Oxygen Reactions in a Non-Aqueous Li+ Electrolyte†

TLDR: In situ spectroscopic data are presented that provide direct evidence that LiO2 is indeed an intermediate on O2 reduction, which then disproportionates to the final product Li2O2.

Abstract: Oxygen (O2) reduction is one of the most studied reactions in chemistry1 Widely investigated in aqueous media, O2 reduction in non-aqueous solvents, such as CH3CN, has been studied for several decades2–7 Today, O2 reduction in non-aqueous Li+ electrolytes is receiving considerable attention because it is the reaction on which operation of the Li–air (O2) battery depends8–29 The Li–O2 battery is generating a great deal of interest because theoretically its high energy density could transform energy storage8, 9 As a result, it is crucial to understand the O2 reaction mechanisms in non-aqueous Li+ electrolytes Important progress has been made using electrochemical measurements including recently by Laoire et al29 No less than five different mechanisms for O2 reduction in Li+ electrolytes have been proposed over the last 40 years based on electrochemical measurements alone25–29 The value of using spectroelectrochemical methods is that they can identify directly the species involved in the reaction Here we present in situ spectroscopic data that provide direct evidence that LiO2 is indeed an intermediate on O2 reduction, which then disproportionates to the final product Li2O2 Spectroscopic studies of Li2O2 oxidation demonstrate that LiO2 is not an intermediate on oxidation, that is, oxidation does not follow the reverse pathway to reduction