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Chapter 1. Introduction 9 current density (the slope of the i-V curve). Because the i-V curve has curvature, one must define common points – the arrows mark ±0.75 A/cm2 in the figure – and calculate the ASR based on a chord from OCV to those points. In this example, OCV is at 0.90 V, the potential at +0.75 A/cm2 is 0.74 V and the potential at –0.75 A/cm2 is 1.12 V. Therefore the fuel cell ASR is0.21Ωcm2 (=(0.90–0.74)/0.75)andtheelectrolysisASRis0.29Ωcm2 (=(0.90–1.12) / –0.75 ). These are not far from real values measured at these conditions. In comparison with low-temperature PEM and alkaline cells, solid oxide cells have much lower ASR. Figure 1-3. Illustration of a typical polarization curve for a solid oxide cell at 850 °C in 50% H2 + 50% H2O with important thermodynamic potentials labeled. The relative lack of curvature of the i-V curve in comparison with low-temperature cells, especially near OCV, indicates very fast electrode reaction kinetics with high exchange current densities for both electrodes. The traditional fundamental relationships used to describe electrode kinetics, the Butler-Volmer equation and its derivatives, cannot be used in their basic forms to describe the i-V curves of these high temperature cells because these equations are based on electrochemical charge-transfer as the rate-limiting step. The electrode reactions still contribute to the cell resistance but reaction processes such as adsorption/desorption and diffusion may be slower than the actual electrochemical reactions in these electrodes. Other contributions to the cell resistance are gas concentration based effects (based on gas diffusion and non-equilibrium gas conversion) in the electrodes and in the gas flow channels, and finally the ohmic resistance of the ion-conducting electrolyte (as well as the ohmic resistance of the electron-conducting materials in the electrode, the interconnect plates, the wiring, etc, however this is all typically negligible). These complex processes are studied throughout this thesis, in Chapters 4, 5, and 6. The resistance of a single electrode can be isolated and studied individually, which is employed in Chapters 5 and 6. Increasing the temperature even higher can further reduce the ASR, however higher temperature can also cause the performance to degrade more quickly as the materials andPDF Image | Electrolysis of CO2 and H2O
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