Ionic conductivity temperature dependence

One of the important properties of a polymer electrolyte leading to its development activity is the ionic conductivity. Temperature dependence on the conductivity of amorphous polymer electrolytes generally follows the Vogel-Tammann-Fulcher [VTF] equation [14] ... 

Fig. 3.45 The comparison of the theory [143] solid and dashed lines) with experiment for R = 10 nm (open circles) and / = 1,200 nm filled circles) [91] for ionic conductivity temperature dependence...

Self-diffusivity, cooperatively with ionic conductivity, provides a coherent account of ionicity of ionic liquids. The PGSE-NMR method has been found to be a convenient means to independently measure the self-diffusion coefficients of the anions and the cations in the ionic liquids. Temperature dependencies of the self-diffusion coefficient, viscosity and ionic conductivity for the ionic liquids, cannot be explained simply by Arrhenius equation rather, they follow the VFT equation. There is a simple correlation of the summation of the cationic and the anionic diffusion coefficients for each ionic liquid with the inverse of the viscosity. The apparent cationic transference number in ionic liquids has also been found to have dependence on the... 

Differences between normal ionic solids and ionic conductors. Temperature dependence of conductivity. 

For many nonaqueous systems temperature modulation is one of the most effective methods of perturbation-based analysis. Conductivity-temperature dependence in various systems with ionic conductivity typical of activated mechanisms can usually be described by the Arrhenius equation, derived from the Nernst-Einstein and Pick equations describing DC conductivity based on ion hopping through a structure [13] ... 

Increases in the testing temperature significantly reduce Rgy K (Figure 10-5) and increase media conductivity. Conductivity-temperature dependence in industrial lubricants is typical of polymeric systems with ionic conductivity and follows the Arrhenius (Eq. 5-11) or Vogel-Tammann-Fulcher (Eq. 5-12) dependencies [36]. 

Some polymer electrolytes show conductivity temperature dependence that falls outside the three types described above, with neither the Arrhenius law nor the VTF (or WLF) law being followed in the temperature ranges studied." Here, if there are no phase changes, effects associated with ionic aggregate equilibria are likely, superimposed on the simple variation in ionic mobility. In all cases, it is important to consider not only this parameter, but also the number and types of charge carriers, which are influenced by the ionic association that probably exists in ionic transport. ... 

The concentration of dissolved ionic substances can be roughly estimated by multiplying the specific conductance by an empirical factor of 0.55—0.9, depending on temperature and soluble components. Since specific conductance is temperature dependent, all samples should be measured at the same temperature. Alternatively, an appropriate temperature-correction factor obtained by comparisons with known concentrations of potassium chloride may be used. Instmments are available that automatically correct conductance measurements for different temperatures. 

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. 

There is a wide variety of solid electrolytes and, depending on their composition, these anionic, cationic or mixed conducting materials exhibit substantial ionic conductivity at temperatures between 25 and 1000°C. Within this very broad temperature range, which covers practically all heterogeneous catalytic reactions, solid electrolytes can be used to induce the NEMCA effect and thus activate heterogeneous catalytic reactions. As will become apparent throughout this book they behave, under the influence of the applied potential, as active catalyst supports by becoming reversible in situ promoter donors or poison acceptors for the catalytically active metal surface. 

Detailed information about the conductivity of solid electrolytes can be found elsewhere.2,3,6 8,10,11 As shown in Fig. 3.1, the temperature dependence of the ionic conductivity o can, in general, be described by the semiempirical equation ... 

Figure 3.1. Temperature dependence of the ionic conductivity of some solid electrolytes. The conductivity of concentrated H2S04 (37 wt%) is included for comparison.16 Reprinted with permission from WILEY-VCH.

The dramatic slowing down of molecular motions is seen explicitly in a vast area of different probes of liquid local structures. Slow motion is evident in viscosity, dielectric relaxation, frequency-dependent ionic conductance, and in the speed of crystallization itself. In all cases, the temperature dependence of the generic relaxation time obeys to a reasonable, but not perfect, approximation the empirical Vogel-Fulcher law ... 

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. 

The electrical conduction in a solution, which is expressed in terms of the electric charge passing across a certain section of the solution per second, depends on (i) the number of ions in the solution (ii) the charge on each ion (which is a multiple of the electronic charge) and (iii) the velocity of the ions under the applied field. When equivalent conductances are considered at infinite dilution, the effects of the first and second factors become equal for all solutions. However, the velocities of the ions, which depend on their size and the viscosity of the solution, may be different. For each ion, the ionic conductance has a constant value at a fixed temperature and is the same no matter of which electrolytes it constitutes a part. It is expressed in ohnT1 cm-2 and is directly proportional to the mobilities or speeds of the ions. If for a uni-univalent electrolyte the ionic mobilities of the cations and anions are denoted, respectively, by U+ and U, the following relationships hold ... 

The mechanism of ion transport in such systems is not fully elucidated, but it is presumably dependent on the degree of crystallinity of the polymeric complex (which further depends on the temperature and the salt type). The ionic conductivity was initially attributed to cation hopping between fixed coordination sites in the depicted helical tunnel, i.e. in the crystalline part of the polymer. 

Using Eq. (2.6.18) the temperature dependence of various transport properties of polymers, such as diffusion coefficient D, ionic conductivity a and fluidity (reciprocal viscosity) 1/rj are described, since all these quantities are proportional to p. Except for fluidity, the proportionality constant (pre-exponential factor) also depends, however, on temperature,... 

The electrocrystallization and characterization of a novel molecular metal which displays both electronic and ionic conduction has been reported. The complex Li0.6(15-crown-5-ether)[Ni-(dmit)2] H20 is composed of stacks of [Ni(dmit)2] units which provide pathways for electronic conduction. The stacks are separated by parallel stacks of 15-crown-5-ether moieties in a channellike formation which facilitates ion conduction. The salt has a room temperature conductivity of 240 Scm-1. Temperature-dependent magnetic susceptibility and NMR measurements were used to prove the existence of Li+ movement within the crown ether channels.1030... 

Figure 3 Temperature dependence of ionic conductivity for polymers 1 and 2 in the presence of various lithium salts.

In the presence of lithium salts, the temperature dependence of ionic conductivity for the polymer electrolytes obtained was evaluated. In the presence of LiCF3S03,... 

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