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Chapter 6. Molybdate Based Ceramic Electrode Materials 177 (a) (b) Figure 6-1. Illustration of solid oxide cell electrodes comprised of an electrocatalytic coating of networked particles (a) which also provides ionic conductivity and is coated onto an electron-conducting backbone, and (b) which also provides electronic conductivity and is coated onto an ionic conducting backbone. The purpose of this work was study some fundamental properties of a variety of molybdate based materials and to test them for electrolysis of H2O and CO2 (as well as oxidation of H2 and CO). A few of the materials have been studied as fuel cell anodes in prior work and others are new materials from related families that have not been tested as solid oxide cell electrodes. None of the materials, including those that have been studied as fuel cell anodes, have been tested for electrolysis. Furthermore, the prior anode studies used porous electrodes, and most of them only reported the performance of the full cell (not isolating the performance of the electrode). In the present study, simplified geometry electrodes are employed, similar to that used for metal materials in Chapter 5. The electrodes contact YSZ with a well-defined three-phase boundary, enabling study of the electrochemical properties and relative electrocatalytic performance of the materials without the effects of a complex microstructure of porous electrodes. Using such point-contact electrodes is generally less straightforward for ceramics than for metals because the electrode materials are not soft like metals and do not creep and form a well-defined interface and TPB. In the present study, methods were developed to successfully measure the TPB for ceramic materials, improving upon prior point- contact ceramic electrodes studies. This will be briefly discussed in section 6.2 and reported in more detail in the future. In the following sections, the prior studies of molybdate materials in solid oxide cells are reviewed, followed by a discussion about designing a molybdenum-based ceramic electrode. 6.1.1. Prior Work with Mo Based Ceramics in Solid Oxide Cells The first major material based on Mo that was studied for use in solid oxide cells was the oxide ion conductor, La2Mo2O9 [17]. This material was found to have higher O2- ion conductivity than YSZ at temperatures above 600 °C, suggesting that it could be a good electrolyte material. However, it is unstable in reducing atmospheres in this temperature range, limiting its practical applicability.PDF Image | Electrolysis of CO2 and H2O
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