Probing the Thermal-Driven Structural and Chemical Degradation of Ni-Rich Layered Cathodes by Co/Mn Exchange

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Xiang Liu
  • Gui-Liang Xu
  • Liang Yin
  • Inhui Hwang
  • Yan Li
  • Languang Lu
  • Wenqian Xu
  • Xuequan Zhang
  • Yanbin Chen
  • Cheng-Jun Sun
  • Zonghai Chen
  • Minggao Ouyang
  • Khalil Amine

Detail(s)

Original languageEnglish
Pages (from-to)19745-19753
Journal / PublicationJournal of the American Chemical Society
Volume142
Issue number46
Online published4 Nov 2020
Publication statusPublished - 18 Nov 2020
Externally publishedYes

Abstract

The intrinsic poor thermal stability of layered LiNixCoyMn1-x-yO2 (NCM) cathodes and the exothermic side reactions triggered by the associated oxygen release are the main safety threats for their large-scale implantation. In the NCM family, it is widely accepted that Ni is the stability troublemaker, while Mn has long been considered as a structure stabilizer, whereas the role of Co remains elusive. Here, via Co/Mn exchange in a Ni-rich LiNi0.83Co0.11Mn0.06O2 cathode, we demonstrate that the chemical and structural stability of the deep delithiated NCM cathodes are significantly dominated by Co rather than the widely reported Mn. Operando synchrotron X-ray characterization coupling with in situ mass spectrometry reveal that the Co4+ reduces prior to the reduction of Ni4+ and could thus prolong the Ni migration by occupying the tetrahedra sites and, hence, postpone the oxygen release and thermal failure. In contrast, the Mn itself is stable, but barely stabilizes the Ni4+. Our results highlight the importance of evaluating the intrinsic role of compositional tuning on the Ni-rich/Co-free layered oxide cathode materials to guarantee the safe operation of high-energy Li-ion batteries.

Citation Format(s)

Probing the Thermal-Driven Structural and Chemical Degradation of Ni-Rich Layered Cathodes by Co/Mn Exchange. / Liu, Xiang; Xu, Gui-Liang; Yin, Liang; Hwang, Inhui; Li, Yan; Lu, Languang; Xu, Wenqian; Zhang, Xuequan; Chen, Yanbin; Ren, Yang; Sun, Cheng-Jun; Chen, Zonghai; Ouyang, Minggao; Amine, Khalil.

In: Journal of the American Chemical Society, Vol. 142, No. 46, 18.11.2020, p. 19745-19753.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review