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Chapter 3. Sustainable Hydrocarbon Fuels by Recycling CO2 with Renewable/Nuclear Energy 67 Cathode: H2O(g) + 2e– H2(g) + O2– or CO2(g) + 2e– CO(g) + O2– Anode: O2– 2e– + 1⁄2 O2(g) As with low-temperature electrolysis, cells designed as solid oxide fuel cells (SOFCs) can be used reversibly for electrolysis. However, due to differing conditions (the gas compositions at the electrodes and the direction of polarization across cell components and across interfaces between materials) between fuel cell and electrolysis operation, it may be desirable to make specialized cells for optimal electrolysis performance. Electrolysis of CO2, H2O, and co-electrolysis of CO2/H2O mixtures using solid oxide cells was first demonstrated in the 1960s under NASA contracts, for the purpose of O2 production for life support and propulsion in submarines and spacecraft [142-147] and research on using the cells for this purpose continues to this day [148-153]. The first solid oxide electrolysis research project unrelated to space exploration appears to be the HOT ELLY project in Germany started in 1975 [154], which focused on H2 production. The most common material composition of typical state-of-the-art SOECs today were already being used – a porous metal-ceramic Ni-YSZ composite cathode and a porous ceramic composite anode composed of lanthanum strontium manganite and YSZ, sandwiching a dense ceramic YSZ electrolyte (YSZ = yttria-stabilized zirconia, a material that conducts O2- ions at high temperatures). The performance, durability and materials used in high temperature electrolysis cells have been recently reviewed [100, 155]. A variety of alternative materials with improved properties for SOFCs are under development [156-159], many of which might be appropriate for use in SOECs. Much work has been done in testing cells and optimizing electrode and electrolyte materials for steam electrolysis [32, 99, 160-180], CO2 electrolysis [14, 32, 33, 39, 99, 148, 174, 181-183], and co-electrolysis of both H2O and CO2 simultaneously to produce syngas [19, 30, 34-38, 174, 184-186] (and see Chapter 4). In co-electrolysis, CO2 may be either electrolyzed or indirectly split via reverse-WGS. One can see in Figure 3-4 that the WGS equilibrium can go either way at the operating temperatures of an SOEC. Since CO2 electrolysis has a slightly higher resistance than H2O electrolysis [32, 35-39, 99, 174], it is expected that part of the CO produced results from RWGS. Whether part of the syngas is produced by the WGS equilibrium has little effect on the energy demand of syngas production in the cell, because the cell’s internal resistance can supply the heat needed for either the electrochemical or catalytic reactions. Systems integrating steam SOECs with solar [18, 19, 187-189] and nuclear energy [67, 190] have been examined and SOECs have been proposed for use in CO2-recycled synthetic fuel cycles [15, 18, 19, 34, 37, 38] (and see Chapter 4). A high current density of –3.6 A/cm2 was reported when operating an SOEC for steam electrolysis at 950 °C at 1.48 V [32]. At 850 °C a similar cell showed area specific resistances (ASRs) of 0.19 and 0.24 Ω cm2 for H2O electrolysis and CO2 electrolysis respectively, measuredPDF Image | Electrolysis of CO2 and H2O
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