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Chapter 3. Sustainable Hydrocarbon Fuels by Recycling CO2 with Renewable/Nuclear Energy 65 lower than the other electrolysis systems to be competitive in terms of H2 production price, assuming they have a similar operating life. However, the operating life of this type of cell might be significantly longer due to the possibly self-healing nature of the catalyst layer which is constantly re-forming on the surface. Furthermore, due to the potentially simple construction and materials requirements of the cell, the cell production cost could indeed be orders of magnitude lower than the other cell types, and future electrode designs might yield improved current density. This electrode technology and cell type is at a very early stage of research. Further study and development of this type of cell is necessary to assess economic viability. Electrolyzing CO2 in non-aqueous organic solvents such as methanol or acetonitrile can yield CO [117, 132] via the cathode reaction 2CO2 + 2e– CO + CO32– . Similarly, electrolysis of supercritical CO2 has also been examined. Pure supercritical CO2 exhibits zero or negligible conductivity, so electrolytes composed of additives dissolved in supercritical CO2 [16] or ionic liquids (as solvent and electrolyte into which supercritical CO2 is dissolved) [139] have been studied. Co-production of CO and H2 via electrolysis of supercritical CO2 and water dissolved in an ionic liquid electrolyte has been initially demonstrated [139]. The large overpotentials observed in that study may be the result of the use of a basic unoptimized cell, so at present it is difficult to assess the potential of this method. 3.2.2.3.2. High-temperatureelectrolysis As mentioned earlier, performing electrolysis at high temperature has both a thermodynamic advantage and an advantage in reaction rates. With increasing temperature, a larger portion of heat and corresponding smaller portion of electricity is needed for the dissociation. This can be seen in the lower open-circuit voltage for the high temperature cells in Figure 3-5. This heat can be supplied from external sources, or it can be the Joule heat that is inevitably produced, due to the internal electric resistance of the cell, when applying the overvoltage necessary to achieve sufficient production rates. Rather than losing this ohmic heat, it is used in the disassociation of steam and/or CO2. High temperature electrolysis therefore relies in part on thermolysis pushing the equilibrium toward dissociation. The high temperature also results in faster reaction kinetics which reduces the need for expensive catalyst materials. These differences between low and high temperature electrolysis cells can be seen in the polarization curves illustrated in Figure 3-5. These advantages enable very efficient operation (at near the thermoneutral voltage) at very high current densities (potentially leading to low capital cost). There are two types of high temperature electrolyzers (typically >600 °C operation), those with molten carbonate electrolytes and those with solid oxide electrolytes. Since the electrolytes of solid oxide electrolysis cells (SOECs) and molten carbonate cells conduct O2- andPDF Image | Electrolysis of CO2 and H2O
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