Estimation of electric field effects on the adsorption of molecular superoxide species on Au based on density functional theory.

Superoxide species are key intermediates in the oxygen reduction reactions (ORR) that occur at the cathodes of aprotic metal-air batteries. Herein we report a DFT study of the effects of an externally applied electric field (ε) on the stability of various molecular superoxide species, including MO (M = Li, Na, K) and O, on gold surfaces, which shows that the stability of such species on Au electrodes can be materially affected by the presence of an electric field and solvent molecules, suggesting that such effects should be included in the first-principles modeling of cathode reactions in metal-O cells. In the ε range of ±0.