With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H(-)) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm(-1) at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.
Contents S1. Synthesis and Initial Characterisation S2. Crystallographic details of the refined hydrated Na-, (K-and K, Hand nd Cs-MER S3. Structural response to dehydration S4. Adsorption studies S5. In situ laboratory PXRD of M-MER with adsorbed CO2 S6. Crystallographic details of the refined dehydrated solids with adsorbed CO2 S7. CO2/CH4 separation and breakthrough curves S8. Kinetic measurements using the Zero Length Column technique S9. K,H-MER zeolite structural and adsorption results S2 S1. Synthesis and Initial Characterisation Synthesis Colloidal silica, Ludox HS-40 (12.5 g; 40%, suspension in water; Sigma-Aldrich) was added to 35% aqueous solution of tetraethylammonium hydroxide (3.15 g; 35% TEOAH, Sigma-Aldrich) and the resulting mixture was stirred for 1 h. To this mixture, a solution made by dissolving metal Al (0.8 g, 99%, Alfa Aesar) in 3 g TEAOH and KOH (0.6 g, 85%, Fisher Chemicals), which was also mixed for 1 h, was added. The gel formed was continuously stirred for 10 min, transferred to a PTFE-lined stainless-steel autoclave and hydrothermally treated at 423 K under slow rotation (60 rpm). The resultant solid product, collected after 96 h, was
Doped strontium titanates have been widely studied as potential anode materials in solid oxide fuel cells (SOFCs). The high n-type conductivity that can be achieved in these materials makes them well suited for use as the electronically conductive component in SOFC anodes. This makes them a potential alternative to nickel, the presence of which can be a major cause of degradation due to coking, sulfur poisoning and low tolerance to redox cycling. Here anode performance results are presented for an A-site deficient strontium titanate co-doped with lanthanum and calcium on the perovskite A-site, La 0.20 Sr 0.25 Ca 0.45 TiO 3 (LSCT A-). LSCT A-anodes and LSM cathodes were screen printed on 160 μm thick 6-ScSZ electrolyte supports. The LSCT A-anode backbone showed poor electrode performance, but its conductivity was sufficient to keep ohmic losses low. Upon impregnation with combinations of ceria and nickel, ohmic losses and polarization impedances are significantly reduced, resulting in a drastic improvement in anode performance. Unexpectedly, the performance of cells impregnated with both ceria and nickel showed an improvement upon redox cycling. A stable area specific resistance of 0.37 cm 2 was achieved after 20 redox cycles and 250 hours of operation at 900 • C in H 2 with 8% H 2 O, showing excellent redox stability.
Modified strontium titanates have received much attention recently for their potential as anode material in solid oxide fuel cells (SOFC). Their inherent redox stability and superior tolerance to sulphur poisoning and coking as compared to Ni based cermet anodes could improve durability of SOFC systems dramatically.Various substitution strategies can be deployed to optimise materials properties in these strontium titanates, such as electronic conductivity, electrocatalytic activity, chemical stability and sinterability, and thus mechanical strength. Substitution strategies not only cover choice and amount of substituent, but also perovskite defect chemistry, distinguishing between A-site deficiency (A 1Àx BO 3 ) and cationstoichiometry (ABO 3+d ). Literature suggests distinct differences in the materials properties between the latter two compositional approaches. After discussing the defect chemistry of modified strontium titanates, this paper reviews three different A-site deficient donor (La, Y, Nb) substituted strontium titanates for their electrical behaviour and fuel cell performance. Promising performances in both electrolyte as well as anode supported cell designs have been obtained, when using hydrogen as fuel.Performances are retained after numerous redox cycles. Long term stability in sulphur and carbon containing fuels still needs to be explored in greater detail.
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