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Eutectic salt-assisted planetary centrifugal deagglomeration for single-crystalline cathode synthesis

Nature Energy volume 8, pages 482–491 (2023)Cite this article

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Abstract

Single-crystalline layered cathodes are often desirable for advanced lithium-ion batteries. However, constrained by the accessible temperature range to prevent lithium evaporation, lattice defects and particle agglomerations, the production of single-crystalline cathodes with high phase purity, good electrochemical performance and scalability remains challenging. Here we invent a new mechanochemical activation process that offers a general solution to the conundrum of synthesizing coarse single-crystal cathodes with Li-/Mn-rich or Ni-rich chemistry, which differs from the equipment- and energy-intense and long-duration mechanochemical routes that are difficult to scale up. Our approach is based on interfacial reactive wetting, mediated by transient eutectic salts in situ melted by moderate mechanical agitations, to form a colloidal suspension of nanosized oxides dispersed in liquified lithium salts. It efficiently deagglomerates the polycrystalline precursors, repacks the crystals and homogenizes the lithium-salt distribution, thus enabling facile particle coarsening later into the single-crystalline morphology with improved electrochemical performance.

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Fig. 1: Planetary centrifugal deagglomeration for single-crystalline cathode synthesis.
Fig. 2: Secondary-particle deagglomeration by molten lithium salts during planetary centrifugal mixing.
Fig. 3: Mechanochemical reactive wetting at nanoscale.
Fig. 4: Structural characterizations of micro-sized single-crystalline LMR.
Fig. 5: Superior electrochemical performance of SC-LMR over PC-LMR.
Fig. 6: Demonstration of single-crystalline Ni-rich layered cathodes.

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Data generated and analysed in the present work are available in the paper and Supplementary Information. Source data are provided with this paper.

References

  1. Larcher, D. & Tarascon, J. M. Towards greener and more sustainable batteries for electrical energy storage. Nat. Chem. 7, 19–29 (2015).

    Article  Google Scholar 

  2. Choi, J. W. & Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 1, 16013 (2016).

    Article  Google Scholar 

  3. Yoon, M. et al. Reactive boride infusion stabilizes Ni-rich cathodes for lithium-ion batteries. Nat. Energy 6, 362–371 (2021).

    Article  Google Scholar 

  4. Namkoong, B. et al. High-energy Ni-rich cathode materials for long-range and long-life electric vehicles. Adv. Energy Mater. 12, 2200615 (2022).

    Article  Google Scholar 

  5. Xu, G.-L. et al. Building ultraconformal protective layers on both secondary and primary particles of layered lithium transition metal oxide cathodes. Nat. Energy 4, 484–494 (2019).

    Article  Google Scholar 

  6. Zhang, J. et al. Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands. Nat. Commun. 12, 3071 (2021).

    Article  Google Scholar 

  7. Li, H. et al. Toward high-energy Mn-based disordered-rocksalt Li-ion cathodes. Joule 6, 53–91 (2022).

    Article  Google Scholar 

  8. Zhang, M. et al. Pushing the limit of 3d transition metal-based layered oxides that use both cation and anion redox for energy storage. Nat. Rev. Mater. 7, 522–540 (2022).

    Article  Google Scholar 

  9. Li, W. et al. A sulfur cathode with pomegranate-like cluster structure. Adv. Energy Mater. 5, 1500211 (2015).

    Article  Google Scholar 

  10. Xue, W. et al. Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte. Nat. Energy 6, 495–505 (2021).

    Article  Google Scholar 

  11. Kim, J. et al. Nickel-rich cathodes: prospect and reality of Ni-rich cathode for commercialization. Adv. Energy Mater. 8, 1870023 (2018).

    Article  Google Scholar 

  12. Hwang, J. et al. Lattice-oxygen-stabilized Li- and Mn-rich cathodes with sub-micrometer particles by modifying the excess-Li distribution. Adv. Mater. 33, 2100352 (2021).

    Article  Google Scholar 

  13. You, B. et al. Research progress of single-crystal nickel-rich cathode materials for lithium ion batteries. Small Methods 5, 2100234 (2021).

    Article  Google Scholar 

  14. Ryu, H.-H. et al. Capacity fading mechanisms in Ni-rich single-crystal NCM cathodes. ACS Energy Lett. 6, 2726–2734 (2021).

    Article  Google Scholar 

  15. Li, H. et al. Synthesis of single crystal LiNi0.88Co0.09Al0.03O2 with a two-step lithiation method. J. Electrochem. Soc. 166, A1956–A1963 (2019).

