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Deep eutectic solvents for cathode recycling of Li-ion batteries

Nature Energy volume 4, pages 339–345 (2019)Cite this article

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Abstract

As the consumption of lithium-ion batteries (LIBs) for the transportation and consumer electronic sectors continues to grow, so does the pile of battery waste, with no successful recycling model, as exists for the lead–acid battery. Here, we exhibit a method to recycle LIBs using deep eutectic solvents to extract valuable metals from various chemistries, including lithium cobalt (iii) oxide and lithium nickel manganese cobalt oxide. For the metal extraction from lithium cobalt (iii) oxide, leaching efficiencies of ≥90% were obtained for both cobalt and lithium. It was also found that other battery components, such as aluminium foil and polyvinylidene fluoride binder, can be recovered separately. Deep eutectic solvents could provide a green alternative to conventional methods of LIB recycling and reclaiming strategically important metals, which remain crucial to meet the demand of the exponentially increasing LIB production.

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Fig. 1: Battery recycling schematic.
Fig. 2: Extraction of cobalt using ChCl:EG DES.
Fig. 3: Characterization of precipitate from leaching cobalt ions from the DES.
Fig. 4: Recyclability of the DES.
Fig. 5: Leaching efficiency of NMC powder dissolved in the DES at 180 °C.

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Data availability

The data that support the plots and tables within this paper and its Supplementary Information files, as well as the other findings of this study, are available from the corresponding author upon reasonable request.

References

  1. Zheng, X. et al. A mini-review on metal recycling from spent lithium ion batteries. Engineering 4, 361–370 (2018).

    Article  Google Scholar 

  2. Zeng, X., Li, J. & Singh, N. Recycling of spent lithium-ion battery: a critical review. Crit. Rev. Env. Sci. Tech. 44, 1129–1165 (2014).

    Article  Google Scholar 

  3. Frankel, T. C. The cobalt pipeline: tracing the path from deadly hand-dug mines in Congo to consumers' phones and laptops. The Washington Post (30 September 2016); https://www.washingtonpost.com/graphics/business/batteries/congo-cobalt-mining-for-lithium-ion-battery/?noredirect=on

  4. Peters, J. F., Baumann, M., Zimmermann, B., Braun, J. & Weil, M. The environmental impact of Li-ion batteries and the role of key parameters—a review. Renew. Sustain. Energy Rev. 67, 491–506 (2017).

    Article  Google Scholar 

  5. Zhang, P., Yokoyama, T., Itabashi, O., Suzuki, T. M. & Inoue, K. Hydrometallurgical process for recovery of metal values from spent lithium-ion secondary batteries. Hydrometallurgy 47, 259–271 (1998).

    Article  Google Scholar 

  6. Li, J., Wang, G. & Xu, Z. Environmentally-friendly oxygen-free roasting/wet magnetic separation technology for in situ recycling cobalt, lithium carbonate and graphite from spent LiCoO2/graphite lithium batteries. J. Hazard. Mater. 302, 97–104 (2016).

    Article  Google Scholar 

  7. Guo, Y. et al. Improved extraction of cobalt and lithium by reductive acid from spent lithium-ion batteries via mechanical activation process. J. Mater. Sci. 53, 13790–13800 (2018).

    Article  Google Scholar 

  8. Chagnes, A. & Swiatowska, J. Lithium Process Chemistry: Resources, Extraction, Batteries, and Recycling (Elsevier, 2015).

  9. Huang, B., Pan, Z., Su, X. & An, L. Recycling of lithium-ion batteries: recent advances and perspectives. J. Power Sources 399, 274–286 (2018).

    Article  Google Scholar 

  10. Chen, W.-S. & Ho, H.-J. Recovery of valuable metals from lithium-ion batteries NMC cathode waste materials by hydrometallurgical methods. Metals 8, 321 (2018).

