Confining Bulk Molecular O2 by Inhibiting Charge Transfer on Surface Anions Toward Stable Redox Electrochemistry in Layered Oxide Cathodes

Molecular O2 has been clarified as an important O-oxidation model in anionic redox, the charge compensation provided by which pushes energy-density limits of layered oxide cathodes. However, how to confine the bulk-formed molecular O2 and retard its conversation to free gaseous O2 (↑), an origin of unstable redox electrochemistry, remains open questions. Here, we propose a strategy via tuning relative values of Mott–Hubbard U and charge-transfer energy Δ to suppress charge transfer on surface anions to confine the bulk molecular O2. Supported by theoretical calculations, Nb5+ without 4d electrons which can enable U < < Δ is selected as a charge-transfer insulator. The thus Nb5+-surface-tailored model compound Na0.67Fe0.5Mn0.5O2 shows an oxygen-redox-inactive surface and well-confined bulk molecular O2 as directly uncovered by soft X-ray absorption spectroscopy and 50 K-electron paramagnetic resonance results respectively. Meanwhile, a stable redox electrochemistry with enhanced cycling stability, inhibited voltage decay and eliminated P2-O2 phase transitions is observed because of the well-caged bulk O2. More broadly, this work presents a versatile access to stabilize the important O-oxidation model, enriching approaches of stabilizing the anionic redox electrochemistry.