJiangsu University of Science and TechnologyZhenjiangPeople’s Republic of China

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