Limiting Current of Oxygen Reduction on Gas‐Diffusion Electrodes for Phosphoric Acid Fuel Cells

Various models have been devoted to the operation mechanism of porous diffusion electrodes. They are, however, suffering from the lack of accuracy concerning the acid‐film thickness on which they are based. In the present paper the limiting current density has been measured for oxygen reduction on polytetrafluorine‐ethyl bonded gas‐diffusion electrodes in phosphoric acid with and without fluorinated additives. This provides an alternative to estimate the film thickness by combining it with the acid‐adsorption measurements and the porosity analysis of the catalyst layer. It was noticed that the limiting current density can be accomplished either by gas‐phase diffusion or liquid‐phase diffusion, and it is the latter that can be used in the film‐thickness estimation. It is also important to mention that at such a limiting condition, both the thin‐film model and the filmed agglomerate model reach the same expression for the limiting current density. The acid‐film thickness estimated this way was found to be of 0.1 μm order of magnitude for the two types of electrodes used in phosphoric acid with and without fluorinated additives at 150°C.