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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Larcher, D. & Tarascon, J. M. Towards greener and more sustainable batteries for electrical energy storage. Nat. Chem. 7, 19–29 (2015).
Choi, J. W. & Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 1, 16013 (2016).
Yoon, M. et al. Reactive boride infusion stabilizes Ni-rich cathodes for lithium-ion batteries. Nat. Energy 6, 362–371 (2021).
Namkoong, B. et al. High-energy Ni-rich cathode materials for long-range and long-life electric vehicles. Adv. Energy Mater. 12, 2200615 (2022).
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).
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).
Li, H. et al. Toward high-energy Mn-based disordered-rocksalt Li-ion cathodes. Joule 6, 53–91 (2022).
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).
Li, W. et al. A sulfur cathode with pomegranate-like cluster structure. Adv. Energy Mater. 5, 1500211 (2015).
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).
Kim, J. et al. Nickel-rich cathodes: prospect and reality of Ni-rich cathode for commercialization. Adv. Energy Mater. 8, 1870023 (2018).
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).
You, B. et al. Research progress of single-crystal nickel-rich cathode materials for lithium ion batteries. Small Methods 5, 2100234 (2021).
Ryu, H.-H. et al. Capacity fading mechanisms in Ni-rich single-crystal NCM cathodes. ACS Energy Lett. 6, 2726–2734 (2021).
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).
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).
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).
Bi, Y. et al. Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode. Science 370, 1313–1317 (2020).
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).
James, S. L. et al. Mechanochemistry: opportunities for new and cleaner synthesis. Chem. Soc. Rev. 41, 413–447 (2012).
Friščić, T., Mottillo, C. & Titi, H. M. Mechanochemistry for synthesis. Angew. Chem. Int. Ed. 59, 1018–1029 (2020).
Schlem, R. et al. Energy storage materials for solid-state batteries: design by mechanochemistry. Adv. Energy Mater. 11, 2101022 (2021).
Hong, J. et al. Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides. Nat. Mater. 18, 256–265 (2019).
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).
Lee, J. et al. Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials. Nature 556, 185–190 (2018).
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).
Pennycook, S. J. & Nellist, P. D. Scanning Transmission Electron Microscopy: Imaging and Analysis (Springer Science & Business Media, 2011).
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).
Gu, M. et al. Conflicting roles of nickel in controlling cathode performance in lithium ion batteries. Nano Lett. 12, 5186–5191 (2012).
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).
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).
Hwang, J. et al. Excess-Li localization triggers chemical irreversibility in Li- and Mn-rich layered oxides. Adv. Mater. 32, 2001944 (2020).
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).
Yan, P. et al. Injection of oxygen vacancies in the bulk lattice of layered cathodes. Nat. Nanotechnol. 14, 602–608 (2019).
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).
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).
Freunberger, S. A. et al. Reactions in the rechargeable lithium–O2 battery with alkyl carbonate electrolytes. J. Am. Chem. Soc. 133, 8040–8047 (2011).
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).
Xiao, B. et al. Revealing the atomic origin of heterogeneous Li-ion diffusion by probing Na. Adv. Mater. 31, 1805889 (2019).
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).
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).
Dong, Y. & Li, J. Oxide cathodes: functions, instabilities, self healing, and degradation mitigations. Chem. Rev. 123, 811–833 (2023).
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).
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).
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).
Lin, F. et al. Profiling the nanoscale gradient in stoichiometric layered cathode particles for lithium-ion batteries. Energy Environ. Sci. 7, 3077–3085 (2014).
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).
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).
Bale, C. W. et al. FactSage thermochemical software and databases, 2010-2016. Calphad 54, 35–53 (2016).
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.
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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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