Nonaqueous lithium–air batteries have garnered considerable research interest over the past decade due to their extremely high theoretical energy densities and potentially low cost. Significant advances have been achieved both in the mechanistic understanding of the cell reactions and in the development of effective strategies to help realize a practical energy storage device. By drawing attention to reports published mainly within the past 8 years, this review provides an updated mechanistic picture of the lithium peroxide based cell reactions and highlights key remaining challenges, including those due to the parasitic processes occurring at the reaction product–electrolyte, product–cathode, electrolyte–cathode, and electrolyte–anode interfaces. We introduce the fundamental principles and critically evaluate the effectiveness of the different strategies that have been proposed to mitigate the various issues of this chemistry, which include the use of solid catalysts, redox mediators, solvating additives for oxygen reaction intermediates, gas separation membranes, etc. Recently established cell chemistries based on the superoxide, hydroxide, and oxide phases are also summarized and discussed.

NMR and operando gas measurements show that at low potentials, EC is dehydrogenated to VC, whereas at high potentials, EC is chemically oxidised to CO2, CO and H2O, where the water that is formed induces secondary decomposition reactions.

Anatase TiO2−x–C nanotubes demonstrate a superior Li storage capacity as high as 320(±68) mA h g−1 compared to 180(±38) mA h g−1 for TiO2−x.

Understanding the mechanistic details of the superoxide induced solvent degradation, is important in the development of stable electrolytes for lithium-oxygen (Li-O2) batteries. Propylene carbonate (PC) decomposition on a model electrode surface is studied here using in situ attenuated total reflectance surface enhanced infrared absorption spectroscopy (ATR-SEIRAS). The sensitivity of the SEIRAS technique to the interfacial region allows investigation of subtle changes in the interface region during electrochemical reactions. Our SEIRAS studies show that the superoxide induced ring opening reaction of PC is determined by the electrolyte cation. Computational modeling of the proposed reaction pathway of superoxide with PC revealed a large difference in the activation energy barriers when Li(+) was the countercation compared with tetraethylammonium (TEA(+)), due to the coordination of Li(+) to the carbonate functionality. While the degradation of cyclic organic carbonates during the Li-O2 battery discharge process is a well-established case, understanding these details are of significant importance toward a rational selection of the Li-O2 battery electrolytes; our work signifies the use of SEIRAS technique in this direction.