The Role of Metal Substitution in Tuning Anion Redox in Sodium Metal Layered Oxides Revealed by X-Ray Spectroscopy and Theory.

Autor: Abate I; Department of Materials Science and Engineering, Stanford University, 496 Lomita Mall, Stanford, CA, 94305, USA.; Stanford Institute for Materials & Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA., Kim SY; Department of Chemistry and the Waterloo Institute for, Nanotechnology, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada., Pemmaraju CD; Stanford Institute for Materials & Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA., Toney MF; Department of Materials Science and Engineering, Stanford University, 496 Lomita Mall, Stanford, CA, 94305, USA.; Stanford Synchrotron Radiation Light Source, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA., Yang W; Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA., Devereaux TP; Department of Materials Science and Engineering, Stanford University, 496 Lomita Mall, Stanford, CA, 94305, USA.; Stanford Institute for Materials & Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA., Chueh WC; Department of Materials Science and Engineering, Stanford University, 496 Lomita Mall, Stanford, CA, 94305, USA.; Stanford Institute for Materials & Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA., Nazar LF; Department of Chemistry and the Waterloo Institute for, Nanotechnology, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2021 May 03; Vol. 60 (19), pp. 10880-10887. Date of Electronic Publication: 2021 Mar 30.
DOI: 10.1002/anie.202012205
Abstrakt: We investigate high-valent oxygen redox in the positive Na-ion electrode P2-Na 0.67-x [Fe 0.5 Mn 0.5 ]O 2 (NMF) where Fe is partially substituted with Cu (P2-Na 0.67-x [Mn 0.66 Fe 0.20 Cu 0.14 ]O 2 , NMFC) or Ni (P2-Na 0.67-x [Mn 0.65 Fe 0.20 Ni 0.15 ]O 2 , NMFN). From combined analysis of resonant inelastic X-ray scattering and X-ray near-edge structure with electrochemical voltage hysteresis and X-ray pair distribution function profiles, we correlate structural disorder with high-valent oxygen redox and its improvement by Ni or Cu substitution. Density of states calculations elaborate considerable anionic redox in NMF and NMFC without the widely accepted requirement of an A-O-A' local configuration in the pristine materials (where A=Na and A'=Li, Mg, vacancy, etc.). We also show that the Jahn-Teller nature of Fe 4+ and the stabilization mechanism of anionic redox could determine the extent of structural disorder in the materials. These findings shed light on the design principles in TM and anion redox for positive electrodes to improve the performance of Na-ion batteries.
(© 2020 Wiley-VCH GmbH.)
Databáze: MEDLINE
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