    Article  Google Scholar 

  16. Liu, A. et al. Synthesis of Co-free Ni-rich single crystal positive electrode materials for lithium ion batteries: part I. Two-step lithiation method for Al- or Mg-doped LiNiO2. J. Electrochem. Soc. 168, 040531 (2021).

    Article  Google Scholar 

  17. Wang, T. et al. Synthesis and manipulation of single-crystalline lithium nickel manganese cobalt oxide cathodes: a review of growth mechanism. Front. Chem. 8, 747 (2020).

    Article  Google Scholar 

  18. Bi, Y. et al. Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode. Science 370, 1313–1317 (2020).

    Article  Google Scholar 

  19. Kubota, K., Pang, Y., Miura, A. & Ito, H. Redox reactions of small organic molecules using ball milling and piezoelectric materials. Science 366, 1500–1504 (2019).

    Article  Google Scholar 

  20. James, S. L. et al. Mechanochemistry: opportunities for new and cleaner synthesis. Chem. Soc. Rev. 41, 413–447 (2012).

    Article  Google Scholar 

  21. Friščić, T., Mottillo, C. & Titi, H. M. Mechanochemistry for synthesis. Angew. Chem. Int. Ed. 59, 1018–1029 (2020).

    Article  Google Scholar 

  22. Schlem, R. et al. Energy storage materials for solid-state batteries: design by mechanochemistry. Adv. Energy Mater. 11, 2101022 (2021).

    Article  Google Scholar 

  23. Hong, J. et al. Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides. Nat. Mater. 18, 256–265 (2019).

    Article  Google Scholar 

  24. Clément, R. J., Lun, Z. & Ceder, G. Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes. Energy Environ. Sci. 13, 345–373 (2020).

    Article  Google Scholar 

  25. Lee, J. et al. Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials. Nature 556, 185–190 (2018).

    Article  Google Scholar 

  26. Janz, G. J. Thermodynamic and transport properties for molten salts: correlation equations for critically evaluated density, surface tension, electrical conductance, and viscosity data. J. Phys. Chem. Ref. Data 17, 1–309 (1988).

    Google Scholar 

  27. Pennycook, S. J. & Nellist, P. D. Scanning Transmission Electron Microscopy: Imaging and Analysis (Springer Science & Business Media, 2011).

  28. Park, H. et al. In situ multiscale probing of the synthesis of a Ni-rich layered oxide cathode reveals reaction heterogeneity driven by competing kinetic pathways. Nat. Chem. 14, 614–622 (2022).

    Article  Google Scholar 

  29. Gu, M. et al. Conflicting roles of nickel in controlling cathode performance in lithium ion batteries. Nano Lett. 12, 5186–5191 (2012).

    Article  Google Scholar 

  30. Chen, H., Dawson, J. A. & Harding, J. H. Effects of cationic substitution on structural defects in layered cathode materials LiNiO2. J. Mater. Chem. A 2, 7988–7996 (2014).

    Article  Google Scholar 

  31. Xiao, P. et al. Effects of oxygen pressurization on Li+/Ni2+ cation mixing and the oxygen vacancies of LiNi0.8Co0.15Al0.05O2 cathode materials. ACS Appl. Mater. Interfaces 14, 31851–31861 (2022).

    Article  Google Scholar 

  32. Hwang, J. et al. Excess-Li localization triggers chemical irreversibility in Li- and Mn-rich layered oxides. Adv. Mater. 32, 2001944 (2020).

    Article  Google Scholar 

  33. Ku, K. et al. Suppression of voltage decay through manganese deactivation and nickel redox buffering in high-energy layered lithium-rich electrodes. Adv. Energy Mater. 8, 1800606 (2018).

    Article  Google Scholar 

  34. Yan, P. et al. Injection of oxygen vacancies in the bulk lattice of layered cathodes. Nat. Nanotechnol. 14, 602–608 (2019).

    Article  Google Scholar 

  35. Zhu, Z. et al. Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment. Nat. Energy 4, 1049–1058 (2019).

    Article  Google Scholar 

  36. Dong, Y., Qi, L., Alvarez, A., Li, J. & Chen, I. W. Enhanced mobility of cations and anions in the redox state: the polaronium mechanism. Acta Mater. 232, 117941 (2022).

    Article  Google Scholar 

  37. Freunberger, S. A. et al. Reactions in the rechargeable lithium–O2 battery with alkyl carbonate electrolytes. J. Am. Chem. Soc. 133, 8040–8047 (2011).

    Article  Google Scholar 

  38. Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M. Li–O2 and Li–S batteries with high energy storage. Nat. Mater. 11, 19–29 (2012).

