Charge transfer resistance, effective area

Figure 6.21 shows the AC impedance spectra for the cathodic ORR of the cell electrodes prepared using the conventional method and the sputtering method. It can be seen that the spectra of electrodes 2 and 3 do not indicate mass transport limitation at either potentials. For electrode 1, a low-frequency arc develops, due to polarization caused by water transport in the membrane. It is also observable that the high-frequency arc for the porous electrode is significantly depressed from the typical semicircular shape. Nevertheless, the real-axis component of the arc roughly represents the effective charge-transfer resistance, which is a function of both the real surface area of the electrode and the surface concentrations of the species involved in the electrode reaction. 

The effective area of the OTS-coated PtO electrode can be derived if the charge transfer resistance (K ) is known. Rct can be obtained from impedance data measured at a potential near the reversal potential (37, 33) Rct = RT/(nFAI0), where R is the universal gas constant, T is absolute temperature, n is the number of electrons transferred per molecule of TONE, F is Faraday s constant, I0 is the exchange current density, and A is the effective surface area. Because the impedance spectra of the PtO and PtO-OTS electrodes were measured under the same conditions, the value of Rct may be assumed to be affected only by the effective surface area. In Figure 3, the impedance data are replotted as 2 versus 1 /a)1 2, where a) is the angular frequency (2 tt/). Rct is estimated from the intercept on the Z axis by extrapolation. The Rct values are 95 and 980 fl for PtO and PtO-OTS, respectively. An OTS coverage factor, 0, can then be estimated from (1 — 0) = ct(Pto)/ ct(Pto-OTS> In is case 0 = 0.9. 

Finally, it is important to point out that although in localised corrosion the anodic and cathodic areas are physically distinguishable, it does not follow that the total geometrical areas available are actually involved in the charge transfer process. Thus in the corrosion of two dissimilar metals in contact (bimetallic corrosion) the metal of more positive potential (the predominantly cathodic area of the bimetallic couple) may have a very much larger area than that of the predominantly anodic metal, but only the area adjacent to the anode may be effective as a cathode. In fact in a solution of high resistivity the effective areas of both metals will not extend appreciably from the interface of contact. Thus the effective areas of the anodic and cathodic sites may be much smaller than their geometrical areas. 

The cycle life within one cycle-set depends strongly on the nature and properties of the carbon or graphite additives used. These materials differ in particle size, structure and affinity to lead and to the expander. Of special importance is the interface between carbon and lead particles, and its area as it determines the resistance that electrons have to overcome when transferred between these two phases and thus affects the potential and the rate of the electrochemical reactions at the carbon/solution interface. Only a limited number of carbon and graphite materials have optimum structural characteristics and may improve substantially the cycle life performance of the cells. It is of crucial importance to identify the most effective carbon (graphite) additives, i.e. with most beneficial effect on the parallel mechanism of charge of the negative plates. 

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