Carbon Corrosion in Proton-Exchange Membrane Fuel Cells: From Model Experiments to Real-Life Operation in Membrane Electrode Assemblies

The electrochemical oxidation of carbon is a pivotal problem for low-temperature electrochemical generators, among which are proton-exchange membrane fuel cells (PEMFCs), and (non)­aqueous-electrolyte Li–air batteries. In this contribution, the structure-sensitivity of the electrochemical corrosion of high-surface area carbon (HSAC) used to support catalytic materials in PEMFC electrodes is investigated in model (liquid electrolyte, 96 h potentiostatic holds at different electrode potentials ranging from 0.40 to 1.40 V at <i>T</i> = 330 K) and real PEMFC operating conditions (solid polymer electrolyte, 12,860 h of operation at constant current). Characterizations from Raman spectroscopy demonstrate that the disordered domains of HSAC supports (amorphous carbon and defective graphite crystallites) are preferentially oxidized at voltages related to the PEMFC cathode (0.40 < <i>E</i> < 1.00 V). Excursions to high electrode potential <i>E</i> > 1.00 V, witnessed during start-up and shut-down of PEMFC systems, accelerate this phenomenon and propagate the electrochemical oxidation to the graphitic domains of the HSAC. Thanks to X-ray photoelectron spectroscopy, a better understanding of the relationships existing between structural changes and carbon surface oxides coverage is also emerging for the first time