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.


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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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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 or Chongmin Wang or Ji-Guang Zhang.

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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). https://doi.org/10.1038/s41560-018-0191-3

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