Electrolytes fluorites

Four solid oxide electrolyte systems have been studied in detail and used as oxygen sensors. These are based on the oxides zirconia, thoria, ceria and bismuth oxide. In all of these oxides a high oxide ion conductivity could be obtained by the dissolution of aliovalent cations, accompanied by the introduction of oxide ion vacancies. The addition of CaO or Y2O3 to zirconia not only increases the electrical conductivity, but also stabilizes the fluorite structure, which is unstable with respect to the tetragonal structure at temperatures below 1660 K. The tetragonal structure transforms to the low temperature monoclinic structure below about 1400 K and it is because of this transformation that the pure oxide is mechanically unstable, and usually shatters on cooling. The addition of CaO stabilizes the fluorite structure at all temperatures, and because this removes the mechanical instability the material is described as stabilized zirconia (Figure 7.2). 

Fluorine compounds from fluorite (fluorspar, CaF2) are used in water treatment (to suppress dental caries) and to make fluoropolymers (such as Teflon), lubricants, and refrigerants. Molten cryolite (Na3AlF6) is essential as a solvent for Al203 in the electrolytic production of aluminum metal, while the isotopic enrichment of uranium for nuclear power reactors is usually achieved by diffusion or gas centrifugation of volatile UF6. 

In generalizing these results, we can apply them to other solid electrolytes as well, for example, to other fluorite type oxides (e.g., Hf02, CeOz) that have been doped with heterovalent cations (e.g., SrO, BaO, Y203, La203). 

Yttria-stabilized zirconia f[Zrlj YJ02, /2) is known in the literature as YSZ and has a fluorite-type structure [67] (see Figure 2.16). This material has a high oxygen ion conductivity and is, therefore, applied as a high-temperature electrolyte material, for example, in high-temperature fuel cells [68,73],... 

Fluorine occurs in nature in the form of the minerals fluorite, CaF2, cryolite, Na3AlF6, and fluoroapatite, Ca5(P04)3F, and one commercial source of natural cryolite is Greenland. Both of the other minerals are widespread in nature, although the major use of fluoroapatite is in the production of fertilizers, not as a primary source of fluorine. Extensive fluorite deposits are found in Southeastern Illinois and Northwestern Kentucky. From the standpoint of fluorine utilization, both cryolite and fluorite are extremely important minerals. Cryolite is used as the electrolyte in the electrochemical production of aluminum from bauxite, and fluorite is used as a flux in making steel. Today, most of the cryolite used is synthetic rather than the naturally occurring mineral. 

Let us briefly consider in this context two important classes of materials. The first are the oxides of fluorite type such as Zr02 or Ce02. They can accommodate high concentrations of lower valent cations. Y203 doping of Zr0210 leads to the very important YSZ electrolyte. 

The fluorite oxides are the classical oxygen ion conducting oxide materials the study of these materials as electrolytes derives from the early investigations of Walther Nemst 1900. The fluorite structure illustrated in Figure 13 is best described for the purposes of the present discussion as a primitive cubic array of anions (O ) with half the cube centers occupied by cations the latter form a face-centered-cubic (fee) arrangement of the cation sublattice. The unoccupied cube centers play a central role in the defect physics and ionic conductivity of fluorites, because they... 

Oxides exhibiting only high ion conductivity are mainly fluorite-related structures based on zirconia or ceria. Zirconia-based electrolytes are currently used in solid oxide fuel cells (SOFCs). The MIEC oxides are more attractive for separative membrane applications, and these oxides mainly belong to the following types fluorite-related oxides doped to improve their electron conduction, - ... 

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