Clarifying the origin of molecular O2 in cathode oxides
Résumé
Anionic redox has reshaped the conventional way of exploring advanced cathode materials for Li-ion batteries. However, how anions participate in the redox process has been the subject of intensive debate, evolving from electron holes to O-O dimerization and currently to a focus on trapped molecular O2 based on high-resolution resonant X-ray inelastic scattering research. Here we show that the resonant X-ray inelastic scattering signal of molecular O2 is not exclusive to Li-rich oxide cathodes, but appears consistently in O-redox-inactive oxide materials even with a short beam exposure time as low as 1 min, indicating that molecular O2 species are not directly related to voltage hysteresis and voltage decay. We further demonstrated that molecular O2 is not a direct product of electrochemistry but more likely a consequence of the core excitation process in resonant X-ray inelastic scattering, for which the possible scenarios of the dissociation of 'M-(O-O)'-like species on beam excitation must be considered. Collectively, our results reconcile the conflicting reported results on the (non-)observation of molecular O2 signal collected from different beamlines and suggest that molecular O2 is not the energetic engine of new battery oxide cathodes.
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