Rethinking Oxygen Redox: Does Oxygen Dimerization Occur without Oxidation in Li₂NiO₃?

In layered lithium transition metal oxide cathodes, high-voltage operation is accompanied by the formation of oxygen dimers, which are widely used as an indicator of oxygen-redox activity. However, understanding the role that oxygen dimerization plays in facilitating charge compensation is still needed. Li2NiO3 (a 3d8L2-containing compound, where L is a ligand hole) is studied as a model system, where oxygen dimerization is shown to occur without cathode oxidation. Electrochemical cycling results in a net reduction of the cathode, accompanied by structural transformations, despite spectroscopic features of oxygen dimers arising at the top-of-charge. Here, oxygen dimerization is shown to coexist alongside a structurally transformed and electronically reduced cathode structure, thus highlighting that O dimerization is independent of bulk redox processes. This makes it clear that a thermodynamically derived transformation toward a reduced phase remains the only variable capable of generating O–O dimers in Li2NiO3.