Partial Ionic Conductivity

Cul) is not due to point defects but to partial occupation of crystallographic sites. The defective structure is sometimes called structural disorder to distinguish it from point defects. There are a large number of vacant sites for the cations to move into. Thus, ionic conductivity is enabled without use of aliovalent dopants. A common feature of both compounds is that they are composed of extremely polarizable ions. This means that the electron cloud surrounding the ions is easily distorted. This makes the passage of a cation past an anion easier. Due to their high ionic conductivity, silver and copper ion conductors can be used as solid electrolytes in solid-state batteries. 

Unique combinations of properties continue to be discovered in inorganic and organometallic macromolecules and serve to continue a high level of interest with regard to potential applications. Thus, Allcock describes his collaborative work with Shriver (p. 250) that led to ionically conducting polyphosphazene/salt complexes with the highest ambient temperature ionic conductivities known for polymer/salt electrolytes. Electronic conductivity is found via the partial oxidation of unusual phthalocyanine siloxanes (Marks, p. 224) which contain six-coordinate rather than the usual four-coordinate Si. 

Defect populations and physical properties such as electronic conductivity can be altered and controlled by manipulation of the surrounding atmosphere. To specify the exact electronic conductivity of such a material, it is necessary to specify its chemical composition, the defect types and populations present, the temperature of the crystal, and the surrounding partial pressures of all the constituents. Brouwer diagrams display the defect concentrations present in a solid as a function of the partial pressure of one of the components. Because the defect populations control such properties as electronic and ionic conductivity, it is generally easy to determine how these vary as the partial pressure varies. 

The improvement in cell performance at higher pressure and high current density can be attributed to a lower diffusion polarization at the cathode and an increase in the reversible cell potential. In addition, pressurization decreases activation polarization at the cathode because of the increased oxygen and water partial pressures. If the partial pressure of water is allowed to increase, a lower acid concentration will result. This will increase ionic conductivity and bring about a higher exchange current density. The net outcome is a reduction in ohmic losses. It was reported (33) that an increase in cell pressure (100% H3PO4, 169°C (336°F)) from 1 to 4.4 atm (14.7 to 64.7 psia) produces a reduction in acid concentration to 97%, and a decrease of about 0.001 ohm in the resistance of a small six cell stack (350 cm electrode area). 

Cell Voltage - For an identical stack the overall cell voltage will be lower as temperature decreases due to the decreased kinetics, diffusion, and ionic conductivity versus the improved electrical conductivity which typically does not dominate the cell polarizations. This is partially but not fully offset by the increased theoretical open circuit voltage of the electrochemical reaction at the lower temperature. 

Such a chemical approach which links ionic conductivity with thermodynamic characteristics of the dissociating species was initially proposed by Ravaine and Souquet (1977). Since it simply extends to glasses the theory of electrolytic dissociation proposed a century ago by Arrhenius for liquid ionic solutions, this approach is currently called the weak electrolyte theory. The weak electrolyte approach allows, for a glass in which the ionic conductivity is mainly dominated by an MY salt, a simple relationship between the cationic conductivity a+, the electrical mobility u+ of the charge carrier, the dissociation constant and the thermodynamic activity of the salt with a partial molar free energy AG y with respect to an arbitrary reference state ... 

Experiment shows that the variation of ionic conductivity with the content of MY salt depends on its partial molar free energy through the term exp(AGMY/2J r)- If X is any concentration scale, for instance the molar ratio, which allows a measure of MY content, experimental results follow an Arrhenius law that can be expressed by ... 

The diffusivity is independent of the motion of any other species (e.g. electrons or holes) and is not influenced by internal electrical fields as in the case of chemical diffusion processes which require the simultaneous motion of electronic or other ionic species. The partial ionic conductivity of the mixed ionic and (predominantly) electronic conducting electrode is given by the product of the concentration and the diffusivity and may be related to the variations of the steady state and transient voltage ... 

In recent years, research on catalysts for the ATR of hydrocarbons has paid considerable attention to perovskite systems of general formula ABO3. In the perovskite stmcture, both A and B ions can be partially substituted, leading to a wide variety of mixed oxides, characterized by structural and electronic defects. The oxidation activity of perovskites has been ascribed to ionic conductivity, oxygen mobility within the lattice [64], reducibility and oxygen sorption properties [65, 66]. 

Figure 10. Ionic conductivity of jully and partially stabilized zirconia bodies...

As can be seen, the mechanical strength of the partially stabilized body is approximately twice that of the fully stabilized and the thermal expansion is approximately 30% lower. Because of this, the thermal shock resistance of the PSZ body is greatly improved. The ionic conductivity of the PSZ body is lower but is still adequate for automotive applications. Figure 10 compares the conductivity of a yttria partially stabilized zirconia body with several fully stabilized bodies. 

CaO has been used to some degree as a stabilizer and is attractive due to its low cost. Its ionic conductivity, however, is approximately an order of magnitude less than an equivalent yttria stabilized body. There has also been some question about the chemical stability of a CaO stabilized body, although this may be more of a factor with a partially stabilized body than a fully stabilized body. Calcia fully stabilized ZrO has been and may still be used in commercial production of oxygen sensors. 

The special electrical properties of a-AgI inevitably led to a search for other solids exhibiting high ionic conductivity preferably at temperatures lower than 146°C. The partial replacement of Ag by Rb, forms the compound RbAgJs. This compound has an ionic conductivity at room temperature of 25 S m , with an activation energy of only 0.07 eV. The crystal structure is different from that of a-AgI, but similarly the Rb and T ions form a rigid array while the Ag ions are randomly distributed over a network of tetrahedral sites through which they can move. 

Over a large range partial pressures of oxygen ionic conductivity dominates and the material behaves as a solid electrolyte. Under these conditions there is an equilibrium established between oxygen ion vacancies, interstitial oxygen ions and lattice oxygen. 

Hence the partial pressure of oxygen and the temperature determine whether the solid will exhibit n-type, p-type or ionic conduction. Although the concentration of defects is important it is also necessary to consider the mobilities of the individual defects higher ionic mobilities will result in a larger domain for electrolytic conduction. Figure l4 shows the dominant mode of conduction in some mixed oxide materials, exhibiting solid electrolyte behaviour, as a function of temperature and oxygen partial pressure. 

AGa0 is the Gibbs energy of formation of AO from metal A and oxygen gas at ambient atmosphere with partial pressure p0j (AGao = AGao + (RT/2) ln (po/PoJ)-2) If products with predominantly ionic conduction are formed, the tarnishing layer is very thin in view of tel< l. From Eqn. (7.3), one has with tkm = 1... 

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