Design of Nickel-based cation-disordered rock-salt oxides: The effect of transition metal (M = V, Ti, Zr) substitution in LiNi0.5M0.5O2 binary systems

Musa Ali Cambaz, B. P. Vinayan, Holger Euchner, Rune E. Johnsen, Alexander A. Guda, Andrey Mazilkin, Yury V. Rusalev, A. L. Trigub, Axel Gross, M. Fichtner*

*Corresponding author for this work

Research output: Contribution to journalJournal articlepeer-review

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Abstract

Cation-disorderedoxides have been ignored as positive electrode material for a long time, due tostructurally limited lithium insertion/extraction capabilities. In this work, acase study is carried outon nickel based cation-disordered Fm-3m LiNi0.5M0.5O2 positive electrode materials.The present investigation targets tailoring the electrochemical properties fornickel basedcation-disordered rock-salt by electronic considerations. The compositionalspace for binary LiM+3O2 with metals active for +3/+4 redoxcouples are extended to ternary oxides with LiA0.5B0.5O2 with A=Ni+2 and B=Ti+4 , Zr+4 and V+4 in order to assess the impact of the differenttransition metal in the isostructural oxides. The direct synthesis of variousnew unknownternary nickel based Fm-3m cation-disordered rock-salt positiveelectrode materials ispresented with a particular focus on the LiNi0.5V0.5O2 system. This positive electrode materialfor Li ion batteries displays an average voltage of ~ 2.55 V and a highdischarge capacity of264 mAhg-1 corresponding to 0.94 Li. For appropriate cut-off voltages, a long cyclelife is achieved. The charge compensation mechanism is probed by XANES,confirming thereversible oxidation and reduction of V4+/V5+. The enhancement in theelectrochemical performanceswithin the presented compounds stresses the importance of mixedcationdisordered transitionmetal oxides with different electronic configuration.

Original languageEnglish
JournalA C S Applied Materials and Interfaces
Volume10
Issue number26
Pages (from-to)21957-21964
ISSN1944-8244
DOIs
Publication statusPublished - 2018

Keywords

  • Cation-disordered
  • Nickel-based
  • Cathode
  • Lithium-ion battery
  • Mechanochemical synthesis
  • Vanadium

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