The Mechanisms of Oxygen Reduction and Evolution Reactions in Nonaqueous Lithium-Oxygen Batteries

A fundamental understanding of the mechanisms of both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in nonaqueous lithium–oxygen (Li–O2) batteries is essential for the further development of these batteries. In this work, we systematically investigate the mechanisms of the ORR/OER reactions in nonaqueous Li–O2 batteries by using electron paramagnetic resonance (EPR) spectroscopy, using 5,5‐dimethyl‐pyrroline N‐oxide as a spin trap. The study provides direct verification of the formation of the superoxide radical anion (O2.−) as an intermediate in the ORR during the discharge process, while no O2.− was detected in the OER during the charge process. These findings provide insight into, and an understanding of, the fundamental reaction mechanisms involving oxygen and guide the further development of this field. Chasing radicals: The fundamental understanding of the mechanisms for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in nonaqueous Li‐O2 batteries is essential for the further development of these batteries. Here, we systematically investigated the ORR/OER reaction mechanisms in nonaqueous Li‐O2 batteries using electron paramagnetic resonance spectroscopy.