Conduction unipolar ionic

The majority of unipolar ionic conductors identified to date are polymorphic compounds with several phase transitions, where the phases have different ionic conductivities owing to modifications in the substructure of the mobile ions [28], One of the first studied cationic conductors was a-Agl [21]. Silver iodide exhibits different polymorphic structures. Agl has a low-temperature phase, that is, [3-Agl, which crystallizes in the hexagonal wurtzite structure type, and a high-temperature cubic phase, a-Agl, which shows a cubic CsCl structure type [20,22] (see Section 2.4.5). 

Unlike classical electrolytes mostly only raie i(Mi is mobile, whereas the counterion is fixed in the sublattice. Sometimes this phenomenon is called as unipolare ionic conductivity. 

AU these features—low values of a, a strong temperature dependence, and the effect of impurities—are reminiscent of the behavior of p- and n-type semiconductors. By analogy, we can consider these compounds as ionic semiconductors with intrinsic or impurity-type conduction. As a rule (although not always), ionic semiconductors have unipolar conduction, due to ions of one sign. Thus, in compounds AgBr, PbCl2, and others, the cation transport number is close to unity. In the mixed oxide ZrOj-nYjOj, pure 0 anion conduction t = 1) is observed. 

Because of the high values of conductivity which in individual cases are found at room temperature, such compounds are often called superionic conductors or ionic superconductors but these designations are unfounded, and a more correct designation is solid ionic conductors. Strictly unipolar conduction is typical for all solid ionic conductors in the silver double salts, conduction is due to silver ion migration, whereas in the sodium polyaluminates, conduction is due to sodium ion migration. 

Electrical conductivity measurements on silicate melts indicate an essentially ionic conductivity of unipolar type (Bockris et al., 1952a,b Bockris and Mellors, 1956 Waffe and Weill, 1975). Charge transfer is operated by cations, whereas anionic groups are essentially stationary. Transference of electronic charges (conductivity of h- and n-types) is observed only in melts enriched in transition elements, where band conduction and electron hopping phenomena are favored. We may thus state that silicate melts, like other fused salts, are ionic liquids. 

As a rule (though not always), ionic semiconductors have unipolar conduction because of ions of one sign. Thus, in compounds AgBr, PbCl2, and others the cation transport number is close to unity. In the mixed oxide Zr02 nY20 pure anion conduction = 1) is observed. 

Strictly unipolar conduction is typical for all solid ionic conductors in the silver double salts, conduction is because of silver ion migration, while in the sodium polyaluminates, conduction is because of sodium ion migration. 

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