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Chapter 6. Molybdate Based Ceramic Electrode Materials 178 The pyrochlore Gd2TiyMo1-yO7 was considered as a potential solid oxide fuel cell (SOFC) anode material due to its high electronic conductivity in reducing atmospheres as well as its ionic conductivity, making it a mixed conductor [18]. At first, the stability in the pO2 range relevant to operating conditions was not sufficient [19], but by tuning the composition it was made more stable and tested as an anode [20]. It was still certainly not redox-stable. The oxidation performance was notable, with an area-specific polarization resistance (ASRP) of 0.2 Ω cm2 at 950 °C at OCV. This material exhibited high sulfur tolerance. In fact, remarkably, this anode had almost as high performance in H2S as in H2. Recently, the double perovskite Sr2MgMoO6 (SMM) was reported as an excellent SOFC anode material [21, 22]. In fact, a variant with some La substituted for Sr is the highest performing single-phase anode material reported for H2 and CH4 oxidation to date [23]. Replacing Mn with Mg was also tested but had slightly lower performance [21, 22]. With a lanthanum-doped ceria (LDC) layer between the SMM anode and a electrolyte to prevent undesirable reaction and interdiffusion, an ASRP of 0.1-0.15 Ω cm2 (for 0 to 0.5-1 A/cm2 on a polarization curve) was reported at 800 °C in H2. Up to at least 50 ppm H2S tolerance, with minimal impact on performance, was reported. An anode made of SMM is also believed to be redox-stable (although that is not the case with the La-substituted variant). The electrochemical activity is believed to be related to the mixed ionic-electronic conductivity of the material. The mechanism that leads to the mixed conductivity will be further discussed in the next section and later in the Results sections of this chapter. The conductivity of 4-9 S/cm in reducing atmospheres is sufficient, although there have been a wider range of conductivity values reported since the initial study (discussed further in section 6.3.2). This material and some related double perovskites are studied further in the present work. Some studies of the related double perovskites were reported while the present work was carried out, and will be discussed and compared to the results obtained here in the Results sections. The results are able to explain some of the inconsistencies in this recent literature. Finally, an amorphous lanthanum molybdate (LaMoO) was recently reported as a high performance SOFC anode material. This material was in fact prepared by reducing the oxide- ion conductor mentioned above, La2Mo2O9, which decomposed it to an amorphous phase. For a full cell with an LDC buffer layer, similar performance was reported [24] as the full cell performance reported for SMM [21, 22]. 20 ppm sulfur tolerance was also reported. This material is also included in the present study. 6.1.2. Designing an Mo-based Electrode The elements molybdenum and tungsten have interesting properties. They are the only elements that prefer the +6 valence state at normal oxidized conditions. MoO3 and WO3 are perovskites with all vacancies for the A-sites. They have a large valence range of 0 to 6, rivaled only by Mn and the more expensive elements Ru, Os, Rh, and Ir. The tungsten bronzePDF Image | Electrolysis of CO2 and H2O
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