In Situ probing of solid/liquid interfaces of potassium–oxygen batteries via ambient pressure X-ray photoelectron spectroscopy: New reaction pathways and root cause of battery degradation

Abstract

Direct probing of metal–oxygen chemistry at the solid/liquid interface is essential to unravel the reaction mechanism of metal–air batteries. Ambient pressure X-ray photoelectron spectroscopy (APXPS) is an effective tool to study metal–oxygen reactions but has been limited to solid-state environments. Here, for the first time, we demonstrate in situ probing of potassium oxygen reduction/evolution reaction (ORR/OER) via APXPS in ionic liquid-based air batteries. We reveal the formation and oxidation of K2O and K2O2 in K–O2 batteries, highlighting new reaction pathways in addition to the widely established one-electron process in K–O2 batteries. Importantly, we show that the formation and subsequent oxidation of K2O2 trigger irreversible cell chemistry, which could be responsible for capacity decay in K–O2 batteries. We further show that common impurities in air such as H2O and CO2 reduce chemical reversibility of ORR and OER. This study reveals root causes of irreversible cell chemistry in K–air batteries via direct probing of ionic liquid-based air batteries via APXPS, which can be widely applied to study the chemistry of solid/liquid interfaces of metal–air batteries.