Anion conductors fluorites

The final anion-deficient fluorite structure type material to mention is 8-Bi203. The formula of this phase makes it surprising that a fluorite structure form exists, but such a structure occurs at high temperatures. The resulting phase is an excellent O2- ion conductor with many potential applications. Unfortunately, the high-temperature form is not maintained when the compound is cooled to room temperature. However, fluorite structure anion-deficient phases of the same type can be prepared by reaction with many other oxides, and these are stable at room temperature. The majority of these materials have a modulated anion substructure (Section... 

Anion-deficient fluorite oxides are also present, for example, U02- c, Ce02-x The presence of anion vacancies in reduced fluorites has been confirmed by diffraction studies. In reduced ceria for example, some well-ordered phases has been reported (Sharma et al 1999). The defective compounds show very high anion mobilities and are useful as conductors and as catalytic materials as will be described later. However, the structures of many anion-deficient fluorite oxides remain unknown because of the shear complexity of the disordered phases. There are, therefore, many opportunities for EM studies to obtain a better understanding of the defect structures and properties of these complex materials which are used in catalysis. 

There has been a strong effort to rationalise and elucidate a structural principle which will account for all the anion-deficienl, fluorite-related, mixed-valent binary oxides of cerium, praseodymium and terbium. This is a key step not only for the solid-state chemistry of these materials but also for a large class of fluorite-related materials involved in applications such as fast oxygen conductors and as catalysts. The two main theoretical approaches to the problem were developed by Martin and by Kang and Eyring, and will be illustrated in the following sections. 

The pyrochlore-type compounds, where the crystal structure is usually considered as a cation-ordered fluorite derivative with % vacant oxygen site per fluorite formula unit, constitute another large family of oxygen anion conductors [9, 33, 41—43, 84—88]. The unoccupied sites provide pathways for oxygen migration furthermore, the pyrochlore structure may tolerate formation of cation and anion vacancies, doping in both cation sublattices, and antistructural cation disorder. Regardless of these factors. 

Anion conduction, particularly oxide and fluoride ion conduction, is found in materials with the fluorite structure. Examples are Cap2 and Zr02 which, when doped with aliovalent impurities. Fig. 2.2, schemes 2 and 4, are F and 0 ion conductors, respectively, at high temperature. The 3 polymorph of 61303 has a fluorite-related structure with a large number of oxide vacancies. It has the highest oxide ion conductivity found to date at high temperatures, > 660 °C. 

Ionic Conductivity (see Ionic Conductors). Pluoride anionic conductivity is observed mainly in derivatives of fluorite (Cap2) and tysonite (Lap3). If Cap2 is doped by a tervalent rare-earth metal ion, the additional fluoride ions are positioned in interstitials where they become mobile by a hopping mechanism. 

Electrolytes are distinguished from pure electronic conductors by the fact that the passage of an electric current is only insured by displacement of charged species called ions and hence accompanied by a transfer of matter. Therefore, electrolytes are entirely ionic electrical conductors without exhibiting any electronic conductivity (i.e., no free electrons). They can be found in the solid state (e.g., fluorite, beta-aluminas, yttria-stabilized zirconia, and silver iodide), liquid state (e.g., aqueous solutions, organic solvents, molten salts and ionic liquids), and gaseous state (e.g., ionized gases and plasmas). The ions (i.e., anions or cations)... 

The fluorite-type oxides are not the only possible 0 ion conductors. Perovskite-t e oxides wit anion acancies can be formed by substituting M for M or M for M. The ionic... 

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