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Chapter 6. Molybdate Based Ceramic Electrode Materials 193 These questions are answered below, but first, it is important to note that, while working on this, Wei et al [89] and Huang et al [90] published results for Sr2NiMoO6 – but did not explain them. Again, the values were widely different – 67 S/cm at 850 °C in H2 [89] and ~1 S/cm at 850 °C in H2 [90]. Like SMM, the values must depend on the extent of reduction before or during measurement, but to a much greater degree. Overall, the conductivity of the molybdates clearly depends significantly on the thermal history, the pO2 during sintering and during measurement, and on the length of time allowed for equilibration during the measurement. Wei et al did provide an explanation for their high values: ―After being reduced in H2 at 1123 K for more than 2 h, the sample’s conductivity increases greatly, because reduction in H2 leads to the formation of oxygen vacancies in the double-perovskite structure.‖ [89] However, we will show in the next section that this mechanism, which seems to be accurate for SMM, is clearly not the mechanism for such high conductivity in SNM. The conductivity of the Fe-variant SFM was higher than any of the other double- perovskites (Figure 6-11), in agreement with reports in literature [43, 91]. Its conductivity was metallic type, and stable up to 1000 °C (800 °C with pO2=10-23 atm was held for 68 h, and 1000 °C pO2=10-18.5 atm was held for 3 h), suggesting that the conductivity mechanism is not the same as that for SMM, SNM and SCM. SFM has different properties because the Fe-Mo ion couple is mixed-valent for both ions, according to literature [42, 92 subref 26] and as shown in Table 6-4 (Fe2+/3+ and Mo5+/6+). This mixed-valency enhances the electronic conductivity [93]. It has been proposed that metallic conductivity in a double perovskite depends on the 3+/5+ couple [94]. On the other hand, SNM and SCM are expected to show semiconductor type conductivity [95], not metallic as was observed in the present study. Figure 6-11. Electricity conductivity of Sr2FeMoO6 in dry 9% H2/Ar.PDF Image | Electrolysis of CO2 and H2O
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