Redox Chemistry and the Role of Trapped Molecular O2in Li-Rich Disordered Rocksalt Oxyfluoride Cathodes

Ryan Sharpe, Robert A. House, Matt J. Clarke, Dominic Förstermann, John Joseph Marie, Giannantonio Cibin, Ke Jin Zhou, Helen Y. Playford, Peter G. Bruce, M. Saiful Islam

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73 Citations (SciVal)
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In the search for high energy density cathodes for next-generation lithium-ion batteries, the disordered rocksalt oxyfluorides are receiving significant attention due to their high capacity and lower voltage hysteresis compared with ordered Li-rich layered compounds. However, a deep understanding of these phenomena and their redox chemistry remains incomplete. Using the archetypal oxyfluoride, Li2MnO2F, we show that the oxygen redox process in such materials involves the formation of molecular O2 trapped in the bulk structure of the charged cathode, which is reduced on discharge. The molecular O2 is trapped rigidly within vacancy clusters and exhibits minimal mobility unlike free gaseous O2, making it more characteristic of a solid-like environment. The Mn redox process occurs between octahedral Mn3+ and Mn4+ with no evidence of tetrahedral Mn5+ or Mn7+. We furthermore derive the relationship between local coordination environment and redox potential; this gives rise to the observed overlap in Mn and O redox couples and reveals that the onset potential of oxide ion oxidation is determined by the degree of ionicity around oxygen, which extends models based on linear Li-O-Li configurations. This study advances our fundamental understanding of redox mechanisms in disordered rocksalt oxyfluorides, highlighting their promise as high capacity cathodes.

Original languageEnglish
Pages (from-to)21799-21809
Number of pages11
JournalJournal of the American Chemical Society
Issue number52
Early online date15 Dec 2020
Publication statusPublished - 30 Dec 2020

Bibliographical note

Funding Information:
We thank the EPSRC (LiBatt programme grant EP/M0009521/1), the Faraday Institution CATMAT project (EP/S003053/1, FIRG016) and the Henry Royce Institute for financial support. We also thank the HEC Materials Chemistry Consortium (EP/R029431), the Isambard HPC (EP/P020224/1), and the Balena HPC service (Bath) for supercomputer facilities. We gratefully acknowledge Diamond Light Source/STFC beamtime allocation (SP20363, MM23889), and useful discussions with Dr Oriol Lamiel-Garcia (Bath) and Dr Kit McColl (Bath). M.J.C. thanks the CDT in Sustainable Chemical Technologies (EP/L016354/1) and CFH Docmail for his PhD studentship.

Publisher Copyright:
© 2020 American Chemical Society.

Copyright 2021 Elsevier B.V., All rights reserved.

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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