Electrochemical Oxidation of Li₂O₂ Surface-Doped with Li₂CO₃

Electrochemical oxidation of Li₂O₂, i.e., the charging reaction of the aprotic lithium–oxygen batteries (Li–O₂ batteries), is significantly influenced by its surface chemistry. Here, the surface species of Li₂CO₃, widely identified together with Li₂O₂ at the end of discharge, is investigated to understand its implication for the oxidation of Li₂O₂. In situ doping Li₂O₂ with various amounts of Li₂CO₃ has been obtained by reacting with CO₂ gas in a controlled way, and the electrochemical oxidation of the doped Li₂O₂ is studied with a quantitative differential electrochemical mass spectrometer (DEMS). Instead of a single charging potential plateau and one O₂ gas evolution stage for the pristine Li₂O₂, Li₂CO₃-doped Li₂O₂ exhibits two O₂/CO₂ gas evolution stages and three charging plateaus characterized with the larger overpotential for the initial and final stages. The conductivity of Li₂CO₃ dopant is invoked to explain the different oxidation behaviors of Li₂CO₃-doped Li₂O₂. The DEMS study of the electrochemical oxidation of isotope-labeled Li₂¹³CO₃ is also conducted to identify the origins of O₂ and CO₂ evolution during the oxidation of Li₂CO₃-doped Li₂O₂. The results reported here provide an improved understanding of the Li₂O₂ oxidation in the presence of parasitic Li₂CO₃ species and will contribute to the future development of Li–O₂ batteries.