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Chapter 5. Aspects of Metal-YSZ Electrode Kinetics 161 authors they observed fine Ni-YSZ nanostructures as a result of the treatment (not yet published). 5.4. Discussion of Reaction Mechanisms Widely different responses of different metals to the same parameter changes were observed. The gas partial pressure dependencies of LSRP were different between the different metals, and shapes of the polarization curves and impedance spectra were different. These observations provide evidence that the different metals do not generally share the same reaction mechanisms, contrary to recent studies that suggested that the relative electrochemical activity of various metals, including those studied here, is simply correlated to metal oxide formation enthalpy [28] or the stability of surface-adsorbed atomic oxygen [81]. The electrocatalytic activities may be more complicated than a single correlated property of the metals could describe. Those studies were based on a more limited set of measurements – only anodic polarization in dry H2 (a single experimental condition). Also, the purities of the different metals used were not specified. Based on the phenomena observed in this study, the reaction mechanisms that take place for oxidation and reduction of H2/H2O and CO/CO2 at metal-YSZ interfaces must be able to explain the following: —Inconsistencies between studies: For the different metals: 1. The differences in relative performance between different studies For a given metal: 2. The variability of the magnitude of LSRP in the same conditions in different studies 3. The differences in the activation energies in different studies For Ni electrodes specifically (they have been the most studied in literature): 4. Thedifferentnumberofrate-limitingprocessesidentifiedindifferentstudiesbased on impedance spectra measured at the same conditions 5. The large difference, usually around an order of magnitude, of LSRP between H2/H2O and CO/CO2 observed for all metals in this study and in other studies versus the relatively little difference in other studies 6. The differences in the degree of gas partial pressure dependencies in different studies (the trends are generally consistent but the degree of the dependency differs) 7. The differences in the bias dependency of the LSRP in different studies —The responses of the different metals observed in this study: 8. The gas partial pressure dependencies of the impedance of the different metals (section 5.3.3.1 and 5.3.3.2) including the shapes of the impedance dataPDF Image | Electrolysis of CO2 and H2O
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