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Chapter 6. Molybdate Based Ceramic Electrode Materials 210 the negative-electrode, whereas the best molybdates have high electronic conductivity and most likely moderate ionic conductivity. Figure 6-32. Electrochemistry measurements made on the STN-CGO cone-shaped electrode contacting the polished YSZ surface: (a) Impedance spectra measured at OCV, (b) Potential sweeps measured at 2 mV/s. 6.4. Conclusions In this study, a number of Mo-based ceramics were studied for their fundamental properties of phase, microstructure and electronic conductivity, and they were tested as solid oxide cell negative-electrodes. The results show that molybdenum can be used on the B-site of a variety of ceramic materials that have high electrochemical performance for H2O/CO2 reduction and H2/CO oxidation. These materials are therefore very promising as electrodes or as components of electrodes. Most of the rich properties that Mo-based ceramics have to offer seem to be related to the valence flexibility of the Mo ion. These Mo-based ceramics can provide high electronic conductivity, high electrocatalytic activity, and mixed ionic-electronic conductivity via oxygen vacancies (which also often enhances the electrocatalytic activity). Many of the materials were significantly activated by cathodic polarization, and they exhibited much higher performance for cathodic (electrolysis) polarization than anodic (fuel cell) polarization, which makes them especially interesting for electrolysis electrodes. For some materials such as the double-perovskites Sr2NiMoO6 and Sr2CoMoO6, a decomposition phenomenon that leads to a unique nanostructured surface and multiple desirable electrocatalytic and electron-conductive phases was observed under operating conditions (certain reducing atmospheres). The material was reduced and decomposed in a beneficial way, precipitating Ni and Ni-Mo nanoparticles to the surface and grain boundaries and forming other ceramic phases with high electronic conductivity. This phenomenon explains the wide range of electrical conductivity results reported in literature. The decomposition might be performed in situ and controlled by temperature and pO2 (and possibly even applied potential) to obtain desired properties.PDF Image | Electrolysis of CO2 and H2O
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