Unraveling transition-metal-mediated stability of spinel oxide via in situ neutron scattering

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Abstract

The energy materials performance is intrinsically determined by structures from the average lattice structure to the atom arrangement, valence, and distribution of the containing transition metal (TM) elements. Understanding the mechanism of the structure transition and atom rearrangement via synthesis or processing is key to expediting the exploration of excellent energy materials. In this work, in situ neutron scattering is employed to reveal the real-time structure evolution, including the TM-O bonds, lattice, TM valence and the migration of the high-voltage spinel cathode LiNi0.5Mn1.5O4. The transition-metal-mediated spinel destabilization under the annealing at the oxygen-deficient atmosphere is pinpointed. The formation of Mn3+ is correlated to the TM migration activation, TM disordered rearrangement in the spinel, and the transition to a layered-rocksalt phase. The further TM interdiffusion and Mn2+ reduction are also revealed with multi-stage thermodynamics and kinetics. The mechanisms of phase transition and atom migrations as functions of temperature, time and atmosphere present important guidance on the synthesis in various-valence element containing oxides.

Original languageEnglish
Pages (from-to)60-70
Number of pages11
JournalJournal of Energy Chemistry
Volume68
DOIs
StatePublished - May 2022

Funding

This work was supported by the Division of Materials Science and Engineering, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). This research used resources at the Spallation Neutron Source (SNS), a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The authors thank Dr. M. Feygenson, Dr. J. Neuefeind, Mrs. R. A. Mills, Mr. J. Carruth and Dr. M. Kirkham at SNS for their support of neutron experiments. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). This work was supported by the Division of Materials Science and Engineering, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). This research used resources at the Spallation Neutron Source (SNS), a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The authors thank Dr. M. Feygenson, Dr. J. Neuefeind, Mrs. R. A. Mills, Mr. J. Carruth and Dr. M. Kirkham at SNS for their support of neutron experiments. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).

Keywords

  • Atomic interdiffusion
  • Disordering
  • Energy storage material
  • High-temperature phase transition
  • In situ neutron diffraction
  • Material synthesis
  • Pair distribution function

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