Oxide ions in transition metal oxide cathodes can store charge at high voltage offering a route towards higher energy density batteries. However, upon charging these cathodes, the oxidized oxide ions condense to form molecular O2 trapped in the material. Consequently, the discharge voltage is much lower than charge, leading to undesirable voltage hysteresis. Here we capture the nature of the electron holes on O2− before O2 formation by exploiting the suppressed transition metal rearrangement in ribbon-ordered Na0.6[Li0.2Mn0.8]O2. We show that the electron holes formed are delocalized across the oxide ions coordinated to two Mn (O–Mn2) arranged in ribbons in the transition metal layers. Furthermore, we track these delocalized hole states as they gradually localize in the structure in the form of trapped molecular O2 over a period of days. Establishing the nature of hole states on oxide ions is important if truly reversible high-voltage O-redox cathodes are to be realized.
