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Chapter 6. Molybdate Based Ceramic Electrode Materials 204 6.3.4. Electrochemical Activity for H2O/CO2 Electrolysis and H2/CO Oxidation The electrochemical activity of the molybdate materials was investigated using point- contact electrodes. A series of experiments were performed to determine the best geometry and method to estimate the TPB length. Even if some of the materials exhibit mixed conductivity, the TPB length is still the most useful normalization parameter. In the end, the normalization method was as successful as the metal point contact electrode methods described in Chapter 5. An example of the contact area for one of the electrodes is shown in Figure 6-26. The area and perimeter were measured. Then the same method as for the metals – applying correction factors to the area and TPB estimated by the Newman relation (from the serial resistance RS) – was used. The measurements on different electrodes of the same material were reproducible within ~50%, which is sufficient for this quick test and considering that the performance of the different materials spans orders of magnitude. Since none of the electrodes exhibited a rapidly and/or constantly increasing RS which would be indicative of the formation of an insulating layer, none of the electrodes were strongly reactive with YSZ at the operating conditions (700- 850 °C). SMM has been reported to react with YSZ at higher temperatures [103]. Figure 6-26. Contact area of the tip of an SFM cone type electrode that had been in contact with the smooth polished YSZ surface. The outline of the measured contact area is shown at the right. Example impedance spectra measured at OCV are shown in Figure 6-27. A detailed analysis of the IS was not carried out in the present study. The IS were used only to determine RS and RP to assess the relative performance of the materials. From these spectra one can see that SFM has much higher performance than STM for all atmospheres. Furthermore, the difference in performance in CO/CO2 vs H2/H2O is much greater for STM than for SFM.PDF Image | Electrolysis of CO2 and H2O
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