Transmission Electron Microscopy Observation of Corrosion Behaviors of Platinized Carbon Blacks under Thermal and Electrochemical Conditions

Carbon blacks such as Vulcan XC-72 are widely used to support platinum (Pt) or Pt alloy catalysts in proton exchange membrane fuel cells. Despite their widespread use, carbon blacks are susceptible to corrosion during fuel cell operations. In this work, the corrosion behaviors of platinized Vulcan XC-72 nanoparticles under thermal and electrochemical conditions were monitored by transmission electron microscopy (TEM). The thermal corrosion experiment was carried out in a gas-cell TEM, which allows for a direct observation of the thermal oxidation behavior of the nanoparticles. The electrochemical corrosion experiment was performed outside of the TEM by loading the nanoparticles on a TEM grid and then electrochemically corroding them step by step followed by taking TEM images from exactly the same nanoparticles after each step. This work revealed four types of structural changes: (i) total removal of structurally weak aggregates, (ii) breakdown of aggregates via neck-breaking, (iii) center-hollowed primary particles caused by an inside-out corrosion starting from the center to outer region, and (iv) gradual decrease in the size of primary particles caused by a uniform removal of material from the surface. These structural changes took place in sequence or simultaneously depending on the competition of carbon corrosion dynamical processes. The results obtained from this work provide insight on carbon corrosion and its effects on fuel cells' long-term performance and durability. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3391737] All rights reserved.