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Non-aqueous metal-oxygen batteries depend critically on the reversibleformation/decomposition of metal oxides on cycling. Irreversible parasiticreactions cause poor rechargeability, efficiency, and cycle life and havepredominantly been ascribed to the reactivity of reduced oxygen species withcell components. These species, however, cannot fully explain the sidereactions. Here we show that singlet oxygen forms at the cathode of alithium-oxygen cell during discharge and from the onset of charge, and accountsfor the majority of parasitic reaction products. The amount increases duringdischarge, early stages of charge, and charging at higher voltages, and isenhanced by the presence of trace water. Superoxide and peroxide appear to beinvolved in singlet oxygen generation. Singlet oxygen traps and quenchers canreduce parasitic reactions effectively. Awareness of the highly reactivesinglet oxygen in non-aqueous metal-oxygen batteries gives a rationale forfuture research towards achieving highly reversible cell operation.

Singlet Oxygen Generation as a Major Cause for Parasitic Reactions during Cycling of Aprotic Lithium-Oxygen Batteries