Spinel block, solid electrolytes

The )5-aluminas are described in some detail in Chapter 2, only a few specific features are noted here. In the "-aluminas, the spinel blocks are stacked in such a way that the energetically equivalent sites occupied by Na" ions are ideally just half-filled in the -aluminas the spinel blocks are stacked so as to distinguish two types of Na" -ion sites of different potential energy, the Beevers-Ross (BR) and anti-Beevers-Ross (aBR) sites. In the Na-O planes, the shortest bottleneck distance 2.7 A is just a little greater than the sum of the ionic radii, 2.4 A, at room temperature, so a small value of AH can be anticipated. The discovery of fast Na -ion conductivity in the Na j5-aluminas (Yao and Kummer, 1967 Kummer and Weber, 1967) led to the invention of the Na/S battery that triggered extensive interest in the solid-electrolyte problem. 

The discovery of a solid conductor of sodium ions by Kummer and Weber made possible the construction of sodium-sulfur cells which utilize molten or dissolved reactants separated by the ceramic electrolyte j3-(cf. Fig. 12), or, usually, j3"-alumina. The latter ceramic has a three Al-0 spinel block structure, a molar ratio of Al203-Na20 = 5, and contains 1-4% of MgO or Li20. The resistivity of the polycrystalline material at 350°C is about 5 H cm, -4 times lower than that of alumina. Other recently reported solid Na ion conductors containing phosphorus oxides do not seem to be stable in contact with sodium at elevated temperatures. ... 

S. W. Smoot, D. H. Whitmore and W. P. Halperin, Influence of stoichiometry and the nature of the spinel-block stabilizing element on proton transport behavior in solid electrolyte with the p"-alumina structure, Solid States Ionics 18/19 (1986) 687-93. 

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