Solvent Degradation in Nonaqueous Li-O2 Batteries: Oxidative Stability versus H-Abstraction.

Developing rechargeable Li-O2 batteries hinges on identifying stable solvents resistant to decomposition. Here, we focus on solvent stability against adsorption-induced H-abstraction during discharge. Using a detailed thermodynamic analysis, we show that a solvent's propensity to resist H-abstraction is determined by its acid dissociation constant, pKa, in its own environment. Upon surveying hundreds of solvents for their pKa values in different media, we find linear correlations between the pKa values across various classes of solvents in any two given media. Utilizing these correlations, we choose DMSO as the common standard to compare the relative stability trends. We construct a stability plot based on the solvent's HOMO level and its pKa in DMSO, which reveals that most solvents obey a correlation where solvents with lower HOMO levels tend to have lower pKa values in DMSO. However, this is at odds with the stability requirement that demands deep HOMO levels and high pKa values. Thus, stable solvents need to be outliers to this observed correlation.