Spinel blocks

The structure of / -alumina is shown in Fig. 5. The aluminum and oxygen ions (green and red, respectively) form spinel blocks. The mobile sodium ions (blue) are located in layers between them. The spinel blocks are connected to each other by oxygen ion bridges within the conducting layer. 

Figure 5. Schematic representation of the ft -alumina structure. The aluminum (green) and oxygen (red) ions form spinel blocks which are separated from each other by oxygen bridges. The mobile sodium ions (blue) are located in the layer. The unit cell is indicated.

The unit cell of (3-alumina is hexagonal, with lattice parameters a = 0.595 nm, c = 2.249 nm. The dominant features of the idealized structure of (3-alumina, with composition NaAlnOi7, are layers called spinel blocks stacked perpendicular to the c axis (Fig. 6.10a). These blocks are composed of four oxygen layers in a... 

The spinel blocks in (3-alumina are related by mirror planes that mn through the conduction planes that is, the orientation of one block relative to another is derived by a rotation of 180°. A second form of this compound, called (3"-alumina, has similar spinel blocks. However, these are related to each other by a rotation of 120°, so that three spinel block layers are found in the unit cell, not two. The ideal composition of this phase is identical to that of (3-alumina, but the unit cell is now rhombohedral. Referred to a hexagonal unit cell, the lattice parameters are a = 0.614 nm, c = 3.385 nm. The thickness of the spinel blocks and the conduction planes is similar in both structures.3... 

There are two other phases that are similar to (3- and (3"-alumina but are built from spinel blocks that are six close-packed oxygen layers thick. The material (3" -alumina is the analog of (3-alumina, with the spinel blocks related by 180° mirror-plane (hexagonal) symmetry, while the phase (3""-alumina, the analog of (3"-alumina, has blocks related by 120° rotation and rhombohedral symmetry. 

This is due to charge neutrality, 1 Na + = jM2+ = jM31. If more is added, there must either be more O2 in the interlayers or V, in the spinel blocks. Interstitial O in the spinel blocks is unlikely. 

The beta-alumina structures show a strong resemblance to the spinel structure. They are layered structures in which densely packed blocks with spinel-like structure alternate with open conduction planes containing the mobile Na ions. The and /S" structures differ in the detailed stacking arrangement of the spinel blocks and conduction planes. Fig. 2.9. 

In P", (a), the oxide packing arrangement comprises close packed layers in a cubic close packed,. .. ABC. .., stacking sequence, which continues throughout the structure. The spinel blocks are four oxide layers thick and contain AP" ions (and stabilising Li, Mg ions) distributed over tetrahedral and octahedral sites, as in spinel, MgAl204. These sites... 

The excess of Na ions (above the NaAlnOi7 stoichiometry) requires some means of charge balance and the mechanism is found to be different in the P and P" structures. In P", some AP ions in the spinel blocks are replaced by Li /Mg " the consequent reduction in positive charge compensates that of the excess Na" ions in the conduction planes. In P,... 

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. 

Fig. 7.17 Relation of the spinel structure (left) io the structure of sodium beta alumina (right). The sodium ions are free to move in the open spaces between spinel blocks, held apart by Al—O—Al pillars in the "parking garage structure. [In part from Wells. A. F. Structural Inorganic Chemistry, 5th ed. Oxford University Oxford, 1984. Reproduced with permission. ...

Fig. 8.6 Schematic diagram of -alumina showing loosely packed planes containing mobile sodium ions situated between spinel blocks of Al3+ and O2- ions...

---