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Reactive boride infusion stabilizes Ni-rich cathodes for lithium-ion batteries


Engineered polycrystalline electrodes are critical to the cycling stability and safety of lithium-ion batteries, yet it is challenging to construct high-quality coatings at both the primary- and secondary-particle levels. Here we present a room-temperature synthesis route to achieve a full surface coverage of secondary particles and facile infusion into grain boundaries, and thus offer a complete ‘coating-plus-infusion’ strategy. Cobalt boride metallic glass was successfully applied to a Ni-rich layered cathode LiNi0.8Co0.1Mn0.1O2. It dramatically improved the rate capability and cycling stability, including under high-discharge-rate and elevated-temperature conditions and in pouch full-cells. The superior performance originates from a simultaneous suppression of the microstructural degradation of the intergranular cracking and of side reactions with the electrolyte. Atomistic simulations identified the critical role of strong selective interfacial bonding, which offers not only a large chemical driving force to ensure uniform reactive wetting and facile infusion, but also lowers the surface/interface oxygen activity, which contributes to the exceptional mechanical and electrochemical stabilities of the infused electrode.

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Fig. 1: ‘Coating-plus-infusion’ microstructure for CoxB-infused NCM.
Fig. 2: Uniform amorphous CoxB infusion at the NCM surface and GBs.
Fig. 3: Superior electrochemical performance of CoxB–NCM over pristine NCM.
Fig. 4: CoxB infusion simultaneously suppresses microstructural degradation and side reactions.
Fig. 5: Morphology and chemical characteristics of cycled LMA.
Fig. 6: Strong interfacial bonding suppresses oxygen activity.

Data availability

Data generated and analysed in this study are included in the manuscript and its Supplementary Information.


  1. 1.

    Nitta, N., Wu, F., Lee, J. T. & Yushin, G. Li-ion battery materials: present and future. Mater. Today 18, 252–264 (2015).

    Google Scholar 

  2. 2.

    Kim, J. et al. Prospect and reality of Ni‐rich cathode for commercialization. Adv. Energy Mater. 8, 1702028 (2018).

    Google Scholar 

  3. 3.

    Li, W., Erickson, E. M. & Manthiram, A. High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat. Energy 5, 26–34 (2020).

    Google Scholar 

  4. 4.

    Edström, K., Gustafsson, T. & Thomas, J. O. The cathode–electrolyte interface in the Li-ion battery. Electrochim. Acta 50, 397–403 (2004).

    Google Scholar 

  5. 5.

    Sharifi-Asl, S., Lu, J., Amine, K. & Shahbazian-Yassar, R. Oxygen release degradation in Li-ion battery cathode materials: mechanisms and mitigating approaches. Adv. Energy Mater. 9, 1900551 (2019).

    Google Scholar 

  6. 6.

    Xie, Q., Li, W. & Manthiram, A. A Mg-doped high-nickel layered oxide cathode enabling safer, high-energy-density Li-ion batteries. Chem. Mater. 31, 938–946 (2019).

    Google Scholar 

  7. 7.

    Schipper, F. et al. From surface ZrO2 coating to bulk Zr doping by high temperature annealing of nickel-rich lithiated oxides and their enhanced electrochemical performance in lithium ion batteries. Adv. Energy Mater. 8, 1701682 (2018).

    Google Scholar 

  8. 8.

    Xu, X. et al. Radially oriented single-crystal primary nanosheets enable ultrahigh rate and cycling properties of LiNi0.8Co0.1Mn0.1O2 cathode material for lithium-ion batteries. Adv. Energy Mater. 9, 1803963 (2019).

    Google Scholar 

  9. 9.

    Kim, J. et al. A highly stabilized nickel-rich cathode material by nanoscale epitaxy control for high-energy lithium-ion batteries. Energy Environ. Sci. 11, 1449–1459 (2018).

    Google Scholar 

  10. 10.

    Yan, P. et al. Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries. Nat. Energy 3, 600–605 (2018).

    Google Scholar 

  11. 11.

    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).

    Google Scholar 

  12. 12.

    Li, L. et al. Hidden subsurface reconstruction and its atomic origins in layered oxide cathodes. Nano Lett. 20, 2756–2762 (2020).

    Google Scholar 

  13. 13.

    Liu, H. et al. Intergranular cracking as a major cause of long-term capacity fading of layered cathodes. Nano Lett. 17, 3452–3457 (2017).

    Google Scholar 

  14. 14.

    Yan, P. et al. Coupling of electrochemically triggered thermal and mechanical effects to aggravate failure in a layered cathode. Nat. Commun. 9, 2437 (2018).

    Google Scholar 

  15. 15.

    Watanabe, S., Kinoshita, M., Hosokawa, T., Morigaki, K. & Nakura, K. Capacity fade of LiAlyNi1−xyCoxO2 cathode for lithium-ion batteries during accelerated calendar and cycle life tests (surface analysis of LiAlyNi1−xyCoxO2 cathode after cycle tests in restricted depth of discharge ranges). J. Power Sources 258, 210–217 (2014).

    Google Scholar 

  16. 16.

    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).

    Google Scholar 

  17. 17.

    Freiberg, A. T. S., Roos, M. K., Wandt, J., de Vivie-Riedle, R. & Gasteiger, H. A. Singlet oxygen reactivity with carbonate solvents used for Li-ion battery electrolytes. J. Phys. Chem. A 122, 8828–8839 (2018).

    Google Scholar 

  18. 18.

    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).

    Google Scholar 

  19. 19.

    Huang, Y. et al. Lithium manganese spinel cathodes for lithium-ion batteries. Adv. Energy Mater. 11, 2000997 (2021).

    Google Scholar 

  20. 20.

    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).

    Google Scholar 

  21. 21.

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

    Google Scholar 

  22. 22.

    Armstrong, A. R. et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2. J. Am. Chem. Soc. 128, 8694–8698 (2006).

    Google Scholar 

  23. 23.

    House, R. A. et al. What triggers oxygen loss in oxygen redox cathode materials? Chem. Mater. 31, 3293–3300 (2019).

    Google Scholar 

  24. 24.

    Yoon, M. et al. Unveiling nickel chemistry in stabilizing high-voltage cobalt-rich cathodes for lithium-ion batteries. Adv. Funct. Mater. 30, 1907903 (2020).

    Google Scholar 

  25. 25.

    Jain, A. et al. Commentary: The Materials Project: a materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013).

    Google Scholar 

  26. 26.

    Mu, D. & Yang, C. Shen, B.-l. & Jiang, H. Oxidation resistance of borided pure cobalt. J. Alloy. Compd 479, 629–633 (2009).

    Google Scholar 

  27. 27.

    Yang, Y., Kushima, A., Han, W., Xin, H. & Li, J. Liquid-like, self-healing aluminum oxide during deformation at room temperature. Nano Lett. 18, 2492–2497 (2018).

    Google Scholar 

  28. 28.

    Li, J., Lenosky, T. J., Först, C. J. & Yip, S. Thermochemical and mechanical stabilities of the oxide scale of ZrB2+SiC and oxygen transport mechanisms. J. Am. Ceram. Soc. 91, 1475–1480 (2008).

    Google Scholar 

  29. 29.

    Hasegawa, R. & Ray, R. Iron–boron metallic glasses. J. Appl. Phys. 49, 4174–4179 (1978).

    Google Scholar 

  30. 30.

    Gaskell, P. H. A new structural model for amorphous transition metal silicides, borides, phosphides and carbides. J. Non-Cryst. Solids 32, 207–224 (1979).

    Google Scholar 

  31. 31.

    Masa, J. et al. Amorphous cobalt boride (Co2B) as a highly efficient nonprecious catalyst for electrochemical water splitting: oxygen and hydrogen evolution. Adv. Energy Mater. 6, 1502313 (2016).

    Google Scholar 

  32. 32.

    Deng, J. et al. Co–B nanoflakes as multifunctional bridges in ZnCo2O4 micro-/nanospheres for superior lithium storage with boosted kinetics and stability. Adv. Energy Mater. 9, 1803612 (2019).

    Google Scholar 

  33. 33.

    Jiang, B. et al. A mesoporous non-precious metal boride system: synthesis of mesoporous cobalt boride by strictly controlled chemical reduction. Chem. Sci. 11, 791–796 (2020).

    Google Scholar 

  34. 34.

    Chen, Z. et al. Study of cobalt boride-derived electrocatalysts for overall water splitting. Int. J. Hydrog. Energy 43, 6076–6087 (2018).

    Google Scholar 

  35. 35.

    Zhang, C. et al. Revealing the role of NH4VO3 treatment in Ni-rich cathode materials with improved electrochemical performance for rechargeable lithium-ion batteries. Nanoscale 10, 8820–8831 (2018).

    Google Scholar 

  36. 36.

    Yu, Y. et al. Optimal annealing of Al foil anode for prelithiation and full-cell cycling in Li-ion battery: the role of grain boundaries in lithiation/delithiation ductility. Nano Energy 67, 104274 (2020).

    Google Scholar 

  37. 37.

    Miller, D. J., Proff, C., Wen, J. G., Abraham, D. P. & Bareño, J. Observation of microstructural evolution in Li battery cathode oxide particles by in situ electron microscopy. Adv. Energy Mater. 3, 1098–1103 (2013).

