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Chapter 6. Molybdate Based Ceramic Electrode Materials 211 By modifying the composition (adding Ti to the B-site), it was possible to prevent decomposition. Another member of the double-perovskite molybdate family, Sr2FeMoO6, exhibited similarly high electronic conductivity and electrocatalytic activity but did not decompose. The high activity was the result of a different mechanism (besides a nanostructured surface), probably related to the defect chemistry of the material (possibly high mixed ionic- electronic conductivity) and/or the mixed valency of the Fe and Mo ions. The polarization resistances of the best molybdate materials were two orders of magnitude lower than that of donor-doped strontium titanates. Whereas nearly all of the molybdates showed higher performance for H2O electrolysis than CO2 electrolysis, one with vanadium showed nearly equal performance, and a non-molybdate which exhibits some complementary properties to the best molybdates, Gd-doped ceria in nanoparticle form, was found to be an excellent electrocatalyst for CO2 electrolysis and CO oxidation (moreso than for H2O/H2 for which it is known to be good). In terms of the stability of molybdate based materials, Mo needs a partner. If a redox- stable or near-redox-stable material is desired, one must allow the fully oxidized valence of 6+. Alternatively, if one can deal with reversible phase changes accompanied by large volume expansion and contraction (as with Ni-NiO in conventional electrodes), one can use Mo with 4+ valence. In terms of cost, Mo is a somewhat more expensive metal than Ni – currently just less than twice as expensive per unit mass. However, it is important to note that in these ceramic materials Mo comprises only half of the B site – it makes up only 1/10th of the atoms in the crystal lattice of a double perovskite (~25 wt% depending on the other elements). Although Mo is an order of magnitude scarcer than Ni is the Earth’s crust, it is 2-3 orders of magnitude more abundant than Pt, Pd and other expensive metals that are considered for low-temperature fuel cell catalysts, so there does not appear to be a resource limitation for Mo especially if it is used in a thin layer. Finally, according to cost estimates of solid oxide cell systems, the total manufacturing cost is dominated not by the raw materials but by the fabrication process and balance of system [112, 113]. Therefore, the use of these molybdate materials is not expected to be economically prohibitive. On the contrary, if in a porous technological electrode they can provide the exceptional level of electrocatalytic activity observed in the present study, they would most likely improve the economics of solid oxide cells. 6.5. References 1. Steele BCH, Survey of materials selection for ceramic fuel cells II. Cathodes and anodes. Solid State Ionics, (1996). 86-88(Part 2): p. 1223-1234. 2. Atkinson A, Barnett S, Gorte RJ, Irvine JTS, McEvoy AJ, Mogensen M, et al., Advanced anodes for high-temperature fuel cells. Nature Materials, (2004). 3(1): p. 17-27.PDF Image | Electrolysis of CO2 and H2O
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