Chemical versus Electrochemical Electrolyte Oxidation on NMC111, NMC622, NMC811, LNMO, and Conductive Carbon

We compare the stability of alkyl carbonate electrolyte on NMC111, -622, and -811, LNMO, and conductive carbon electrodes. We prove that CO₂ and CO evolution onset potentials depend on the electrode material and increase in the order NMC811 < NMC111 ≈ NMC622 < conductive carbon ≈ LNMO, which we rationalize by two fundamentally different oxidation mechanisms, the chemical and the electrochemical electrolyte oxidation. Additionally, in contrast to the widespread understanding that transition metals in cathode active materials catalyze the electrolyte oxidation, we will prove that such a catalytic effect on the electrochemical electrolyte oxidation does not exist.