Jump to main content
Jump to site search


Multiorbital bond formation for stable oxygen-redox reaction in battery electrodes

Author affiliations

Abstract

High-energy-density batteries have been a long-standing target toward sustainability, but the energy density of state-of-the-art lithium-ion batteries is limited in part by the small capacity of the positive electrode materials. Although employing the additional oxygen-redox reaction of Li-excess transition-metal oxides is an attractive approach to increase the capacity, an atomic-level understanding of the reaction mechanism has not been established so far. Here, using bulk-sensitive resonant inelastic X-ray scattering spectroscopy combined with ab initio computations, we demonstrate the presence of a localized oxygen 2p orbital weakly hybridized with transition metal t2g orbitals that was theoretically predicted to play a key role in oxygen-redox reactions. After oxygen oxidation, the hole in the oxygen 2p orbital is stabilized by the generation of either a (σ + π) multiorbital bond through strong π back-donation or peroxide O22− through oxygen dimerization. The multiorbital bond formation with σ-accepting and π-donating transition metals can thus lead to reversible oxygen-redox reaction.

Graphical abstract: Multiorbital bond formation for stable oxygen-redox reaction in battery electrodes

Back to tab navigation

Supplementary files

Article information


Submitted
30 Dec 2019
Accepted
10 Mar 2020
First published
12 Mar 2020

This article is Open Access

Energy Environ. Sci., 2020, Advance Article
Article type
Paper

Multiorbital bond formation for stable oxygen-redox reaction in battery electrodes

T. Sudayama, K. Uehara, T. Mukai, D. Asakura, X. Shi, A. Tsuchimoto, B. Mortemard de Boisse, T. Shimada, E. Watanabe, Y. Harada, M. Nakayama, M. Okubo and A. Yamada, Energy Environ. Sci., 2020, Advance Article , DOI: 10.1039/C9EE04197D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements