Rationalizing the Effect of Oxygen Vacancy on Oxygen Electrocatalysis in Li–O2 Battery

Abstract Albeit the effectiveness of surface oxygen vacancy in improving oxygen redox reactions in Li–O 2 battery, the underpinning reason behind this improvement remains ambiguous. Herein, the concentration of oxygen vacancy in spinel NiCo 2 O 4 is first regulated via magnetron sputtering and its relationship with catalytic activity is comprehensively studied in Li–O 2 battery based on experiment and density functional theory (DFT) calculation. The positive effect posed by oxygen vacancy originates from the up shifted antibond orbital relative to Fermi level ( E f ), which provides extra electronic state around E f , eventually enhancing oxygen adsorption and charge transfer during oxygen redox reactions. However, with excessive oxygen vacancy, the negative effect emerges because the metal ions are mostly reduced to low valence based on the electrical neutral principle, which not only destabilizes the crystal structure but also weakens the ability to capture electrons from the antibond orbit of Li 2 O 2 , leading to poor catalytic activity for oxygen evolution reaction (OER).