Perovskite chemical stability

LaMn03 is an intrinsic p-type conductor. Electronic conductivity is enhanced by substitution of the La3+ site with divalent ions such as strontium or calcium. Of the alkaline-earth dopants, Sr substitution is preferred for SOLC applications because the resultant perovskite forms stable compounds with high conductivity in the oxidizing atmosphere found at the cathode [41], Extensive data show that La, xSi. MnO where x = 0.1 - 0.2, provides high conductivity while maintaining mechanical and chemical stability with YSZ [41, 42],... 

Haile, S. M., Staneff, G., and Ryu, K. H. Non-stoichiometry, Grain Boundary Transport and Chemical Stability of Proton Conducting Perovskites, Journal of Materials Science, 36, 1149 (2001). 

Thin films, to attain enough sensitivity and response time, of oxide materials normally deposited on a substrate are typically used as gas sensors, owing to their surface conductivity variation following surface chemisorption [183,184], Surface adsorption on a Sn02 film deposited on alumina produces a sensitive and selective H2S gas sensor [185]. In addition, a number of perovskite-type compounds are being used as gas sensor materials because of their thermal and chemical stabilities. BaTi03, for example, is used as sensor for C02 [183],... 

Chemical stability indicates that in the cubic, metallic perovskites the interstitial C and N are probably neutral. They represent, therefore, an M atom with half filled p or s-p orbitals, and in the cubic structure the metal-M-metal interaction is defined by Figure 86. [This is to be contrasted with low-temperature CrN, which has considerable ionic character and an ordering of its covalent character along a given axis.] In contrast to the M atoms of the Heusler alloys, the p electrons of C and N correlate with, and therefore spin pair, the near-neighbor eg electrons. The metal- -metal interactions are determined by the Ug electron-spin correlations since Hu 2.76 A < Rc. 

Electrodes The anodes of SOFC consist of Ni cermet, a composite of metallic Ni and YSZ, Ni provides the high electrical conductivity and catalytic activity, zirconia provides the mechanical, thermal, and chemical stability. In addition, it confers to the anode the same expansion coefficient of the electrolyte and renders compatible anode and electrolyte. The electrical conductivity of such anodes is predominantly electronic. Figure 14 shows the three-phase boundary at the interface porous anode YSZ and the reactions which take place. The cathode of the SOFC consists of mixed conductive oxides with perovskite crystalline structure. Sr doped lanthanum manganite is mostly used, it is a good /7-type conductor and can contain noble metals. 

An example of a complex material used in syngas applications is Lag jSro gFeo g. Coo.iCro.203 [26]. This composition contains many of the features previously discussed. It is predominately an iron-based perovskite, providing both electronic and ionic conductivity. In order to improve the chemical stability and resistance to chemical expansion, the B-site is doped with chromium. A small amount of cobalt is added in order to improve the electronic conductivity, and cobalt wiU also increase the ionic conductivity slightly. Strontium is used as the A-site dopant in order to avoid the problems associated with calcium, and particularly with barium, in regard to reaction with CO2. In addition, the material has been made substantially A-site deficient to improve its stability. 

A second-generation immobilization material, synroc, is in development. This synthetic rock, based on mixed titanate phases such as zirconolite, hollandite, or perovskite, incorporates the HLW elements into its crystal structure, yielding excellent chemical stability. Synroc features leach rates more than an order of magnitude lower than borosilicate glass. 

Chemical Stability of Perovskite Membranes Under Flue-Gas Conditions... 

A material for which the chemical stability in the presence of CO2 and SO2 has been extensively studied is BSCF, as it is one of the membrane materials with the highest flux. The presence of CO2 causes a reversible decline in oxygen flux. Even at concentrations of 500 ppm CO2 (ambient air), a slight decrease in the oxygen permeation rate is observed [34]. This decrease is caused by the formation of carbonates of alkaline earth metals on the exposed surface of the membrane. The carbonate formation of perovskite materials AB03 g in the presence of CO2 can be expressed as follows [72] ... 

For perovskite-type oxides, the proton solubility decreases, but the stability to CO2 increases as the basicity of B-site ions decreases in the order of Ce Zr Sn Nb Ti [156]. The best compromise for high proton conductivity and chemical stability is found for Y-doped BaZr03, but unfortunately, this material exhibits large grain boundary resistance, and it stiU reacts slightly with CO2 under certain conditions [157]. Chemical stability against CO2 has been demonstrated recently with BaCeo,3Zro,5Yo.203 8 by Fabbri et al. [158]. 

Broadly, interconnect materials for SOFC fall into two categories conductive ceramic (perovskite) materials for operation at high temperature (900 to 1000 °C) and metallic alloys for lower temperature operation. Though the shape of SOFC interconnects depends heavily on the cell and stack design, the materials choice is almost entirely determined by physical and chemical stability under operating conditions. 

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