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Chapter 5. Aspects of Metal-YSZ Electrode Kinetics 138 Figure 5-18. Impedance spectra measured under DC bias from +300 to –300 mV in 150 mV increments on a Ni electrode at 1000 °C in 3% H2O/H2. The order was +150, +300, –150, –300 mV, and then OCV 6 hours later. The impedance at OCV is somewhat less than that measured before the polarizations; see the next section. Impedance spectra measured under DC bias in the range of +300 to –300 mV in 100 mV increments at 850 °C for both 50% H2O/H2 and 50% CO2/CO atmospheres are shown in Figure 5-19, Figure 5-20, Figure 5-21, and Figure 5-22 for Cu, Ni, Pd, and Pt electrodes respectively. The spectra are consistent with the polarization curves of Figure 5-16 and provide more detail. Cu and Ni have higher anodic than cathodic activity in both atmospheres (Figure 5-19 and Figure 5-20). Pt has higher anodic activity in H2/H2O, but lower anodic than cathodic activity in CO/CO2 (Figure 5-22). Pd has higher cathodic than anodic activity in both atmospheres except at high anodic overpotential in H2/H2O (Figure 5-21). Pd is more active under both directions of polarization than at OCV in both atmospheres, whereas Cu, Ni, and Pt are all more active at OCV than under cathodic bias in H2/H2O. Since charge transfer resistance decreases with increasing overpotential, this higher resistance at cathodic overpotentials than at OCV suggests that charge transfer is not limiting. The shapes and apparent number of processes contributing to the impedance spectra change under polarization. For Cu, Ni and Pt in H2/H2O and Cu and Ni in CO/CO2, the anodic polarized spectra exhibit low-frequency inductive loops. These loops are also observed for some cathodic polarized spectra – Ni in H2/H2O and Pd in both H2/H2O and CO/CO2.PDF Image | Electrolysis of CO2 and H2O
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