Engineering considerations for practical lithium-air electrolytes.

Lithium-air batteries promise exceptional energy density while avoiding the use of transition metals in their cathodes, however, their practical adoption is currently held back by their short lifetimes. These short lifetimes are largely caused by electrolyte breakdown, but despite extensive searching, an electrolyte resistant to breakdown has yet to be found. This paper considers the requirements placed on an electrolyte for it to be considered usable in a practical cell. We go on to examine ways, through judicious cell design, of relaxing these requirements to allow for a broader range of compounds to be considered. We conclude by suggesting types of molecules that could be explored for future cells. With this work, we aim to broaden the scope of future searches for electrolytes and inform new cell design.

Spiers Memorial Lecture: Lithium air batteries - tracking function and failure.

The lithium-air battery (LAB) is arguably the battery with the highest energy density, but also a battery with significant challenges to be overcome before it can be used commercially in practical devices. Here, we discuss experimental approaches developed by some of the authors to understand the function and failure of lithium-oxygen batteries. For example, experiments in which nuclear magnetic resonance (NMR) spectroscopy was used to quantify dissolved oxygen concentrations and diffusivity are described. 17O magic angle spinning (MAS) NMR spectra of electrodes extracted from batteries at different states of charge (SOC) allowed the electrolyte decomposition products at each stage to be determined. For instance, the formation of Li2CO3 and LiOH in a dimethoxyethane (DME) solvent and their subsequent removal on charging was followed. Redox mediators have been used to chemically reduce oxygen or to chemically oxidise Li2O2 in order to prevent electrode clogging by insulating compounds, which leads to lower capacities and rapid degradation; the studies of these mediators represent an area where NMR and electron paramagnetic resonance (EPR) studies could play a role in unravelling reaction mechanisms. Finally, recently developed coupled in situ NMR and electrochemical impedance spectroscopy (EIS) are used to characterise the charge transport mechanism in lithium symmetric cells and to distinguish between electronic and ionic transport, demonstrating the formation of transient (soft) shorts in common lithium-oxygen electrolytes. More stable solid electrolyte interphases are formed under an oxygen atmosphere, which helps stabilise the lithium anode on cycling.