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Transition metal migration and O2 formation underpin voltage hysteresis in oxygen-redox disordered rocksalt cathodes

Author

Listed:
  • Kit McColl

    (University of Bath
    Harwell Science and Innovation Campus)

  • Robert A. House

    (Harwell Science and Innovation Campus
    University of Oxford)

  • Gregory J. Rees

    (Harwell Science and Innovation Campus
    University of Oxford)

  • Alexander G. Squires

    (University of Bath)

  • Samuel W. Coles

    (University of Bath
    Harwell Science and Innovation Campus)

  • Peter G. Bruce

    (Harwell Science and Innovation Campus
    University of Oxford
    University of Oxford)

  • Benjamin J. Morgan

    (University of Bath
    Harwell Science and Innovation Campus)

  • M. Saiful Islam

    (University of Bath
    Harwell Science and Innovation Campus
    University of Oxford)

Abstract

Lithium-rich disordered rocksalt cathodes display high capacities arising from redox chemistry on both transition-metal ions (TM-redox) and oxygen ions (O-redox), making them promising candidates for next-generation lithium-ion batteries. However, the atomic-scale mechanisms governing O-redox behaviour in disordered structures are not fully understood. Here we show that, at high states of charge in the disordered rocksalt Li2MnO2F, transition metal migration is necessary for the formation of molecular O2 trapped in the bulk. Density functional theory calculations reveal that O2 is thermodynamically favoured over other oxidised O species, which is confirmed by resonant inelastic X-ray scattering data showing only O2 forms. When O-redox involves irreversible Mn migration, this mechanism results in a path-dependent voltage hysteresis between charge and discharge, commensurate with the hysteresis observed electrochemically. The implications are that irreversible transition metal migration should be suppressed to reduce the voltage hysteresis that afflicts O-redox disordered rocksalt cathodes.

Suggested Citation

  • Kit McColl & Robert A. House & Gregory J. Rees & Alexander G. Squires & Samuel W. Coles & Peter G. Bruce & Benjamin J. Morgan & M. Saiful Islam, 2022. "Transition metal migration and O2 formation underpin voltage hysteresis in oxygen-redox disordered rocksalt cathodes," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-32983-w
    DOI: 10.1038/s41467-022-32983-w
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