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Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries


A critical challenge for the commercialization of layer-structured nickel-rich lithium transition metal oxide cathodes for battery applications is their capacity and voltage fading, which originate from the disintegration and lattice phase transition of the cathode particles. The general approach of cathode particle surface modification could partially alleviate the degradation associated with surface processes, but it still fails to resolve this critical barrier. Here, we report that infusing the grain boundaries of cathode secondary particles with a solid electrolyte dramatically enhances the capacity retention and voltage stability of the cathode. We find that the solid electrolyte infused in the boundaries not only acts as a fast channel for lithium-ion transport, it also, more importantly, prevents penetration of the liquid electrolyte into the boundaries, and consequently eliminates the detrimental factors, which include cathode–liquid electrolyte interfacial reactions, intergranular cracking and layered-to-spinel phase transformation. This grain-boundary engineering approach provides design ideas for advanced cathodes for batteries.

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Fig. 1: Effects of LPO infusion on the electrochemical performance.
Fig. 2: Tracking the spatial distribution of LPO prior to battery cycling.
Fig. 3: Infusion of LPO into secondary particles eliminates intergranular cracking.
Fig. 4: Infusion of LPO into secondary particles eliminates structural degradation.


  1. Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

    Article  Google Scholar 

  2. Etacheri, V., Marom, R., Elazari, R., Salitra, G. & Aurbach, D. Challenges in the development of advanced Li-ion batteries: a review. Energy Environ. Sci. 4, 3243–3262 (2011).

    Article  Google Scholar 

  3. Zhou, Y.-N. et al. Tuning charge–discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries. Nat. Commun. 5, 5381 (2014).

    Article  Google Scholar 

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

    Article  Google Scholar 

  5. Li, W., Song, B. & Manthiram, A. High-voltage positive electrode materials for lithium-ion batteries. Chem. Soc. Rev. 46, 3006–3059 (2017).

    Article  Google Scholar 

  6. Liu, J. & Sun, X. Elegant design of electrode and electrode/electrolyte interface in lithium-ion batteries by atomic layer deposition. Nanotechnology 26, 024001 (2015).

    Article  Google Scholar 

  7. Manthiram, A., Knight, J. C., Myung, S. T., Oh, S. M. & Sun, Y. K. Nickel-rich and lithium-rich layered oxide cathodes: progress and perspectives. Adv. Energy Mater. 6, 1501010 (2016).

    Article  Google Scholar 

  8. Lee, E.-J. et al. Development of microstrain in aged lithium transition metal oxides. Nano Lett. 14, 4873–4880 (2014).

    Article  Google Scholar 

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

    Article  Google Scholar 

  10. Wang, Y. et al. Ti-substituted tunnel-type Na0.44MnO2 oxide as a negative electrode for aqueous sodium-ion batteries. Nat. Commun. 6, 6401 (2015).

    Article  Google Scholar 

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

    Article  Google Scholar 

  12. Cresce, A. V., Russell, S. M., Baker, D. R., Gaskell, K. J. & Xu, K. In situ and quantitative characterization of solid electrolyte interphases. Nano Lett. 14, 1405–1412 (2014).

    Article  Google Scholar 

  13. Kim, H., Kim, M. G., Jeong, H. Y., Nam, H. & Cho, J. A new coating method for alleviating surface degradation of LiNi0.6Co0.2Mn0.2O2 cathode material: nanoscale surface treatment of primary particles. Nano Lett. 15, 2111–2119 (2015).

    Article  Google Scholar 

  14. Luo, J., Cheng, H. K., Asl, K. M., Kiely, C. J. & Harmer, M. P. The role of a bilayer interfacial phase on liquid metal embrittlement. Science 333, 1730–1733 (2011).

    Article  Google Scholar 

  15. Cho, J., Wang, C. M., Chan, H. M., Rickman, J. M. & Harmer, M. P. Role of segregating dopants on the improved creep resistance of aluminum oxide. Acta Mater. 47, 4197–4207 (1999).

