The development of a successful Li-O2 battery depends to a large extent on the discovery of electrolyte solutions that remain chemically stable through the reduction and oxidation reactions that occur during cell operations. The influence of the electrolyte anions on the behavior of Li-O2 cells was thought to be negligible. However, it has recently been suggested that specific anions can have a dramatic effect on the chemistry of a Li-O2 cell. In the present paper, we describe how LiNO3 in polyether solvents can improve both oxygen reduction (ORR) and oxygen evolution (OER) reactions. In particular, the nitrate anion can enhance the ORR by enabling a mechanism that involves solubilized species like superoxide radicals, which allows for the formation of submicronic Li2O2 particles. Such phenomena were also observed in Li-O2 cells with high donor number solvents, such as dimethyl sulfoxide dimethylformamide (DMF) and dimethylacetamide (DMA). Nevertheless, their instability toward oxygen reduction, lithium metals, and high oxidation potentials renders them less suitable than polyether solvents. In turn, using catalysts like LiI to reduce the OER overpotential might enhance parasitic reactions. We show herein that LiNO3 can serve as an electrolyte and useful redox mediator. NO2(-) ions are formed by the reduction of nitrate ions on the anode. Their oxidation forms NO2, which readily oxidizes to Li2O2. The latter process moves the OER overpotentials down into a potential window suitable for polyether solvent-based cells. Advanced analytical tools, including in situ electrochemical quartz microbalance (EQCM) and ESR plus XPS, HR-SEM, and impedance spectroscopy, were used for the studies reported herein.

The kinetics and thermodynamics of oxygen reduction reactions (ORR) in aprotic Li electrolyte were shown to be highly dependent on the surrounding chemical environment and electrochemical conditions. Numerous reports have demonstrated the importance of high donor number (DN) solvents for enhanced ORR, and attributed this phenomenon to the stabilizing interactions between the reduced oxygen species and the solvent molecules. We focus herein on the often overlooked effect of the Li salt used in the electrolyte solution. We show that the level of dissociation of the salt used plays a significant role in the ORR, even as important as the effect of the solvent DN. We clearly show that the salt used dictates the kinetics and thermodynamic of the ORR, and also enables control of the reduced Li2O2 morphology. By optimizing the salt composition, we have managed to demonstrate a superior ORR behavior in diglyme solutions, even when compared to the high DN DMSO solutions. Our work paves the way for optimization of various solvents with reasonable anodic and cathodic stabilities, which have so far been overlooked due to their relatively low DN.

The stability of electrolyte solutions during lithium–oxygen cells operation is of great importance and interest. This is because oxides formed during reduction are strong nucleophiles which can initiate solvent decomposition. The highly polar amide based solvents have come to the fore as possible candidates for Li–O2 applications. They show typical cycling behavior as compared to other solvents; however, their stability toward lithium oxides is shrouded in doubt. The present study has focused on Li–O2 cells containing electrolyte solutions based on DMA/LiNO3. We have used various analytical tools, to explore the discharge–charge processes and related side reactions. The data obtained from FTIR, NMR, XPS, and EQCM all support a rational decomposition mechanism. The formation of various side products during the course the first discharge, leads to the conclusion that amide based solvents are not suitable for Li–O2 applications; however, electrolyte solution decomposition reduces the OER overpotential by forming oxidation mediators.