Perovskite-related materials

Brown, I. D. (1991a). Internal strain in perovskite related materials. In P. K. Davies and R. S. Roth (eds), Chemistry of Electronic Materials. Washington US Department of Commerce, pp. 471-83. 

J. B. Goodenough and J. M. Longo, in Crystallographic and Magnetic Properties of Perovskite and Perovskite-Related Materials (ed. K.-H. Hellwege), Springer, Berlin, 1970. 

Recently, an unusual series of perovskite related materials has been reported with the composition LasTsT Oie, where T = Mo + or Re + and T = Mg +, Mn +, Fe +,... 

Finally, it should be noted that numerous perovskite-related materials with relatively low oxygen ionic conductivity at 700-1200 K have been excluded from consideration in this brief survey, but may have potential electrochemical applications in fuel cell anodes, current collectors, sensors, and catalytic reactors. Further information on these applications is available elsewhere 1-4, 11, 159, 217-219]. 

Salje, E. (1989) Characteristics of perovskite-related materials. Philos. Trans. R. Soc. London, A328, 409 16. 

Table 20.1 Catalytic activity reported as Tgo% (temperature at which a 90% CO conversion is achieved) and surface-oxygen composition of several perovskite-related materials.

Modular structures are those that can be considered to be built from slabs of one or more parent structures. Slabs can be sections from just one parent phase, as in many perovskite-related structures and CS phases, or they can come from two or more parent structures, as in the mica-pyroxene intergrowths. Some of these crystals possess enormous unit cells, of some hundreds of nanometers in length. In many materials the slab thicknesses may vary widely, in which case the slab boundaries will not fall on a regular lattice and form planar defects. 

The spinel family of oxides with composition AB2O4 has the A and B cations distributed in octahedral and tetrahedral sites in a close-packed oxygen structure (Supplementary Material SI). Impurity doping can take place by the addition of a dopant to octahedral or tetrahedral sites. In this, the spinel family of compounds is quite different from the A2B04 perovskite-related phases of the previous section in that both cation sites are similar in size and can take the same cations. 

In this chapter the technological development in cathode materials, particularly the advances being made in the material s composition, fabrication, microstructure optimization, electrocatalytic activity, and stability of perovskite-based cathodes will be reviewed. The emphasis will be on the defect structure, conductivity, thermal expansion coefficient, and electrocatalytic activity of the extensively studied man-ganite-, cobaltite-, and ferrite-based perovskites. Alterative mixed ionic and electronic conducting perovskite-related oxides are discussed in relation to their potential application as cathodes for ITSOFCs. The interfacial reaction and compatibility of the perovskite-based cathode materials with electrolyte and metallic interconnect is also examined. Finally the degradation and performance stability of cathodes under SOFC operating conditions are described. 

The perovskite structure is capable of high anion conductivity when oxide vacancies are introduced, as in, for example, Lai (Sr Co03 (/2 or in the perovskite-related superconductor phases, La2Cu04 and YBa2Cu307. The oxide ion transport number is not unity since such materials are often electronic conductors as well, due to the presence of... 

One important thing to be kept in mind here is that the ionic radii are derived from the cation-anion bond distances measured experimentally at room temperature, not at the temperatures where the formation reactions take place. At present, there is no way to estimate exactly the tolerance factor at high (or low) temperatures. So, whether one can obtain a perovskite or related material from a given A-B-X combination or not depends mostly upon experimental tests. 

Low-Dimensional Oxides, Materials with 2H-Perovskite Related Structures... 

Perovskite-related Oxides.—The perovskite-related oxides have been studied extensively in recent years because of the large variety of device applications for which these materials are suited. The interaction between structure, properties, and stoicheiometry is significant at all levels, but here we will discuss only the narrow areas where intergrowth is a dominant structural feature. We will not, therefore, consider solid solutions typified by the Pb(Zr Tii )03 ferroelectrics, and neither will we discuss the structurally complex but stoicheiometric phases related to hexagonal BaTiOj, which includes BaNiOj, which has a simple two-layer repeat in the c-direc-tion, the nine layer BaRuOj, the twelve layer Ba4Re2CoOj2, and the twenty-four layer Sr5Re20ig phase. The crystal chemistry of these phases is treated in detail by Muller and Roy. The materials we shall discuss are the two series of phases A B 0 +2 and A + B 02n+, and the bismuth titanates. Some of the anion deficient perovskites, ABO -x, will be considered in Section 5. 

Additional attempts have been presented to render hosts with the fluorite and the related pyrochlore structure electronically conductive by doping with mixed-valence and/or shallow dopants. The list of dopant materials examined includes oxides of elements of, for example, Ti, Cr, Mn, Fe, Zn, Fe, Sn, Ce, Pr, Gd, Tb and U. In general, however, the extent of mixed conductivity that can be obtained in fluorite-type ceramics is rather limited, by comparison with the corresponding values found in some of the perovskite and perovskite-related oxides considered in the next section. 

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