    Google Scholar 

  38. 38.

    Kondrakov, A. O. et al. Anisotropic lattice strain and mechanical degradation of high- and low-nickel NCM cathode materials for Li-ion batteries. J. Phys. Chem. C. 121, 3286–3294 (2017).

    Google Scholar 

  39. 39.

    Kim, J. et al. Controllable solid electrolyte interphase in nickel‐rich cathodes by an electrochemical rearrangement for stable lithium‐ion batteries. Adv. Mater. 30, 1704309 (2018).

    Google Scholar 

  40. 40.

    Zhao, W. et al. High voltage operation of Ni‐rich NMC cathodes enabled by stable electrode/electrolyte interphases. Adv. Energy Mater. 8, 1800297 (2018).

    Google Scholar 

  41. 41.

    Yoon, W.-S. et al. Investigation of the charge compensation mechanism on the electrochemically Li-ion deintercalated Li1–xCo1/3Ni1/3Mn1/3O2 electrode system by combination of soft and hard X-ray absorption spectroscopy. J. Am. Chem. Soc. 127, 17479–17487 (2005).

    Google Scholar 

  42. 42.

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

    Google Scholar 

  43. 43.

    Yang, L., Ravdel, B. & Lucht, B. L. Electrolyte reactions with the surface of high voltage LiNi0.5Mn1.5O4 cathodes for lithium-ion batteries. Electrochem. Solid-State Lett. 13, A95–A97 (2010).

    Google Scholar 

  44. 44.

    Zheng, J. et al. Highly stable operation of lithium metal batteries enabled by the formation of a transient high-concentration electrolyte layer. Adv. Energy Mater. 6, 1502151 (2016).

    Google Scholar 

  45. 45.

    Li, W. et al. Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries. Nat. Commun. 8, 14589 (2017).

    Google Scholar 

  46. 46.

    Nguyen, T. T. D. et al. Understanding the thermal runaway of Ni-rich lithium-ion batteries. World Electr. Veh. J. 10, 79 (2019).

    Google Scholar 

  47. 47.

    Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).

    Google Scholar 

  48. 48.

    Seo, D.-H. et al. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nat. Chem. 8, 692–697 (2016).

    Google Scholar 

  49. 49.

    Luo, K. et al. Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen. Nat. Chem. 8, 684–691 (2016).

    Google Scholar 

  50. 50.

    Hashigami, S. et al. Improvement of cycleability and rate-capability of LiNi0.5Co0.2Mn0.3O2 cathode materials coated with lithium boron oxide by an antisolvent precipitation method. Chem. Sel. 4, 8676–8681 (2019).

    Google Scholar 

  51. 51.

    Park, J.-H. et al. Effect of residual lithium rearrangement on Ni-rich layered oxide cathodes for lithium-ion batteries. Energy Technol. 6, 1361–1369 (2018).

    Google Scholar 

  52. 52.

    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).

    Google Scholar 

  53. 53.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B: Condens. Matter Mater. Phys. 59, 1758 (1999).

    Google Scholar 

  54. 54.

    Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    Google Scholar 

  55. 55.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Google Scholar 

  56. 56.

    Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA + U study. Phys. Rev. B 57, 1505–1509 (1998).

    Google Scholar 

  57. 57.

    Jain, A. et al. Formation enthalpies by mixing GGA and GGA + U calculations. Phys. Rev. B 84, 045115 (2011).

    Google Scholar 

  58. 58.

    Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).

    Google Scholar 

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This work was supported by the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry & Energy (MOTIE) of the Republic of Korea (no. 20172410100140). 2020 Research Funds (1.200029.1) of the Ulsan National Institute of Science and Technology (UNIST) is also acknowledged. Y.D. and J.L. acknowledge support from the Department of Energy, Basic Energy Sciences, under award no. DE-SC0002633 (Chemomechanics of Far-From-Equilibrium Interfaces).

Author information




M.Y., Y.D., J.L. and J.C. conceived the project. M.Y. synthesized the materials and conducted the electrochemical testing. Y.D. conducted the simulations and theoretical analysis. M.Y. and J.H. conducted ex situ and in situ XRD measurements and analysis. H.C. and J.S. conducted the focused ion beam, TEM, SEM and XPS measurements. S.J.K. provided equipment for the DEMS measurements. M.Y. and K.A. assembled and tested the pouch-type full-cells. M.Y. and Y.D. analysed the data. M.Y., Y.D., J.L. and J.C. wrote the paper. All the authors discussed and contributed to the writing.

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Correspondence to Ju Li or Jaephil Cho.

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The authors declare no competing interests.

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Peer review information Nature Energy thanks Payam Kaghazchi, David Wood III and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–33, Tables 1–9 and references.

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

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