In this study, the heteropolyacids of H3+xPVxMO12-xO40 (x = 0, 2, and 3) were applied as redox mediators for the oxygen reduction reaction in polymer electrolyte fuel cells, of which the cathode is free from the usage of noble metals such as Pt/C. In this system, the electrochemical reduction of heteropolyacid over the carbon cathode and the subsequent reoxidation of the partially reduced heteropolyacid by exposure to the dissolved oxygen in the regenerator are important processes for continuous power generation. Thus, the redox properties of catholytes containing these heteropolyacids were investigated in detail. The substitution quantity of V in the heteropolyacid affected the onset reduction potential as well as the reduction current density, resulting in a difference in cell performance. The chemical composition of heteropolyacid also had a significant impact on the reoxidation property. Among the three compounds, H6PV3Mo9O40 was the most suitable redox mediator. Furthermore, the pH of the catholyte was found to be the crucial factor in determining the reoxidation rate of partially reduced heteropolyacid as well as cell performance.
Keywords: Pt-free cathode; heteropolyacid; oxygen reduction reaction; polymer electrolyte fuel cell; polyoxometalate; redox mediator.