Electrolytes mobile ions

Solid electrolyte Mobile ion Conductivity/S cm temperature/°C Activation energy/e-y Reference... 

Ionic conductors arise whenever there are mobile ions present. In electrolyte solutions, such ions are nonually fonued by the dissolution of an ionic solid. Provided the dissolution leads to the complete separation of the ionic components to fonu essentially independent anions and cations, the electrolyte is tenued strong. By contrast, weak electrolytes, such as organic carboxylic acids, are present mainly in the undissociated fonu in solution, with the total ionic concentration orders of magnitude lower than the fonual concentration of the solute. Ionic conductivity will be treated in some detail below, but we initially concentrate on the equilibrium stmcture of liquids and ionic solutions. 

This relationship makes it possible to calculate the maximum ionic conductivity of solid electrolytes. Assuming that the mobile ions are moving with thermal velocity v without resting and oscillating at any lattice site, this results in a jump frequency... 

In the opposite case to that considered above, Cs >ic2 and the difference in concentration Cs of the mobile electrolyte inside and outside the gel may be comparable in magnitude to the concentration C2/ of counter-anions. Hence the ion osmotic pressure is greatly reduced. Calculation of Cs — Cs for this case (see Appendix B) gives for the osmotic pressure due to the mobile ions... 

Three types of methods are used to study solvation in molecular solvents. These are primarily the methods commonly used in studying the structures of molecules. However, optical spectroscopy (IR and Raman) yields results that are difficult to interpret from the point of view of solvation and are thus not often used to measure solvation numbers. NMR is more successful, as the chemical shifts are chiefly affected by solvation. Measurement of solvation-dependent kinetic quantities is often used (<electrolytic mobility, diffusion coefficients, etc). These methods supply data on the region in the immediate vicinity of the ion, i.e. the primary solvation sphere, closely connected to the ion and moving together with it. By means of the third type of methods some static quantities entropy and compressibility as well as some non-thermodynamic quantities such as the dielectric constant) are measured. These methods also pertain to the secondary solvation-sphere, in which the solvent structure is affected by the presence of ions, but the... 

The electrolytic mobility of the ionic atmosphere around the ith ion can then be defined by the expression... 

It is known that organoboron halide-imidazole complexes dissociate diming equilibrium 56 however, charges disappear upon dissociation. In such a matrix, mobile ions should not originate from the matrix. Therefore, the polymer electrolytes composed of boron halide-imidazole complexes were considered to be appropriate for selective ion transport. 

From SAQ 8.15, it can be seen that the mobile ions move very fast through the electrolyte layer. Remember that the AC voltage is sinusoidal, so the polarity of each electrode is changing sign at a frequency of 2 x f, i.e. twice per cycle from the way that a cycle is defined (see Figure 8.8). 

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. 

In crystalline electrolytes, conduction pathways for the mobile ions... 

In most solid electrolyte systems, it is not possible to vary the composition sufficiently so as to have the complete spectrum of mobile ion concentrations, from n,. = 0 to n,. = 1. Instead, the properties are usually limited to one or other of the wings in the type of behaviour... 

The occurrence of such ion trapping is clearly undesirable since it inevitably leads to a decrease in conductivity. In practice, in materials that contain potential traps such as charged aliovalent impurities/dopants, the conductivity values of a particular sample may actually decrease with time as the mobile ions gradually become trapped. Such ageing effects greatly limit the usefulness of a solid electrolyte in any device that needs to have a long working-life. 

Solid electrolyte behaviour has been reported in a wide range of materials and is now known for a considerable number of mobile ions. Some key examples for each ion are listed in Table 2.1. 

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 ... 

Since the polyelectrolytes contain only one type of mobile ion, the interpretation of conductivity data is greatly simplified. Polyelectrolytes have significant advantages for applications in electrochemical devices such as batteries. Unlike polymer-salt complexes, polyelectrolytes are not susceptible to the build up of a potentially resistive layer of high or low salt concentration at electrolyte-electrolyte interfaces during charging and discharging. Unfortunately flexible polyelectrolyte films suitable for use in devices have not yet been prepared. 

In the example above, a short-chain poly(ethylene glycol) was added to a rigid polyelectrolyte to plasticise the material and thereby increase polymer-solvent motion in the vicinity of mobile ions. This strategy has been widely explored as a means of improving ion transport in electrolytes. 

The most important deficiency in the models developed so far concerns the failure to take account of interactions between the mobile ions. As the ionic concentration in polymer electrolytes is frequently greater than 1.0moldm and the mean distance between ions of the order of 0.5-0.7 nm, then relatively stong coulombic interactions exist which must affect ion motion. Ratner and Nitzan have begun to address this problem from a theoretical viewpoint (Ratner and Nitzan, 1989) although it has not been fully developed yet to give a complete description of conduction in ion associated polymer electrolytes. The interactions between ions which lead to ion association are discussed further in the following section. 

Section 8.2) caused by the different concentrations of the mobile ions in the electrode and in the electrolyte. 

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