Improvement of durability of the electrocatalyst has been the key issue to be solved for the practical application of polymer electrolyte membrane fuel cells. One of the promising strategies to improve the durability is to enhance the oxidation stability of the carbon-supporting materials. In this report, we describe in detail the mechanism of the stability improvement of carbon blacks (CBs; Vulcan and Ketjen) by coating with polybenzimidazole (PBI). Nitrogen adsorption experiments reveal that the PBI coating of CBs results in the capping of the gates of the CB-micropores by the PBI. Since the surface of the micropores inside the CBs are inherently highly oxidized, the capping of such pores effectively prevents the penetration of the electrolyte into the pore and works to avoid the further oxidation of interior of the micropore, which is proved by cyclic voltammogram measurements. Above mechanism agrees very well with the dramatic enhancement of the durability of the membrane electrode assembly fabricated using Pt on the PBI-coated CBs as an electrocatalyst compared to the conventional Pt/CB (PBI-non coated) catalyst.
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