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Chapter 6. Molybdate Based Ceramic Electrode Materials 192 measured on SNM_1. Decreasing the pO2 again returned the conductivity to its high value; it seemed the changes taking place were nearly reversible. Figure 6-10. Long-term electrical conductivity measurements of air-sintered samples (a) SNM_4, tested at 800 °C in 10-23 atm O2, and (b) SCM, tested at 800 °C in 10-24 atm O2. The temperature and pO2 profile for (b) was the same as that in Figure 6-7 (this SCM sample and that SMM sample were tested simultaneously), and the conditions for (a) were similar (but with the slightly higher pO2). Finally, a fourth SNM sample, SNM_4, was tested for a long time at 800 °C in 10-23 atm O2 (Figure 6-10a). This sample was not pre-reduced before testing. After about 300 h, the conductivity had reached 240 S/cm at which point it reached a plateau. This plateau was in fact due to a slight variation in the pO2 – the pO2 slightly decreased throughout the test until this point. The test was continued and the conductivity remained near this level, gradually increasing to 270 S/cm during the next 100 h, but the pO2 was slightly unstable so it is not shown here. During the continuation of this test the pO2 was purposely varied as well, and these results are described in the next section 6.3.3. A similar test was conducted with the Co-bearing variant, SCM (Figure 6-10b). The conductivity similarly increased for around 260 hours, after which it reached a plateau at close to 100 S/cm and then decreased over the next 160 hours and stabilized at 40 S/cm. These two materials show similar reduction profiles, based on their conductivity. The pO2 was slightly lower for the SCM sample than for the SNM sample, 10-24 atm, which might explain the slightly faster increase and peaking in the conductivity. The question arises: How can an order of magnitude greater conductivity than SMM (>100 S/cm vs 10 S/cm) be possible with the same oxygen-vacancy Mo5+/6+ conduction mechanism? Why is there a continuous increase of σ in dry H2/N2? Is the phase stable or is it the result of decomposition?PDF Image | Electrolysis of CO2 and H2O
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