In an effort to produce hydrogen without the unwanted greenhouse gas byproducts, high-temperature thermochemical cycles driven by heat from solar energy or next-generation nuclear power plants are being explored. The process being developed is the thermochemical production of Hydrogen. The Sulfur-Iodide (SI) cycle was deemed to be one of the most promising cycles to explore. The first step of the SI cycle involves the decomposition of H{sub 2}SO{sub 4} into O{sub 2}, SO{sub 2}, and H{sub 2}O at temperatures around 850 C. In-situ removal of O{sub 2} from this reaction pushes the equilibrium towards dissociation, thus increasing the overall efficiency of the decomposition reaction. A membrane is required for this oxygen separation step that is capable of withstanding the high temperatures and corrosive conditions inherent in this process. Mixed ionic-electronic perovskites and perovskite-related structures are potential materials for oxygen separation membranes owing to their robustness, ability to form dense ceramics, capacity to stabilize oxygen nonstoichiometry, and mixed ionic/electronic conductivity. Two oxide families with promising results were studied: the double-substituted perovskite A{sub x}Sr{sub 1-x}Co{sub 1-y}B{sub y}O{sub 3-{delta}} (A=La, Y; B=Cr-Ni), in particular the family La{sub x}Sr{sub 1-x}Co{sub 1-y}Mn{sub y}O{sub 3-{delta}} (LSCM), and doped La{sub 2}Ni{sub 1-x}M{sub x}O{sub 4} (M = Cu, Zn). Materials and membranes were synthesized by solid state methods and characterized by X-ray and neutron diffraction, SEM, thermal analyses, calorimetry and conductivity. Furthermore, we were able to leverage our program with a DOE/NE sponsored H{sub 2}SO{sub 4} decomposition reactor study (at Sandia), in which our membranes were tested in the actual H{sub 2}SO{sub 4} decomposition step.
The potential for electrochromic (EC) materials to be incorporated into a Fabry-Perot (FP) filter to allow modest amounts of tuning was evaluated by both experimental methods and modeling. A combination of chemical vapor deposition (CVD), physical vapor deposition (PVD), and electrochemical methods was used to produce an ECFP film stack consisting of an EC WO{sub 3}/Ta{sub 2}O{sub 5}/NiO{sub x}H{sub y} film stack (with indium-tin-oxide electrodes) sandwiched between two Si{sub 3}N{sub 4}/SiO{sub 2} dielectric reflector stacks. A process to produce a NiO{sub x}H{sub y} charge storage layer that freed the EC stack from dependence on atmospheric humidity and allowed construction of this complex EC-FP stack was developed. The refractive index (n) and extinction coefficient (k) for each layer in the EC-FP film stack was measured between 300 and 1700 nm. A prototype EC-FP filter was produced that had a transmission at 500 nm of 36%, and a FWHM of 10 nm. A general modeling approach that takes into account the desired pass band location, pass band width, required transmission and EC optical constants in order to estimate the maximum tuning from an EC-FP filter was developed. Modeling shows that minor thickness changes in the prototype stack developed in this project should yield a filter with a transmission at 600 nm of 33% and a FWHM of 9.6 nm, which could be tuned to 598 nm with a FWHM of 12.1 nm and a transmission of 16%. Additional modeling shows that if the EC WO{sub 3} absorption centers were optimized, then a shift from 600 nm to 598 nm could be made with a FWHM of 11.3 nm and a transmission of 20%. If (at 600 nm) the FWHM is decreased to 1 nm and transmission maintained at a reasonable level (e.g. 30%), only fractions of a nm of tuning would be possible with the film stack considered in this study. These tradeoffs may improve at other wavelengths or with EC materials different than those considered here. Finally, based on our limited investigation and material set, the severe absorption associated with the refractive index change suggests that incorporating EC materials into phase correcting spatial light modulators (SLMS) would allow for only negligible phase correction before transmission losses became too severe. However, we would like to emphasize that other EC materials may allow sufficient phase correction with limited absorption, which could make this approach attractive.