Evolution of lattice structure and chemical composition of the surface reconstruction layer in Li1.2Ni0.2Mn0.6O2 cathode material for lithium ion batteries

Pengfei Yan, Anmin Nie, Jianming Zheng, Yungang Zhou, Dongping Lu, Xiaofeng Zhang, Rui Xu, Ilias Belharouak, Xiaotao Zu, Jie Xiao, Khalil Amine, Jun Liu, Fei Gao, Reza Shahbazian-Yassar, Ji Guang Zhang, Chong Min Wang

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Abstract

Voltage and capacity fading of layer structured lithium and manganese rich (LMR) transition metal oxide is directly related to the structural and composition evolution of the material during the cycling of the battery. However, understanding such evolution at atomic level remains elusive. On the basis of atomic level structural imaging, elemental mapping of the pristine and cycled samples, and density functional theory calculations, it is found that accompanying the hoping of Li ions is the simultaneous migration of Ni ions toward the surface from the bulk lattice, leading to the gradual depletion of Ni in the bulk lattice and thickening of a Ni enriched surface reconstruction layer (SRL). Furthermore, Ni and Mn also exhibit concentration partitions within the thin layer of SRL in the cycled samples where Ni is almost depleted at the very surface of the SRL, indicating the preferential dissolution of Ni ions in the electrolyte. Accompanying the elemental composition evolution, significant structural evolution is also observed and identified as a sequential phase transition of C2/m →I41 → Spinel. For the first time, it is found that the surface facet terminated with pure cation/anion is more stable than that with a mixture of cation and anion. These findings firmly established how the elemental species in the lattice of LMR cathode transfer from the bulk lattice to surface layer and further into the electrolyte, clarifying the long-standing confusion and debate on the structure and chemistry of the surface layer and their correlation with the voltage fading and capacity decaying of LMR cathode. Therefore, this work provides critical insights for design of cathode materials with both high capacity and voltage stability during cycling.

Original languageEnglish
Pages (from-to)514-522
Number of pages9
JournalNano Letters
Volume15
Issue number1
DOIs
Publication statusPublished - 14 Jan 2015

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Keywords

  • ion migration
  • lithium ion battery
  • LMR cathode
  • Ni surface segregation
  • surface reconstruction
  • voltage fading

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Bioengineering
  • Chemistry(all)
  • Materials Science(all)
  • Mechanical Engineering

Cite this

Yan, P., Nie, A., Zheng, J., Zhou, Y., Lu, D., Zhang, X., Xu, R., Belharouak, I., Zu, X., Xiao, J., Amine, K., Liu, J., Gao, F., Shahbazian-Yassar, R., Zhang, J. G., & Wang, C. M. (2015). Evolution of lattice structure and chemical composition of the surface reconstruction layer in Li1.2Ni0.2Mn0.6O2 cathode material for lithium ion batteries. Nano Letters, 15(1), 514-522. https://doi.org/10.1021/nl5038598