Visualization Analysis of Pt and Co Species in Degraded Pt3Co/C Electrocatalyst Layers of a Polymer Electrolyte Fuel Cell Using a Same-View Nano-XAFS/STEM-EDS Combination Technique

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 MEA, using a same-view nano-XAFS‒STEM/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 5,000 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 is 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. Pt and Co chemical species in the Pt3Co/C cathode electrocatalyst in the MEA during the deterioration process, and 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 humid N2 atmosphere, while maintaining the working environment for a fuel cell.