In Situ Infrared Micro and Nanospectroscopy for Discharge Chemical Composition Investigation of Non-Aqueous Lithium-Air Cells

Metal-air batteries, such as Li-air, may be the key for large-scale energy storage as they have the highest energy density among all electrochemical devices. However, these devices suffer from irreversible side reactions leading to battery failure, especially when ambient air is used as the O-2 source, so a deep understanding over the surface chemistry evolution is imperative for building better devices. Herein, a multi-scale (nano-micro) FTIR analysis is made over the electrode surface during cell discharge employing synchrotron infrared nanospectroscopy (SINS) for the first time, to track the chemical composition changes at the nanoscale which are successfully correlated with in operando micro-FTIR characterization. The in situ results reveal homogeneous product distribution from the nano to the micro scale, and that the discharge rate does not interfere in chemical composition. In operando micro-FTIR shows the atmosphere dependency over Li products formation; the presence of HCOO- species occurring due to CO2 electroreduction in water, LiOH and Li2CO3, are also detected and even the lowest concentration of CO2 and H2O affects the O-2 reactions. Finally, evidence of the Li2O2 reaction with DMSO forming DMSO2 after just 140 s of cell discharge shows this new technique's relevance in aiding the search for stable electrolytes.

Automated summary

Research on the surface chemistry evolution of metal-air batteries reveals chemical composition changes from nano to micro scale through nano-scale FTIR analysis and in operando micro-FTIR characterization. The study finds that discharge rate does not interfere in chemical composition, while the formation of Li products is atmosphere-dependent.