Transition ionic conductance

Fig. 3. An overview of atomistic mechanisms involved in electroceramic components and the corresponding uses (a) ferroelectric domains capacitors and piezoelectrics, PTC thermistors (b) electronic conduction NTC thermistor (c) insulators and substrates (d) surface conduction humidity sensors (e) ferrimagnetic domains ferrite hard and soft magnets, magnetic tape (f) metal—semiconductor transition critical temperature NTC thermistor (g) ionic conduction gas sensors and batteries and (h) grain boundary phenomena varistors, boundary layer capacitors, PTC thermistors.

An example of the determination of activation enthalpies is shown in Figs. 11 and 12. A valuable indication for associating the correct minimum with the ionic conductivity is the migration effect of the minimum with the temperature (Fig. 11) and the linear dependence in the cr(T versus 1/T plot (Fig. 12). However, the linearity may be disturbed by phase transitions, crystallization processes, chemical reactions with the electrodes, or the influence of the electronic leads. 

Every ionic crystal can formally be regarded as a mutually interconnected composite of two distinct structures cationic sublattice and anionic sublattice, which may or may not have identical symmetry. Silver iodide exhibits two structures thermodynamically stable below 146°C sphalerite (below 137°C) and wurtzite (137-146°C), with a plane-centred I- sublattice. This changes into a body-centred one at 146°C, and it persists up to the melting point of Agl (555°C). On the other hand, the Ag+ sub-lattice is much less stable it collapses at the phase transition temperature (146°C) into a highly disordered, liquid-like system, in which the Ag+ ions are easily mobile over all the 42 theoretically available interstitial sites in the I-sub-lattice. This system shows an Ag+ conductivity of 1.31 S/cm at 146°C (the regular wurtzite modification of Agl has an ionic conductivity of about 10-3 S/cm at this temperature). 

Before treatment with alcohol, the ionic conductivity of lithium borate polymers was 6.23 X 10-5 to 2.07 X 10-7 Scm-1 at 50°C. The maximum ionic conductivity was observed for the polymer with a PE040o spacer unit. After the polymer reaction with alcohols, glass-transition temperatures of these polymers were found to be -52 to 39°C, which was higher than that of poly(lithium mesitylhydroborate) ( 69°C). 

Table 6 Glass Transition Temperature, Ionic Conductivity and VFT Parameters For Polymer/Salt Hybrids 10...

In many ways, chloroaluminate molten salts are ideal solvents for the electrodeposition of transition metal-aluminum alloys because they constitute a reservoir of reducible aluminum-containing species, they are excellent solvents for many transition metal ions, and they exhibit good intrinsic ionic conductivity. In fact, the first organic salt-based chloroaluminate melt, a mixture of aluminum chloride and 1-ethylpyridinium bromide (EtPyBr), was formulated as a solvent for electroplating aluminum [55, 56] and subsequently used as a bath to electroform aluminum waveguides [57], Since these early articles, numerous reports have been published that describe the electrodeposition of aluminum from this and related chloroaluminate systems for examples, see Liao et al. [58] and articles cited therein. 

Recently, there has been considerable interest in developing molten salts that are less air and moisture sensitive. Melts such as l-methyl-3-butylimidazolium hexa-fluorophosphate [211], l-ethyl-3-methylimidazolium trifluoromethanesulfonate [212], and l-ethyl-3-methylimidazolium tetrafluoroborate [213] are reported to be hydro-phobic and stable under environmental conditions. In some cases, metal deposition from these electrolytes has been explored [214]. They possess a wide potential window and sufficient ionic conductivity to be considered for many electrochemical applications. Of course if one wishes to take advantage of their potential air stability, one loses the opportunity to work with the alkali and reactive metals. Further, since these ionic liquids are neutral and lack the adjustable Lewis acidity common to the chloroaluminates, the solubility of transition metal salts into these electrolytes may be limited. On a positive note, these electrolytes are significantly different from the chloroaluminates in that the supporting electrolyte is not intended to be electroactive. 

In many transition-metal oxides and sulfides, ionic conductivity is augmented by electronic conductivity, and transport numbers need to include contributions from electrons and holes. These mixed conductors are described in Section 8.8. 

The compounds BajInjOj, Agl and PbFj illustrate ionic conductivity in stoichiometric compounds. The first is a fast oxide-ion conductor above a first-order order-disorder transition at 930 °C that leaves the Bain array unchanged the second is a fast Ag -ion conductor above a first-order transition at which the I -ion array changes from close-packed to body-centred cubic and the third exhibits a smooth transition to a fast F ion conductor without changing the face-centred-cubic array of Pb " ions. 

The F -ion conductor first discovered by Faraday represents a more complex order-disorder transition to fast ionic conduction. At all temperatures, PbF2 is reported to have the fluorite structure in which the F ions occupy all the tetrahedral sites of a face-centred-cubic Pb -ion array however, the site potential of the Pb ions is asymmetric, and a measurement of the charge density with increasing temperature indicates that the F ions spend an increasing percentage of the time at the... 

Whatever the mobile ion is, all the vitreous electrolytes have a transport number of unity and below their vitreous transition temperature, ionic conductivity follows an Arrhenius law ... 

Above the vitreous transition temperature Tg, ionic conductivity increases steeply as represented in Fig. 4.6 from data obtained in the Agl-AgMoQ mixture. Above Tg, ionic conductivity is no longer represented by an Arrhenius law (4.1) and experimental results are better represented by an empirical relationship... 

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. 

Some transition metal complexes are excellent conductors. Thin films of cyto-chrome-C3, which contains four heme moieties coordinated by protein, exhibited a high conductivity with mixed valence state (Fe /Fe ) and showed an increase in conductivity as the temperature was decreased (2 x 10 S cm at 268 K) [68-70]. The temperature dependence of conductivity in the highly conductive region is the opposite of that of semiconductors and may preclude the ionic conduction as a dominant contribution. However, since the high conductivity is realized in the presence of hydrogenase and hydrogen, the system is not strictly a single but rather a multicomponent molecular solid. 

The mobility of the ions in polymer electrolytes is linked to the local segmental mobility of the polymer chains. Significant ionic conductivity in these systems will occur only above the glass transition temperature of the amorphous phase, Tg. Therefore, one of the reqnirements for the polymeric solvent is a low glass-transition temperature for example, Tg = —67°C for PEO. 

Hitherto we have dealt with model FICs that are mostly useful as solid electrolytes. The other class of compounds of importance as electrode materials in solid state batteries is mixed electronic-ionic conductors (with high ionic conductivity). The conduction arises from reversible electrochemical insertion of the conducting species. In order for such a material to be useful in high-energy batteries, the extent of insertion must be large and the material must sustain repeated insertion-extraction cycles. A number of transition-metal oxide and sulphide systems have been investigated as solid electrodes (Murphy Christian, 1979). 

Study of (ZrO2)o.85(CuO)o.i5—electronic and ionic conduction ZrO2 shows the following successive phase transitions on heating ... 

In Section 9.4.1, we introduced internal electrochemical reactions by considering heterophase AX/AY assemblages. We now discuss the more general case of internal electrochemical reactions which occur in inhomogeneous systems having various types of disorder. From the foregoing discussion, we expect internal reactions to occur in a crystal matrix whenever the condition V/jon = 0 is not met. The extreme is a transition from n- (or p-) type conduction to ionic conduction (which for brevity we shall call a (n-i) junction). 

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