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Chapter 6. Molybdate Based Ceramic Electrode Materials 207 Potential sweeps were performed on all of the electrodes in 50% H2O/H2. Only one is shown as an example – that for SVM (Figure 6-30). Cathodic polarization (H2O electrolysis, in this case) significantly activates the electrode relative to OCV. The instantaneous slope of the polarization curve at –200 mV vs at OCV, determined by IS measured under bias, was about 0.8 kΩ cm vs 10 kΩ cm, or a factor of 12 lower LSRP. –200 mV is chosen because this magnitude of cathodic bias is relevant for electrolysis cell operation – the total overpotential, including the potential drop at the positive-electrode and the ohmic drop across the electrolyte, should be 500-700 mV for electrolysis at 850 °C if operating at the thermoneutral voltage (see sections 1.1.2, 3.2.2.3, and 4.3.1). Clearly, OCV RP values are not always indicative of the true performance of these molybdates (as well as some other ceramics e.g. titanates [8, 53]). Some ceramic materials activate during reduction, most likely because reducing them leads to defect chemistry changes on the surface of the material, such as oxygen loss and an increase in surface oxygen vacancy concentration. Not all of the electrodes activated so significantly during cathodic polarization; for others the potential sweeps were more linear. The activation or deactivation of the electrodes with anodic or cathodic overpotentials is summarized in Figure 6-31. In Figure 6-31a, an ―activation factor‖ for anodic and cathodic bias is presented for each electrode. This is the ratio of the LSRP at the given overpotential (+200 mV or –200 mV) versus the LSRP at OCV, determined from impedance measurements. An activation factor value below 1 indicates that the OCV LSRP was lower than at the applied potential. Clearly, SVM is not the only material that activates by cathodic polarization. STM and LM activate to a similar degree (by a factor of 7 to 11). Many of the double-perovskites are activated as well, but only slightly by comparison. Most of the materials have lower anodic than cathodic performance, in contrast to some of the metals, such as Ni, studied in Chapter 5. The exception is LM, for which the anodic performance is even higher than the cathodic performance, both relative to the OCV performance. To assess the relative performance of the different materials for oxidation and reduction, the i-V curves must be used. Figure 6-31b shows the absolute length-specific current measured at overpotentials of +200 mV and –200 mV. SFM and the pre-reduced SNM- p show some of the best performance, as indicated by the OCV measurements earlier. However, LM now shows similarly high performance due to its strong activation with anodic and cathodic bias. It should also be noted that the potential sweeps were reversible and repeatable. That is, none of the electrodes remained activated or deactivated after applying potentials. Further study of the observed cathodic activation phenomena of these electrodes will be important for application in electrolysis cell cathodes. The high performance of SNM is most likely due to the nanostructured surface and precipitated nanoparticles discussed earlier. SFM, on the other hand, does not seem to decompose in such a way, yet has even higher performance. The stability can be attributed to the greater stability of Fe against reduction to metal than Ni and Co, and the high performancePDF Image | Electrolysis of CO2 and H2O
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