    Article  Google Scholar 

  11. Sun, C., Xu, L., Chen, X., Qiu, T. & Zhou, T. Sustainable recovery of valuable metals from spent lithium-ion batteries using DL-malic acid: leaching and kinetics aspect. Waste Manage. Res. 36, 113–120 (2018).

    Article  Google Scholar 

  12. Yao, L., Yao, H., Xi, G. & Feng, Y. Recycling and synthesis of LiNi1/3Co1/3Mn1/3O2 from waste lithium ion batteries using d,l-malic acid. RSC Adv. 6, 17947–17954 (2016).

    Article  Google Scholar 

  13. Yao, Y. et al. Hydrometallurgical processes for recycling spent lithium-ion batteries: a critical review. ACS Sustain. Chem. Eng. 6, 13611–13627 (2018).

    Article  Google Scholar 

  14. Sun, L. & Qiu, K. Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries. Waste Manage. 32, 1575–1582 (2012).

    Article  Google Scholar 

  15. Albler, F. J., Bica, K., Foreman, M. R. S. J., Holgersson, S. & Tyumentsev, M. S. A comparison of two methods of recovering cobalt from a deep eutectic solvent: implications for battery recycling. J. Clean. Prod. 167, 806–814 (2017).

    Article  Google Scholar 

  16. Di Marino, D., Shalaby, M., Kriescher, S. & Wessling, M. Corrosion of metal electrodes in deep eutectic solvents. Electrochem. Commun. 90, 101–105 (2018).

    Article  Google Scholar 

  17. Foreman, M. R. S. Progress towards a process for the recycling of nickel metal hydride electric cells using a deep eutectic solvent. Cogent Chem. 2, 1139289 (2016).

    Article  Google Scholar 

  18. Abbott, A. P., Capper, G., Davies, D. L., McKenzie, K. J. & Obi, S. U. Solubility of metal oxides in deep eutectic solvents based on choline chloride. J. Chem. Eng. Data 51, 1280–1282 (2006).

    Article  Google Scholar 

  19. Zhang, Q., De Oliveira Vigier, K., Royer, S. & Jérôme, F. Deep eutectic solvents: syntheses, properties and applications. Chem. Soc. Rev. 41, 7108–7146 (2012).

    Article  Google Scholar 

  20. Zhao, B.-Y. et al. Biocompatible deep eutectic solvents based on choline chloride: characterization and application to the extraction of rutin from Sophora japonica. ACS Sustain. Chem. Eng. 3, 2746–2755 (2015).

    Article  Google Scholar 

  21. García, G., Aparicio, S., Ullah, R. & Atilhan, M. Deep eutectic solvents: physicochemical properties and gas separation applications. Energy Fuels 29, 2616–2644 (2015).

    Article  Google Scholar 

  22. Radošević, K. et al. Evaluation of toxicity and biodegradability of choline chloride based deep eutectic solvents. Ecotoxicol. Environ. Saf. 112, 46–53 (2015).

    Article  Google Scholar 

  23. Millia, L. et al. Bio-inspired choline chloride-based deep eutectic solvents as electrolytes for lithium-ion batteries. Solid State Ion. 323, 44–48 (2018).

    Article  Google Scholar 

  24. Tang, B., Zhang, H. & Row, K. H. Application of deep eutectic solvents in the extraction and separation of target compounds from various samples: other techniques. J. Sep. Sci. 38, 1053–1064 (2015).

    Article  Google Scholar 

  25. Smith, E. L., Abbott, A. P. & Ryder, K. S. Deep eutectic solvents (DESs) and their applications. Chem. Rev. 114, 11060–11082 (2014).

    Article  Google Scholar 

  26. Contestabile, M., Panero, S. & Scrosati, B. A laboratory-scale lithium-ion battery recycling process. J. Power Sources 92, 65–69 (2001).