    Article  Google Scholar 

  16. Buban, J. P. et al. Grain boundary strengthening in alumina by rare earth impurities. Science 311, 212–215 (2006).

    Article  Google Scholar 

  17. Shibata, N. et al. Observation of rare-earth segregation in silicon nitride ceramics at subnanometre dimensions. Nature 428, 730–733 (2004).

    Article  Google Scholar 

  18. Appapillai, A. T., Mansour, A. N., Cho, J. & Shao-Horn, Y. Microstructure of LiCoO2 with and without 'AlPO4' nanoparticle coating: combined STEM and XPS studies. Chem. Mater. 19, 5748–5757 (2007).

    Article  Google Scholar 

  19. Lee, Y. et al. Facile formation of a Li3PO4 coating layer during the synthesis of a lithium-rich layered oxide for high-capacity lithium-ion batteries. J. Power Sources 315, 284–293 (2016).

    Article  Google Scholar 

  20. Sun, K. & Dillon, S. J. A mechanism for the improved rate capability of cathodes by lithium phosphate surficial films. Electrochem. Commun. 13, 200–202 (2011).

    Article  Google Scholar 

  21. Li, X. et al. Atomic layer deposition of solid-state electrolyte coated cathode materials with superior high-voltage cycling behavior for lithium ion battery application. Energy Environ. Sci. 7, 768–778 (2014).

    Article  Google Scholar 

  22. 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).

    Article  Google Scholar 

  23. Bak, S.-M. et al. Structural changes and thermal stability of charged LiNixMnyCozO2 cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy. ACS Appl. Mater. Interfaces 6, 22594–22601 (2014).

    Article  Google Scholar 

  24. Lim, J.-M. et al. Intrinsic origins of crack generation in Ni-rich LiNi0.8Co0.1Mn0.1O2 layered oxide cathode material. Sci. Rep. 7, 39669 (2017).

    Article  Google Scholar 

  25. Wang, H., Jang, Y. I., Huang, B., Sadoway, D. R. & Chiang, Y. M. TEM study of electrochemical cycling‐induced damage and disorder in LiCoO2 cathodes for rechargeable lithium batteries. J. Electrochem. Soc. 146, 473–480 (1999).

    Article  Google Scholar 

  26. 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).

    Article  Google Scholar 

  27. Ryu, H.-H., Park, K.-J., Yoon, C. S. & Sun, Y.-K. Capacity fading of Ni-rich Li[NixCoyMn1–xy]O2 (0.6 ≤ x ≤ 0.95) cathodes for high-energy-density lithium-ion batteries: bulk or surface degradation? Chem. Mater. 30, 1155–1163 (2018).

    Article  Google Scholar 

  28. Yan, P. et al. Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries. Nat. Commun. 8, 14101 (2017).

    Article  Google Scholar 

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We thank R. Liu and Y. Yang from Xiamen University for the DSC test and M. Sui for support on the TEM analysis. This work is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy (DOE) under contract no. DE-AC02-05CH11231, subcontract no. 18769 and no. 6951379 under the Advanced Battery Materials Research program. The microscopic analysis in this work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the DOE under contract DE-AC05-76RL01830. Solid-state electrolyte coating by ALD was conducted in the lab of X.S. and is financially supported by the Nature Sciences and Engineering Research Council of Canada Program, Canada Research Chair Program, Canada Foundation for Innovation and the University of Western Ontario. Part of ALD coating was done in BJUT (Y.Z.) under the support of National Natural Science Foundation of China (21676005). P.Y. thanks the National Natural Science Fund for Innovative Research Groups (grant no. 51621003) and the National Key Research and Development Program of China (grant no. 2016YFB0700700).

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Authors and Affiliations



C.W., J.Z. and J.-G.Z. initiated this research project. J.Z. and J.L. synthesized the cathode materials. J.L., B.W., X.C., Y.Z. and X.S. carried out the ALD coating. J.Z. and X.C. performed battery tests. P.Y. conducted the TEM and SEM analyses. P.Y., J.Z., C.W. and J.-G.Z. prepared the manuscript with the input from all the other co-authors.

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Correspondence to Xueliang Sun, Chongmin Wang or Ji-Guang Zhang.

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The authors declare no competing interests.

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Yan, P., Zheng, J., Liu, J. 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).

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