$\mathrm{O_2}$ reduction at a DMSO/Cu(111) model battery interface

TL;DR

This study uses two-photon photoelectron spectroscopy to investigate the dynamics of oxygen reduction at a DMSO/Cu(111) interface, providing detailed insights into electron transfer processes relevant for metal-air battery development.

Contribution

It offers precise measurements of O2^- binding energy, diffusion parameters, and electron transfer distances at a non-aqueous electrode interface, advancing understanding of electrochemical reactions in battery systems.

Findings

O2^- binding energy measured at 3.80 eV

Diffusion activation energy of 31 meV

Electron transfer quenching distance of 12.4 Å

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.