    Article  Google Scholar 

  27. Pegoretti, V. C. B., Dixini, P. V. M., Smecellato, P. C., Biaggio, S. R. & Freitas, M. B. J. G. Thermal synthesis, characterization and electrochemical study of high-temperature (HT) LiCoO2 obtained from Co(OH)2 recycled of spent lithium ion batteries. Mater. Res. Bull. 86, 5–9 (2017).

    Article  Google Scholar 

  28. Chen, X. et al. Separation and recovery of metal values from leaching liquor of mixed-type of spent lithium-ion batteries. Sep. Purif. Technol. 144, 197–205 (2015).

    Article  Google Scholar 

  29. Joulié, M., Laucournet, R. & Billy, E. Hydrometallurgical process for the recovery of high value metals from spent lithium nickel cobalt aluminum oxide based lithium-ion batteries. J. Power Sources 247, 551–555 (2014).

    Article  Google Scholar 

  30. Coleman, J. S. Chloride complexes of cobalt(II) in anion and cation exchangers. J. Inorg. Nucl. Chem. 28, 2371–2378 (1966).

    Article  Google Scholar 

  31. Hsieh, Y.-T., Lai, M.-C., Huang, H.-L. & Sun, I.-W. Speciation of cobalt-chloride-based ionic liquids and electrodeposition of Co wires. Electrochim. Acta 117, 217–223 (2014).

    Article  Google Scholar 

  32. Wellens, S. et al. Dissolution of metal oxides in an acid-saturated ionic liquid solution and investigation of the back-extraction behaviour to the aqueous phase. Hydrometallurgy 144–145, 27–33 (2014).

    Article  Google Scholar 

  33. Wellens, S., Thijs, B. & Binnemans, K. An environmentally friendlier approach to hydrometallurgy: highly selective separation of cobalt from nickel by solvent extraction with undiluted phosphonium ionic liquids. Green Chem. 14, 1657–1665 (2012).

    Article  Google Scholar 

  34. Toshima, N. & Yonezawa, T. Bimetallic nanoparticles—novel materials for chemical and physical applications. New J. Chem. 22, 1179–1201 (1998).

    Article  Google Scholar 

  35. Luo, C., Zhang, Y., Zeng, X., Zeng, Y. & Wang, Y. The role of poly(ethylene glycol) in the formation of silver nanoparticles. J. Colloid Interface Sci. 288, 444–448 (2005).

    Article  Google Scholar 

  36. Huheey, J. E., Keiter, E. A., Keiter, R. L. & Medhi, O. K. Inorganic Chemistry: Principles of Structure and Reactivity (Pearson Education, 2006).

  37. Du, H. et al. Morphology control of CoCO3 crystals and their conversion to mesoporous Co3O4 for alkaline rechargeable batteries application. CrystEngComm 15, 6101–6109 (2013).

    Article  Google Scholar 

  38. González-López, J., Fernández-González, Á. & Jiménez, A. Precipitation behaviour in the system Ca2+-Co2+-CO3 2−-H2O at ambient conditions—amorphous phases and CaCO3 polymorphs. Chem. Geol. 482, 91–100 (2018).

    Article  Google Scholar 

  39. Barber, D. M., Malone, P. G. & Larson, R. J. The effect of cobalt ion on nucleation of calcium-carbonate polymorphs. Chem. Geol. 16, 239–241 (1975).

    Article  Google Scholar 

  40. Katsikopoulos, D., Fernández-González, Á., Prieto, A. C. & Prieto, M. Co-crystallization of Co(ii) with calcite: implications for the mobility of cobalt in aqueous environments. Chem. Geol. 254, 87–100 (2008).

    Article  Google Scholar 

  41. Xia, X. et al. Freestanding Co3O4 nanowire array for high performance supercapacitors. RSC Adv. 2, 1835–1841 (2012).

    Article  Google Scholar 

  42. Cheng, J. P., Chen, X., Ma, R., Liu, F. & Zhang, X. B. A facile method to fabricate porous Co3O4 hierarchical microspheres. Mater. Charact. 62, 775–780 (2011).

