Study of the heterogeneity of a mixed-conducting electrochemical electrode

The ionic resistance of membrane–electrode assemblies of oxygen–hydrogen fuel cell electrodes containing platinum nanoparticles on carbon black, carbon nanofibers, and proton-conducting Nafion polymer in a wide range of compositions (10–80 wt %) are studied in situ by the methods of current–voltage characteristics, electrochemical impedance spectroscopy, and simulation of the impedance hodograph. Conditions that make it possible to correctly determine the ionic resistance of the electrode on the basis of an analysis of the linear approximation of the high-frequency region of the impedance hodograph are found. It is shown that the occurrence of inhomogeneities and an anomalous increase in the ionic resistance with an increase in the content of Nafion in the electrode are associated with a decrease in the volume fraction of water-generation centers (particles of electrochemically active platinum), which leads to incomplete wetting of Nafion.