Competitive Oxygen Reduction Pathways to Superoxide and Peroxide during Sodium‐Oxygen Battery Discharge

Abstract

AbstractThe sodium‐air battery offers a sustainable, high‐energy alternative to lithium‐ion batteries. Discharge in the cell containing glyme‐based electrolytes can lead to formation of large cubic NaO2 particles via a solution‐precipitation mechanism. While promising, high rates result in sudden death. The exact nature of the discharge product has been a matter of contention, and Na2O2 has never been directly detected in a dry glyme Na−O2 cell. If Na2O2 were to form during discharge in the Na−O2 cell it would have a detrimental impact on cell performance. Here we show that Na2O2 forms during discharge at high overpotential in the glyme‐based Na−O2 batteries. Na2O2 formation is confirmed by spectroscopic and electrochemical analysis and electron microscopy demonstrates that it results in thin insulating films at the electrode surface. The formation of these thin films results in rapid cell death during discharge, introducing an inherent chemical limitation to the Na−O2 battery.