Electrode impedance reduction

Figure 25. Adler s ID macrohomogeneous model for the impedance response of a porous mixed conducting electrode. Oxygen reduction is viewed as a homogeneous conversion of electronic to ionic current within the porous electrode matrix, occurring primarily within a distance A from the electrode/electrolyte interface (utilization region). (Adapted with permission from ref 28. Copyright 1998 Elsevier.)...

The silver-silver chloride electrode has characteristics similar to a perfectly nonpolarizable electrode and is practical for use in many biomedical applications. The electrode (Figure 4.1a) consists of a silver base structure that is coated with a layer of the ionic compound silver chloride. Some of the silver chloride when exposed to light is reduced to metallic silver hence, a typical silver-silver chloride electrode has finely divided metallic silver within a matrix of silver chloride on its surface. Because silver chloride is relatively insoluble in aqueous solutions, this surface remains stable. Moreover, because there is minimal polarization associated with this electrode, motion artifact is reduced compared to polarizable electrodes such as the platinum electrode. Furthermore, owing to the reduction in polarization, there is also a smaller effect of frequency on electrode impedance, especially at low frequencies. 

This reference electrode system is suitable for use between 700 and 950 °C, below which the reference system has too high impedance (typically above 10 2) and above which the silver melts T = 962 °C). Internal standards are used to measure the stability of the electrode. Here, reduction of silicon dioxide and calcium metal deposition (from Ca " ) can be used as indicator potentials and show that the electrode can give stable potentials for times between hours and days. In practice, while carrying out long electrolysis reactions in chloride melts, the group at CSIRO (Australia) have found that the electrodes typically last about 8 h. This is, however, sufficient to carry out many types of experiments. 

Fig. 9 Comparison of the impedance modulus of the Pt electrode and PEDOT-coated Pt electrodes. The PEDOT/PSS was coated potentiometrically at room temperature with variable polymerization charge densities from 20, 40, 80 to 160 mC/cm. All 4 PEDOT-coated electrodes have reductions in impedance modulus at the frequency range of 10 kHz or lower while significant reductions appear at 1 kHz or lower...

Effect of Electrode Shapes on Grounding Impedance Reduction... 

A diffuse-layer minimum in C,E curves has not been found with electrodes kept 3 min at E = -0.74 V, i.e., at a potential close to the rest potential of Fe.728 Complete cathodic reduction at <<-0.74 V (SCE) is not achieved since a diffuse-layer minimum is not found for cathodically reduced electrodes. This effect has been explained by the oxidation of Fe. According to impedance data, strong specific adsorption of Cl anions at renewed Fe electrodes occurs since a very large shift of Eosq takes place going from KF to KC1 solutions. 

Polarographic studies of organic compounds are very complicated. Many of the compounds behave as surfactants, most of them exhibit multiple-electron charge transfer, and very few are soluble in water. The measurement of the capacitance of the double layer, the cell resistance, and the impedance at the electrode/solution interface presents many difficulties. To examine the versatility of the FR polarographic technique, a few simple water-soluble compounds have been chosen for the study. The results obtained are somewhat exciting because the FR polarographic studies not only help in the elucidation of the mechanism of the reaction in different stages but also enable the determination of kinetic parameters for each step of reduction. 

The impedance polarization performance of LSM electrode is closely related to the mechanism and kinetics of the oxygen reduction reactions. 02 reduction at SOFC cathodes is the most heavily studied subject, and this subject is sufficiently broad and complex to warrant its own review. Interested readers should consult the recent excellent articles by Adler [1] and Fleig [55], Here, only the polarization performance and its influencing factors are discussed. 

FIGURE 3.5 (a) Impedance and (b) polarization behavior of a freshly prepared La072Sr018MnO3 electrode for 02 reduction as a function of cathodic polarization time at 200 mAcm 2 and 900°C in air. The impedance was measured at open circuit and the numbers are frequencies in hertz. (From Jiang, S.P. and Love, J.G., Solid State Ionics, 138 183-190, 2001. With permission.)... 

Figure 3.5 [36], For the 02 reduction reaction on freshly prepared LSM electrodes, the initial polarization losses are very high and decrease significantly with the cathodic polarization/current passage (see Figure 3.5b). Consistent with the polarization potential, the impedance responses at open circuit decrease rapidly with the application of the cathodic current passage. For example, the initial electrode polarization resistance, RE, is 6.2 Qcm2 and after cathodic current treatment for 15 min RK is reduced to 0.7 Qcm2 see Figure 3.5 (a). The reduction in the electrode polarization resistance is substantial. The analysis of the impedance responses as a function of the cathodic current passage indicates that the effect of the cathodic polarization is primarily on the reduction in the low-frequency impedance [10]. Such activation effect of cathodic polarization/current on the electrochemical activity of the cathodes was also reported on LSM/YSZ composite electrodes [56-58], Nevertheless, the magnitude of the activation effect on the composite electrodes is relatively small.

A complication that occurs on a low at.% Ru electrode is that, owing to the low Faradaic currents (low Ru content) and hence large Rt value, currents due to other trace redox reactions, e.g. oxygen reduction, become more detectable. This reveals itself in a phase-angle of 45° as co 0 as trace oxygen reduction would be diffusion-controlled. The impedance corresponding to this situation can be shown to be the same as that in Equation 5.3, with U(p) expressed by the relationship ... 

Figure 5. Measurement and analysis of steady-state i— V characteristics, (a) Following subtraction of ohmic losses (determined from impedance or current-interrupt measurements), the electrode overpotential rj is plotted vs ln(i). For systems governed by classic electrochemical kinetics, the slope at high overpotential yields anodic and cathodic transfer coefficients (Ua and aj while the intercept yields the exchange current density (i o). These parameters can be used in an empirical rate expression for the kinetics (Butler—Volmer equation) or related to more specific parameters associated with individual reaction steps.(b) Example of Mn(IV) reduction to Mn(III) at a Pt electrode in 7.5 M H2SO4 solution at 25 Below limiting current the system obeys Tafel kinetics with Ua 1/4. Data are from ref 363. (Reprinted with permission from ref 362. Copyright 2001 John Wiley Sons.)...

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