${\mathrm{O}}_2$ reduction at a DMSO/Cu(111) model battery interface

Abstract

In order to develop a better understanding of electrochemical ${\mathrm{O}}_2$ reduction in non-aqueous solvents, we apply two-photon photoelectron spectroscopy to probe the dynamics of ${\mathrm{O}}_2$ reduction at a DMSO/Cu(111) model battery interface. By analyzing the temporal evolution of the photoemission signal, we observe the formation of ${\mathrm{O}}_2^{-}$ from a trapped electron state at the DMSO/vacuum interface. We find the vertical binding energy of ${\mathrm{O}}_2^{-}$ to be 3.80 $\pm$ 0.05 eV, in good agreement with previous results from electrochemical measurements, but with improved accuracy, potentially serving as a basis for future calculations on the kinetics of electron transfer at electrode interfaces. Modelling the ${\mathrm{O}}_2$ diffusion through the DMSO layer enables us to quantify the activation energy of diffusion (31 $\pm$ 6 meV), the diffusion constant (1 $\pm$ 1$\cdot 10^{-8}$ cm${}^2$/s), and the reaction quenching distance for electron transfer to ${\mathrm{O}}_2$ in DMSO (12.4 $\pm$ 0.4 $\unicode{x212B}$), a critical value for evaluating possible mechanisms for electrochemical side reactions. These results ultimately will inform the development and optimization of metal-air batteries in non-aqueous solvents.

13 pages, 5 figures