Oxygen Redox Activity in Battery Cathodes and the Role of Underbonded Oxygen

It is widely recognised that oxygen redox makes a significant contribution to the high capacity of some cathode materials in addition to the more usual transition metal redox. We attribute this to the presence of underbonded oxide ions, either in bulk structures or at surfaces, which act as the initial source of oxygen redox during charging. Underbonded oxide ions experience departures from local electroneutrality; examples include Li 4 Mn 5 O 12 spinel and Li‐rich layered rock salt structures but not stoichiometric LiCoO 2 or Li 2 MnO 3 . Underbonded oxide ions ionise more readily than fully‐stabilised lattice oxide ions since, using an ionic bonding description, they are associated with a deficiency of positive charge in the coordination sphere of surrounding cations. Pauling's electrostatic bond strength criterion gives a simple guide to structures or compositions that may show departures from local electroneutrality and provides the starting point for a new way to consider oxygen redox. Li 4 Mn 5 O 12 behaves as an anode due to Mn redox below 3 V but also behaves as a cathode due to reversible oxygen redox above ~3.8 V. In the high symmetry cubic structure of Li 4 Mn 5 O 12 , depending on the local distribution of cations over the occupied tetrahedral and octahedral sites, some oxygens are inevitably underbonded whereas others must be overbonded, although none show local electroneutrality expected from the average crystal structure. Underbonded oxygens are also identified in other structures, including high capacity Li‐rich layered rock salt structures.