Electrolysis of CO2 and H2O

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Electrolysis of CO2 and H2O ( electrolysis-co2-and-h2o )

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Chapter 1. Introduction 10 microstructures are more unstable. The performance and durability of a solid oxide electrolysis cell is examined in Chapter 4. The performance and durability of electrode materials are studied in Chapters 5 and 6. 1.2. Experimental Techniques A number of experimental and analytical techniques are employed throughout this thesis. Chapters 4, 5, and 6 include electrochemistry studies, and Chapter 6 also includes a study of other fundamental properties of materials – phase, microstructure, and electrical conductivity. The electrochemistry studies include performing polarization curves like the one described in the prior section. When testing single electrodes instead of full cells, the OCV is expressed as zero and then the voltage axis corresponds to overpotential. The electrochemistry studies also make heavy use of electrochemical impedance spectroscopy (EIS), a powerful experimental technique. The use of EIS to study electrochemical cells, for detailed mechanistic studies and as a diagnostic tool, has grown considerably during the last three decades [1]. In addition to applying direct current electricity, which is how cells are actually operated, alternating currents can be applied. In EIS a small amplitude periodic alternating-current is used. Applied to an electrochemical system at equilibrium or at a non-equilibrium steady-state, the small amplitude perturbs the system without disturbing the equilibrium or steady-state. Sinusoidal AC signals with amplitudes of a few mV or mA (depending on if the measurement is voltage-controlled or current-controlled) and frequency range of around 1 MHz to 1 mHz are typically used for studying solid oxide cells and their electrodes. The measured frequency- dependent response of the electrochemical system provides information about the reactions that take place at different rates, as well as other non-reaction processes that have different relaxation times, and about the capacitance of the processes. EIS is useful to study complex systems and to aid in identifying their mechanisms. Impedance measurements can take a long time when including the low-frequency data points (a single data point at 10 mHz takes at least 1.67 minutes and each data point is measured more than once to ensure noise-free data, and several data points per frequency decade are typically measured), so it is important that the system is nearly at steady-state during measurement or else the measurement will include drift and make data interpretation difficult or impossible. There are a number of ways to present impedance data. The most typical for the systems studied here are Nyquist and Bode plots. An ideal simulated impedance spectrum is shown in these types of plots in Figure 1-4. The measured impedance magnitude (the ratio of the measured voltage and current) and phase angle (the phase shift between the measured voltage and current sine waves) are converted into complex Cartesian coordinates using Euler's formula and displayed as the real part of the complex impedance, Zreal, and the imaginary part of the complex impedance, Zimag, as a function of the perturbation frequency f. In the Nyquist plot, a

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