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Chapter 5. Aspects of Metal-YSZ Electrode Kinetics 145 Table 5-4. Summary of post-bias relaxation for the metals. ―-― signifies little or no effect, ―X‖ signifies significant activation of LSRP followed by relaxation to near the value prior to polarization, and ―XX‖ signifies significant activation from which the electrode does not relax over an extended time. Metal Atmosphere Anodic activation Cathodicactivation - - - -b -b XX X X a Uncertain; the +300 mV polarization was not included as for the other metals. Most likely ―-― would be ―X‖. b The electrode was still activated when these cathodic polarizations were conducted, so these cathodic polarizations might be more activating than they seem. catalyst for carbon deposition. However, carbon deposition is usually expected to deactivate, not activate, Ni electrodes and it should not occur as CO is consumed and CO2 produced since any deposited carbon should be removed by the Boudouard equilibrium reaction (CO2 + C 2 CO). —Morphological changes. It is also conceivable that morphological changes at the interface that lengthen the TPB could produce similar lasting activation effects. For Ni, if structural rearrangements via Ni-NiO occurred and roughened the Ni perimeter at high anodic polarization, as discussed in section 5.3.4.1 and as will be discussed further in section 5.3.5.1, the 850 °C steam in the 50% H2O/H2 atmosphere might accelerate smoothing it back out (see the discussion about Ni transport via Ni hydroxide species in section 5.3.4.1) and reducing the TPBL back to normal, whereas the 50% CO2/CO atmosphere would not. Alternatively, mobilization and removal of impurities from the TPB, thereby lengthening the TPB, might be occurring (see section 5.3.4.1). However, that mechanism is based on the impurities reacting with water, which is consistent with activation by H2 oxidation but would not explain the activations in CO/CO2 which are observed to be just as common. 5.3.5. Effects of Extreme Gas Conditions and Applied Potentials 5.3.5.1. Oxidation One of the smooth electropolished Ni electrodes was oxidized by exposure to air for 2 hours at 850 °C. The impedance spectra measured in 3% H2O/H2 before and after oxidation are shown in Figure 5-24. The LSRP decreased by a factor of 10 (from 22 kΩ cm to 2.3 kΩ cm at 850 °C) as a result of the oxidation. RS, and therefore the contact area, did not change. During the next 4 hours at 850 °C, the LSRP did not change. However, upon increasing the temperature to 1000 °C, the first IS showed an LSRP of 3 kΩ cm, larger than the measurements Cu Ni CO/CO2 H2/H2O - X Pd Pt H2/H2O - CO/CO2 H2/H2O XX XX CO/CO2 H2/H2O X Xa CO/CO2 -aPDF Image | Electrolysis of CO2 and H2O
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