Ohmic Carbonate

In low temperature fuel ceUs, ie, AEG, PAEC, PEEC, protons or hydroxyl ions are the principal charge carriers in the electrolyte, whereas in the high temperature fuel ceUs, ie, MCEC, SOEC, carbonate and oxide ions ate the charge carriers in the molten carbonate and soHd oxide electrolytes, respectively. Euel ceUs that use zitconia-based soHd oxide electrolytes must operate at about 1000°C because the transport rate of oxygen ions in the soHd oxide is adequate for practical appHcations only at such high temperatures. Another option is to use extremely thin soHd oxide electrolytes to minimize the ohmic losses. 

The above brief analysis underlines that the porous structure of the carbon substrate and the presence of an ionomer impose limitations on the application of porous and thin-layer RDEs to studies of the size effect. Unless measurements are carried out at very low currents, corrections for mass transport and ohmic limitations within the CL [Gloaguen et ah, 1998 Antoine et ah, 1998] must be performed, otherwise evaluation of kinetic parameters may be erroneous. This is relevant for the ORR, and even more so for the much faster HOR, especially if the measurements are performed at high overpotentials and with relatively thick CLs. Impurities, which are often present in technical carbons, must also be considered, given the high purity requirements in electrocatalytic measurements in aqueous electrolytes at room temperature and for samples with small surface area. 

Since model compounds reveal well-defined cyclic voltammograms for the Cr(CNR)g and Ni(CNR)g complexes (21) the origin of the electroinactivity of the polymers is not obvious. A possible explanation (12) is that the ohmic resistance across the interface between the electrode and polymer, due to the absence of ions within the polymer, renders the potentially electroactive groups electrochemically inert, assuming the absence of an electronic conduction path. It is also important to consider that the nature of the electrode surface may influence the type of polymer film obtained. A recent observation which bears on these points is that when one starts with the chromium polymer in the [Cr(CN-[P])6] + state, an electroactive polymer film may be obtained on a glassy carbon electrode. This will constitute the subject of a future paper. 

As in the case with PAFC s, voltage obtained from an AFC is affected by ohmic, activation, and concentration losses. Figure 4-7 presents data obtained in the 1960 s (18) which summarizes these effects, excluding ohmic losses, for a catalyzed reaction (0.5-2.0 mg noble metal/cm ) with carbon-based porous electrodes for H2 oxidation and O2 reduction in 9 N KOH at 55-60 C. The electrode technology was similar to that employed in the fabrication of PAFC electrodes. Performance of AFC s with carbon-based electrodes has not changed dramatically since these early results were obtained. 

In parallel, Kasumov et al. [60] reported ohmic behavior of the resistance of A-DNA molecules deposited on a mica surface and stretched between rhenium-carbon electrodes (see Fig. 6). This behavior was measured at temperatures ranging from room temperature down to 1 K. Below 1 K a particularly unexpected result was observed proximity-induced superconductivity. The resistance was measured directly with a lock-in technique and no current-voltage curves were presented. This surprising proximity-induced supercon-... 

The impregnation of porous nickel discs with CoPc was difficult because of the limited solubility of the chelate in the usual solvents. CoPc cathodes with carbon as substrate were therefore prepared for use in H2/O2 fuel cells. A mixture of 72 mg CoPc and 48 mg acetylene black, with PTFE as binder, was pressed into a nickel mesh of area 5 cm2. Electrodes of this type were tested in an H2/O2 fuel cell with 35% KOH electrolyte in an asbestos matrix at 80° C. Figure 5 compares the current/voltage characteristics of CoPc cathodes (14 mg/cm2) with those of other catalysts, including platinum (9 mg/cm2), silver (40 mg/cm2), and pure acetylene black (20 mg/cm2). An hydrogen electrode (9 mg Pt/cm2) was used as the anode in all tests. To facilitate comparison of the activity of different cathodes, the pure ohmic internal resistance of the cells (of the order of 0.02 ohm) was eliminated. 

The modified supported powder electrodes used in the experiments hitherto described on the anodic activity of CoTAA are out of the question for practical application in fuel cells, as they do not have sufficient mechanical stability and their ohmic resistance is very high (about 1—2 ohm). For these reasons, compact electrodes with CoTAA were prepared by pressing or rolling a mixture of CoTAA, activated carbon, polyethylene, and PTFE powders in a metal gauze. The electrodes prepared in this way show different activities depending on the composition and the sintering conditions. Electrodes prepared under optimal conditions can be loaded up to about 40 mA/cm2 at a potential of 350 mV at 70 °C in 3 M HCOOH, with relatively good catalyst utilization (about 5 A/g) and adequate stability. 

This type of sensor utilizes a drastic increase in resistance at the point of dew condensation, since water absorption swells the polymers to counteract ohmic contact between carbon particles. This type sensor is now widely applied to humidity controling systems of video tape recorders or car windows. 

Rs (Figure 1.22a). The double layer capacitance is represented by the capacitance C, and Rs is the series resistance of the EDLC, also named the equivalent series resistance (ESR). This series resistance shows the nonideal behavior of the system. This resistance is the sum of various ohmic contributions that can be found in the system, such as the electrolyte resistance (ionic contribution), the contact resistance (between the carbon particles, at the current collector/carbon film interface), and the intrinsic resistance of the components (current collectors and carbon). Since the resistivity of the current collectors is low when A1 foils or grids are used, it is generally admitted that the main important contribution to the ESR is the electrolyte resistance (in the bulk and in the porosity of the electrode) and to a smaller extent the current collector/active film contact impedance [25,26], The Nyquist plot related to this simple RC circuit presented in Figure 1.22b shows a vertical line parallel to the imaginary axis. 

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