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How Bulk Sensitive is Hard X-ray Photoelectron Spectroscopy: Accounting for the Cathode-Electrolyte Interface when Addressing Oxygen Redox.

Zachary W Lebens-HigginsHyeseung ChungMateusz J ZubaJatinkumar RanaYixuan LiNicholas V FaenzaNathalie PereiraBryan D McCloskeyFanny RodolakisWanli YangM Stanley WhittinghamGlenn G AmatucciYing Shirley MengTien-Lin LeeLouis F J Piper
Published in: The journal of physical chemistry letters (2020)
Sensitivity to the "bulk" oxygen core orbital makes hard X-ray photoelectron spectroscopy (HAXPES) an appealing technique for studying oxygen redox candidates. Various studies have reported an additional O 1s peak (530-531 eV) at high voltages, which has been considered a direct signature of the bulk oxygen redox process. Here, we find the emergence of a 530.4 eV O 1s HAXPES peak for three model cathodes-Li2MnO3, Li-rich NMC, and NMC 442-that shows no clear link to oxygen redox. Instead, the 530.4 eV peak for these three systems is attributed to transition metal reduction and electrolyte decomposition in the near-surface region. Claims of oxygen redox relying on photoelectron spectroscopy must explicitly account for the surface sensitivity of this technique and the extent of the cathode degradation layer.
Keyphrases
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