    Article  Google Scholar 

  39. Xiao, B. et al. Revealing the atomic origin of heterogeneous Li-ion diffusion by probing Na. Adv. Mater. 31, 1805889 (2019).

    Article  Google Scholar 

  40. Jung, R., Metzger, M., Maglia, F., Stinner, C. & Gasteiger, H. A. Chemical versus electrochemical electrolyte oxidation on NMC111, NMC622, NMC811, LNMO, and conductive carbon. J. Phys. Chem. Lett. 8, 4820–4825 (2017).

    Article  Google Scholar 

  41. Zhan, C., Wu, T., Lu, J. & Amine, K. Dissolution, migration, and deposition of transition metal ions in Li-ion batteries exemplified by Mn-based cathodes–a critical review. Energy Environ. Sci. 11, 243–257 (2018).

    Article  Google Scholar 

  42. Dong, Y. & Li, J. Oxide cathodes: functions, instabilities, self healing, and degradation mitigations. Chem. Rev. 123, 811–833 (2023).

    Article  Google Scholar 

  43. Xu, C. et al. Bulk fatigue induced by surface reconstruction in layered Ni-rich cathodes for Li-ion batteries. Nat. Mater. 20, 84–92 (2021).

    Article  Google Scholar 

  44. Li, W., Asl, H. Y., Xie, Q. & Manthiram, A. Collapse of LiNi1–x–yCoxMnyO2 lattice at deep charge irrespective of nickel content in lithium-ion batteries. J. Am. Chem. Soc. 141, 5097–5101 (2019).

    Article  Google Scholar 

  45. Liu, X. et al. Essential effect of the electrolyte on the mechanical and chemical degradation of LiNi0.8Co0.15Al0.05O2 cathodes upon long-term cycling. J. Mater. Chem. A 9, 2111–2119 (2021).

    Article  Google Scholar 

  46. Lin, F. et al. Profiling the nanoscale gradient in stoichiometric layered cathode particles for lithium-ion batteries. Energy Environ. Sci. 7, 3077–3085 (2014).

    Article  Google Scholar 

  47. Kang, Y.-S. et al. Revealing the structural degradation mechanism of the Ni-rich cathode surface: how thick is the surface? J. Power Sources 490, 229542 (2021).

    Article  Google Scholar 

  48. Kang, S. J., Mori, T., Narizuka, S., Wilcke, W. & Kim, H.-C. Deactivation of carbon electrode for elimination of carbon dioxide evolution from rechargeable lithium–oxygen cells. Nat. Commun. 5, 3937 (2014).

    Article  Google Scholar 

  49. Bale, C. W. et al. FactSage thermochemical software and databases, 2010-2016. Calphad 54, 35–53 (2016).

    Article  Google Scholar 

Download references

Acknowledgements

M.Y. acknowledges support by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2022R1A6A3A03069190). J.L. acknowledges support by Defense Advanced Research Projects Agency (DARPA) MINT programme under contract number HR001122C0097.

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Author notes

  1. These authors contributed equally: Moonsu Yoon, Yanhao Dong.

Authors and Affiliations

  1. Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Moonsu Yoon, Yanhao Dong, Baoming Wang, Jin-Sung Park & Ju Li

  2. Department of Energy Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Moonsu Yoon, Jaeseong Hwang, Jaehyun Park, Seok Ju Kang & Jaephil Cho

  3. State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, China

    Yanhao Dong

  4. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Yimeng Huang, Junghwa Kim & Ju Li

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Contributions

M.Y., Y.D., J.C. and J.L. conceived the project. M.Y. and Y.D. designed the experiments and analysed the data. M.Y. synthesized the materials and conducted electrochemical testing. Y.H. and J.-S.P. conducted SEM and ex situ XRD measurements. B.W., J.K. and J.H. conducted focused ion beam and TEM measurements. J.P. and S.J.K. conducted in situ DEMS analysis. M.Y., Y.D., J.C. and J.L. wrote the paper. All authors discussed and contributed to the writing.

Corresponding authors

Correspondence to Jaephil Cho or Ju Li.

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Competing interests

M.Y., Y.D., J.C. and J.L declare that this work has been filed as US Provisional Patent Application (US 63/484,989). The other authors declare no competing interests.

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Supplementary Figs. 1–26, Tables 1–9, Note 1 and References.

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Yoon, M., Dong, Y., Huang, Y. et al. Eutectic salt-assisted planetary centrifugal deagglomeration for single-crystalline cathode synthesis. Nat Energy 8, 482–491 (2023). https://doi.org/10.1038/s41560-023-01233-8

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