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

Abate, Iwnetim; Kim, Se Young; Pemmaraju, C. Das; Toney, Michael F.; Yang, Wanli; Devereaux, Thomas P.; Chueh, William C.; Nazar, Linda F.

doi:10.1002/anie.202012205

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

Journal Article · Tue Mar 30 00:00:00 EDT 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202012205· OSTI ID:1781060

Abate, Iwnetim ^[1]; Kim, Se Young ^[2]; Pemmaraju, C. Das ^[3]; Toney, Michael F. ^[4]; Yang, Wanli ^[5]; Devereaux, Thomas P. ^[1]; Chueh, William C. ^[1]; ^[2]

Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. of Waterloo, ON (Canada)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Stanford Univ., CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

We investigate high-valent oxygen redox in the positive Na-ion electrode P2-Na_0.67-x[Fe_0.5Mn_0.5]O₂ (NMF) where Fe is partially substituted with Cu (P2-Na_0.67-x[Mn_0.66Fe_0.20Cu_0.14]O₂, NMFC) or Ni (P2-Na_0.67-x[Mn_0.65Fe_0.20Ni_0.15]O₂, 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 Fe⁴⁺ 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.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1781060

Alternate ID(s):: OSTI ID: 1786120

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 19 Vol. 60; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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