The role of lithium salts in determining the discharge capacity of Li-O2 batteries has been highlighted in several recent studies; however, questions pertaining to their effect on the cathode surface and in the solution phase still remain unanswered. We conducted galvanostatic discharge experiments with different compositions of a binary mixture of 1 M of LiNO3 and LiTFSI in tetraglyme (TEGDME) as the electrolyte and analyzed the discharge products using techniques such as FT-IR, Raman spectroscopy, and SEM. It was observed that there is a nonlinear correlation between the electrolyte composition and the first discharge capacity, with the highest discharge capacity achieved with the electrolyte composition as 0.75 M LiNO3 and 0.25 M LiTFSI. The ID/IG values obtained from Raman spectroscopy, which represent the degree of order in the carbon cathode surface, were found to be correlated to the measured capacity. Our results indicate that at concentrations of LiNO3 higher than 0.75 M in the electrolyte, nitrogen doping of the carbon surface reaches a critical limit, beyond which it becomes unfavorable for the discharge process. On the other hand, decomposition of the electrolyte and formation of an amorphous layer on the cathode surface was found to intensify with increasing LiTFSI concentration. Our results show that the maximum discharge capacity of the cells is strongly dependent on the surface structure of the carbon cathode, which in turn is heavily influenced by the electrolyte composition. Classical molecular dynamics simulations of the same system indicated no such nonlinearity in the co-ordination of Li+ ions with respect to electrolyte composition, indicating that the ionic association strength of the anion may have only a limited effect.
Keywords: LiNO3; LiTFSI; lithium oxygen discharge chemistry; lithium salts; lithium−air; nonaqueous lithium oxygen batteries.