Origin of Carbon Dioxide Evolved during Cycling of Nickel-Rich Layered NCM Cathodes

Gas formation caused by parasitic side reactions is one of the fundamental concerns in state-of-the-art lithium-ion batteries because gas bubbles might block local parts of the electrode surface, hindering lithium transport and leading to inhomogeneous current distributions. Here, we elucidate on the origin of CO2, which is the dominant gaseous species associated with the layered lithium nickel cobalt manganese oxide (NCM) cathode, by implementing isotope labeling and electrolyte substitution in differential electrochemical mass spectrometry-differential electrochemical infrared spectroscopy measurements. Li2CO3 on the NCM surface was successfully labeled with 13C via a process that involves its removal followed by intentional growth. In situ gas analytics on such NCM samples with 13C-labeled Li2CO3 clearly indicate that Li2CO3 decomposition contributes to CO2 evolution, especially during the first charge. At the same time, the greater contribution of electrolyte decomposition was indicated by the large amount of 12CO2 observed. Employment of butyronitrile as the electrolyte solvent in further measurements helped determine that the majority of electrolyte decomposition occurs via a reaction that involves the lattice oxygen of NCM.