Twin Problems of Interfacial Carbonate Formation in Nonaqueous Li–O2 Batteries

We use XPS and isotope labeling coupled with differential electrochemical mass spectrometry (DEMS) to show that small amounts of carbonates formed during discharge and charge of Li–O2 cells in ether electrolytes originate from reaction of Li2O2 (or LiO2) both with the electrolyte and with the C cathode. Reaction with the cathode forms approximately a monolayer of Li2CO3 at the C–Li2O2 interface, while reaction with the electrolyte forms approximately a monolayer of carbonate at the Li2O2–electrolyte interface during charge. A simple electrochemical model suggests that the carbonate at the electrolyte–Li2O2 interface is responsible for the large potential increase during charging (and hence indirectly for the poor rechargeability). A theoretical charge-transport model suggests that the carbonate layer at the C–Li2O2 interface causes a 10–100 fold decrease in the exchange current density. These twin “interfacial carbonate problems” are likely general and will ultimately have to be overcome to produce a high...