Structure and Its Influence on Superionic Conduction: EXAFS Studies

Part of the Topics in Current Physics book series (TCPHY, volume 15)


Superionic conductors are a class of materials which achieve ionic conductivities comparable with those of molten salts while still in the solid phase. As discussed in Chap.7, the transition from insulating to conducting behavior may take place sharply at a specific temperature, as in the case of AgI, or gradually over a large temperature range, as in the case of PbF2 [2.1]. In either case, it involves a disordering of one of the ion sublattices of the material. At low temperature, all the ions are situated on well-defined lattice sites and have a very low mobility. As the temperature is increased, the mobile ions begin populating interstitial sites. In the superionic phase, these ions are distributed over a large number of available sites [2.2]. It follows that this superionic phase is quite naturally characterized structurally in terms of the mobile and immobile sublattices [2.3]. The immobile ions form a complex structure through which the mobile ions move. This structure is not rigid since these ions execute large vibrations about their lattice sites; nonetheless, they do not leave those sites and so do not contribute to the ionic conductivity. The positions of the immobile ions define characteristic voids which are populated to varying degrees by the mobile ions and through which these ions move. In AgI, for example, the iodine forms a bcc lattice, while the Ag ions are located in and move among the tetrahedral voids, with negligible occupation of the octahedral locations [2.4,5].


Octahedral Site Pair Correlation Function Conduction Path Superionic Conductor Peak Function 
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