Ion-Conductive Transport

A fuel cell consists of an ion-conducting membrane (electrolyte) and two porous catalyst layers (electrodes) in contact with the membrane on either side. The hydrogen oxidation reaction at the anode of the fuel cell yields electrons, which are transported through an external circuit to reach the cathode. At the cathode, electrons are consumed in the oxygen reduction reaction. The circuit is completed by permeation of ions through the membrane. 

Table 8.2 lists the conductivities, transport numbers and molar conductivities of the electrolyte A = olc, and ions Xj = t+A for a number of melts as weU as for 0.1 M KCl solution. Melt conductivities are high, but the ionic mobilities are much lower in ionic liquids than in aqueous solutions the high concentrations of the ions evidently give rise to difficulties in their mutual displacement. 

In polymer electrolytes (even prevailingly crystalline), most of ions are transported via the mobile amorphous regions. The ion conduction should therefore be related to viscoelastic properties of the polymeric host and described by models analogous to that for ion transport in liquids. These include either the free volume model or the configurational entropy model . The former is based on the assumption that thermal fluctuations of the polymer skeleton open occasionally free volumes into which the ionic (or other) species can migrate. For classical liquid electrolytes, the free volume per molecule, vf, is defined as ... 

The main conclusion of the percolation theory is that there exists a critical concentration of the conductive fraction (percolation threshold, c0), below which the ion (charge) transport is very difficult because of a lack of pathways between conductive islands. Above and near the threshold, the conductivity can be expressed as ... 

This type of electrolytic cell consists of anodes and cathodes that are separated by a water impermeable ion-conducting membrane. Brine is fed through the anode where chlorine gas is generated and sodium hydroxide solution collects at the cathode. Chloride ions are prevented from migrating from the anode compartment to the cathode compartment by the membrane and this, consequently, leads to the production of sodium hydroxide, free of contaminants like salts. The condition of the membrane during operation requires more care. They must remain stable while being exposed to chlorine and strong caustic solution on either side they must allow, also, the transport of sodium ions and not chloride ions. 

Figure 6.2 Ionic transport number for oxide ion conductivity in the pyrochlore phases Lu2Ti207, Lu2.096Tii.904O6.952> and Lu2286Tii.7i406.857- [Data adapted from A. V. Shlyakhtina, J. C. C. Abrantes, A. V. Levchenko, A. V. Knot ko, O. K. Karyagina, and L. G. Shcherbakova, Solid State Ionics, 177, 1149-1155 (2006).]...

Both the oxides (3- and (3"-alumina show extremely high Na+ ion conductivity. As the structure suggests, the conductivity is anisotropic, and rapid sodium ion transport is limited to the two-dimensional conduction plane. There is almost unimpeded motion in the Na+ layers, especially in (3"-alumina, which lacks interstitial oxygen ion defects in the conduction plane, and the conductivity is of the same order of magnitude as in a strong solution of a sodium salt in water. The conductivity is a... 

Thus, measurement of the total conductivity together with the cell voltage allows the transport numbers of the ions to be determined (Fig. 8.17). The results show that at lower temperatures proton conductivity is of greatest importance, at middle temperatures oxygen ion conductivity becomes dominant, and at high temperatures the material is predominantly a hole conductor. Between these temperatures, at approximately 350°C the solid is a mixed H+ and O2- conductor while at approximately 650°C it is a mixed hole and O2- conductor. 

Ni, Y. G Chen, J. G., Androutsellis-Theotokis, A., Huang, C. J., Moczydlowski, E., and Rud-nick, G. (2001) A lithium-induced conformational change in serotonin transporter alters cocaine binding, ion conductance, and reactivity of Cys-109. J. Biol. Chem. 276,30942-30947. 

Shown in Figure 1.1 is the oxygen ion conductivity of selected oxides. Among these oxides, only a few materials have been developed as SOFC electrolytes due to numerous requirements of the electrolyte components. These requirements include fast ionic transport, negligible electronic conduction, and thermodynamic stability over a wide range of temperature and oxygen partial pressure. In addition, they must... 

The first half of this chapter concentrates on the mechanisms of ion conduction. A basic model of ion transport is presented which contains the essential features necessary to describe conduction in the different classes of solid electrolyte. The model is based on the isolated hopping of the mobile ions in addition, brief mention is made of the influence of ion interactions between both the mobile ions and the immobile ions of the solid lattice (ion hopping) and between different mobile ions. The latter leads to either ion ordering or the formation of a more dynamic structure, the ion atmosphere. It is likely that in solid electrolytes, such ion interactions and cooperative ion movements are important and must be taken into account if a quantitative description of ionic conductivity is to be attempted. In this chapter, the emphasis is on presenting the basic elements of ion transport and comparing ionic conductivity in different classes of solid electrolyte which possess different gross structural features. Refinements of the basic model presented here are then described in Chapter 3. 

Fig. 8.11 Partial lithium ion conductivity of the predominantly electronically conducting compound Lij+jSb as a function of stoichiometry. The variation in the conductivity is due to changes of the transport mechanism.

The unavailability of data on dissociation degree and mobility has thus made ion conductivity an alternative metric that has been universally adopted by the battery research and development community to evaluate the transport ability of electrolytes. However, it should always be remembered that such a metric of convenience is based on an unstated assumption that is, the increase in the overall conductivity should originate, at least partially, from the improvement in the cation conductivity. Qualitatively, this assumption holds true, since a correlation does usually exist between ion conductivity and power performance in batteries, although quantitatively the distribution of this increase between anions and cations is unknown. 

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