Goldilocks and the three glymes: How Na+ solvation controls Na–O2 battery cycling

In this work we report a framework to understand the role of solvent-salt interactions and how they mediate the performance of sodium-air/O2 batteries. The utilization of suitable electrolyte materials remains a point of major concern within the research community, as their stability and decomposition pathways during cycling are intimately connected with capacity and cycle life. Glyme based solvents have been widely utilized in Na–O2 batteries, however, to date no clear correlation between solvent/electrolyte properties and battery performance has been given. Herein, we have examined the effect of glyme chain length (ethylene glycol dimethyl ether DME; diethylene glycol dimethyl ether, DEGDME; and tetraethylene glycol dimethyl ether, TEGME) on the cycling behaviour of Na–O2 batteries and conclude that overall cell performance is highly dependent on solvent selection, salt concentration and rate of discharge/charge. We demonstrate how solvent selection helps define cell chemistry and performance by linking salt-solvent interactions to enthalpy of dissolution - and subsequently to sodium battery electrolyte properties - through the combination of both experimental and theoretical methodologies. The approaches detailed in this study could be used to predictively prepare electrolytes for Li-air batteries, other glyme-based electrochemical systems and low temperature applications.