    Article  Google Scholar 

  43. Biesinger, M. C. et al. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl. Surf. Sci. 257, 2717–2730 (2011).

    Article  Google Scholar 

  44. Khassin, A. A. et al. Metal–support interactions in cobalt–aluminum co-precipitated catalysts: XPS and CO adsorption studies. J. Mol. Catal. Chem. 175, 189–204 (2001).

    Article  Google Scholar 

  45. Moulder, J. F., Stickle, W. F., Sobol, P. E. & Moben, K. D. Handbook of X-Ray Photoelectron Spectroscopy (Perkin-Elmer Corporation, 1992).

  46. Stoch, J. & Gablankowska-Kukucz, J. The effect of carbonate contaminations on the XPS O 1s band structure in metal oxides. Surf. Interface Anal. 17, 165–167 (1991).

    Article  Google Scholar 

  47. Zeng, X., Li, J. & Singh, N. Recycling of spent lithium-ion battery: a critical review. Crit. Rev. Environ. Sci. Technol. 44, 1129–1165 (2014).

    Article  Google Scholar 

  48. Wanger, T. C. The lithium future—resources, recycling, and the environment: the lithium future. Conserv. Lett. 4, 202–206 (2011).

    Article  Google Scholar 

  49. Harifi-Mood, A. R. & Buchner, R. Density, viscosity, and conductivity of choline chloride + ethylene glycol as a deep eutectic solvent and its binary mixtures with dimethyl sulfoxide. J. Mol. Liq. 225, 689–695 (2017).

    Article  Google Scholar 

  50. Wang, M.-M., Zhang, C.-C. & Zhang, F.-S. An environmental benign process for cobalt and lithium recovery from spent lithium-ion batteries by mechanochemical approach. Waste Manage. 51, 239–244 (2016).

    Article  Google Scholar 

  51. Fan, B., Chen, X., Zhou, T., Zhang, J. & Xu, B. A sustainable process for the recovery of valuable metals from spent lithium-ion batteries. Waste Manage. Res. 34, 474–481 (2016).

    Article  Google Scholar 

  52. Bhargava, S., Pownceby, M. & Ram, R. Hydrometallurgy (MDPI, 2017).

  53. Jo, H., Jo, H., Rha, S. & Lee, P.-K. Direct aqueous mineral carbonation of waste slate using ammonium salt solutions. Metals 5, 2413–2427 (2015).

    Article  Google Scholar 

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Acknowledgements

The authors thank A. Kabbani and A. Puthirath for useful discussion, and L. Alexander for assistance with the NMC dissolution experiments. M.K.T. acknowledges the National Science Foundation for continued support and funding. This study is based on work supported by the National Science Foundation Graduate Research Fellowship Program under grant number 1450681. Any opinions, findings, conclusions or recommendations expressed are those of the authors and do not necessarily reflect the views of the National Science Foundation.

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Authors and Affiliations

  1. Rice University, Houston, TX, USA

    Mai K. Tran, Marco-Tulio F. Rodrigues, Keiko Kato, Ganguli Babu & Pulickel M. Ajayan

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  1. Mai K. Tran
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Contributions

M.-T.F.R. conceived of the experimental design. M.K.T. performed the experiments and, alongside M.-T.F.R., co-wrote the paper and analysed the data. K.K. assisted in figure creation, as well as XPS and electrochemical experimentation and analysis. P.M.A. and G.B. conceived of and contributed to the overall project planning.

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Correspondence to Ganguli Babu or Pulickel M. Ajayan.

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Supplementary Discussion, Supplementary Tables 1–3, Supplementary Figures 1–6, Supplementary References

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Tran, M.K., Rodrigues, MT.F., Kato, K. et al. Deep eutectic solvents for cathode recycling of Li-ion batteries. Nat Energy 4, 339–345 (2019). https://doi.org/10.1038/s41560-019-0368-4

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