Anionic Redox Activity in a Newly Zn-Doped Sodium Layered Oxide P2-Na2/3Mn1− yZnyO2 (0 < y < 0.23)

Xue Bai, Mariyappan Sathiya, Beatriz Mendoza-Sánchez, Antonella Iadecola, Jean Vergnet, Rémi Dedryvère, Matthieu Saubanère, Artem M. Abakumov, Patrick Rozier, Jean Marie Tarascon

Research output: Contribution to journalArticlepeer-review

104 Citations (Scopus)

Abstract

The revival of the Na-ion battery concept has prompted intense research activities toward new sustainable Na-based insertion compounds and their implementation in full Na-ion cells. Efforts are parted between Na-based polyanionic and layered compounds. For the latter, there has been a specific focus on Na-deficient layered phases that show cationic and anionic redox activity similar to a Na0.67Mn0.72Mg0.28O2 phase. Herein, a new alkali-deficient P2-Na2/3Mn7/9Zn2/9O2 phase using a more electronegative element (Zn) than Mg is reported. Like its Mg counterpart, this phase shows anionic redox activity and no O2 release despite evidence of cationic migration. Density functional theory (DFT) calculations show that it is the presence of an oxygen nonbonding state that triggers the anionic redox activity in this material. The phase delivers a reversible capacity of 200 mAh g−1 in Na-half cells with such a value be reduced to 140 mAh g−1 in full Na-ion cells which additionally shows capacity decay upon cycling. These findings establish Na-deficient layered oxides as a promising platform to further explore the underlying science behind O2 release in insertion compounds based on anionic redox activity.

Original languageEnglish
Article number1802379
JournalAdvanced Energy Materials
Volume8
Issue number32
DOIs
Publication statusPublished - 15 Nov 2018

Keywords

  • anionic redox
  • layered oxides
  • Na-ion batteries
  • oxygen activity

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