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Open Access Publications from the University of California

Whither Mn Oxidation in Mn-Rich Alkali-Excess Cathodes?

  • Author(s): Zuba, MJ
  • Grenier, A
  • Lebens-Higgins, Z
  • Fajardo, GJP
  • Li, Y
  • Ha, Y
  • Zhou, H
  • Whittingham, MS
  • Yang, W
  • Meng, YS
  • Chapman, KW
  • Piper, LFJ
  • et al.

Lithium-rich NMC (LR-NMC) compounds exhibit high capacities beyond the traditional redox, but it remains unclear whether the anomalous charge compensation mechanism is due to oxidized lattice oxygen or migration-assisted Mn oxidation. We compare LR-NMC with a model Mn7+ system (KMnO4) using a combination of resonant inelastic X-ray scattering (RIXS) irradiation studies and operando X-ray absorption spectroscopy/X-ray diffraction (XAS/XRD) to quantify transition metal (TM) migration, Mn oxidization, and beam-induced effects. We reveal how for KMnO4 it is possible to observe beam-induced Mn reduction resulting in trapped molecular oxygen. For LR-NMC, we observe negligible evidence for Mn oxidation while stabilized tetrahedral sites correlate more with a reduced TM environment. Finally, the additional spectroscopic structures observed in oxidized oxygen RIXS for LR-NMC are absent for gas-phase molecular oxygen.

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