Visualization Analysis of Pt and Co Species in Degraded Pt₃Co/C Electrocatalyst Layers of a Polymer Electrolyte Fuel...

In order to obtain a suitable design policy for the development of a next-generation polymer electrolyte fuel cell, we performed a visualization analysis of Pt and Co species following aging and degradation processes in membrane-electrode assembly (MEA), using a same-view. Nano-X-ray absorption fine structure (XAFS)/Scanning transmission electron microscope (STEM)-energy dispersive X-ray spectroscopy (EDS) technique that we developed to elucidate durability factors and degradation mechanisms of a MEA Pt₃Co/C cathode electrocatalyst with higher activity and durability than a MEA Pt/C. In the MEA Pt₃Co/C, after 5000 ADT-rec (rectangle accelerated durability test) cycles, unlike the MEA Pt/C, there was no oxidation of Pt. In contrast, Co oxidized and dissolved over a wide range of the cathode layer (∼70% of the initial Co amount). The larger the size of the cracks and pores in the MEA Pt/C and the smaller the ratio of Pt/ionomer of cracks and pores, the faster the rate of catalyst degradation. In contrast, there was no correlation between the size or Co/ionomer ratio of the cracks and pores and the Co dissolution of the MEA Pt₃Co/C. It was shown that Co dissolved in the electrolyte region had an octahedral Co²⁺-O₆ structure, based on a 150 nm × 150 nm nano-XAFS analysis. It was also shown that its existence suppressed the oxidation and dissolution of Pt. The MEA Pt₃Co/C after 10,000 ADT-rec cycles had many cracks and pores in the cathode electrocatalyst layer, and about 90% of Co had been dissolved and removed from the cathode layer. We discovered a metallic Pt-Co alloy band in the electrolyte region of 300-400 nm from the cathode edge and square planar Pt²⁺-O₄ species and octahedral Co²⁺-O₆ species in the area between the cathode edge and the Pt-Co band. The transition of Pt and Co chemical species in the Pt₃Co/C cathode electrocatalyst in the MEA during the degradation process, as well as a fuel cell deterioration suppression process by Co were visualized for the first time at the nano scale using the same-view nano-XAFS/STEM-EDS combination technique that can measure the MEA under a humid N₂ atmosphere while maintaining the working environment for a fuel cell.