Catalyst layer charge-transfer resistivity

As mentioned, the reaction distribution is the main effect on the catalyst-layer scale. Because of the facile kinetics (i.e., low charge-transfer resistance) compared to the ionic resistance of proton movement for the HOR, the reaction distribution in the anode is a relatively sharp front next to the membrane. This can be seen in analyzing Figure 10, and it means that the catalyst layer should be relatively thin in order to utilize the most catalyst and increase the efficiency of the electrode. It also means that treating the anode catalyst layer as an interface is valid. On the other hand, the charge-transfer resistance for the ORR is relatively high, and thus, the reaction distribution is basically uniform across the cathode. This means... 

Equivalent circuits for the catalyst layer are similar to those for porous electrodes, where charge-transfer resistance, capacitance, and Warburg resistance should be considered. The catalyst layer can be conceived of as a whole uniform unit or as a non-uniform circuit. In the case of a uniform unit, the equivalent circuits are similar to the modified ones discussed in Section 4.2.2 2, and the equations in that section apply. In many cases, such as in the presence of adsorbents, the surface is covered by the adsorbed species. For example, in direct methanol fuel cells and in H2/air fuel cells, CO adsorption should be considered. One example is illustrated in Ciureanu s work [7], as shown in Figure 4.31. 

Two impedance arcs, which correspond to two relaxation times (i.e., charge transfer plus mass transfer) often occur when the cell is operated at high current densities or overpotentials. The medium-frequency feature (kinetic arc) reflects the combination of an effective charge-transfer resistance associated with the ORR and a double-layer capacitance within the catalyst layer, and the low-fiequency arc (mass transfer arc), which mainly reflects the mass-transport limitations in the gas phase within the backing and the catalyst layer. Due to its appearance at low frequencies, it is often attributed to a hindrance by finite diffusion. However, other effects, such as constant dispersion due to inhomogeneities in the electrode surface and the adsorption, can also contribute to this second arc, complicating the analysis. Normally, the lower-frequency loop can be eliminated if the fuel cell cathode is operated on pure oxygen, as stated above [18],... 

Figure 5.30. Schematic of the catalyst layer geometry and its composition, exhibiting the different functional parts, a A sketch of the layer, used to construct a continuous model, b A one-dimensional transmission-line equivalent circuit where the elementary unit with protonic resistivity Rp, the charge transfer resistivity Rch and the double-layer capacitance Cj are highlighted [34], (Reprinted from Journal of Electroanalytical Chemistry, 475, Eikerling M, Komyshev AA. Electrochemical impedance of the cathode catalyst layer in polymer electrolyte fuel cells, 107-23, 1999, with permission from Elsevier.)...

In addition to the equivalent circuit method, the impedance results can also be analyzed using mathematical models based on physicochemical theories. Guo and White developed a steady-state impedance model for the ORR at the PEM fuel cell cathode [15]. They assumed that the electrode consists of flooded ionomer-coated spherical agglomerates surrounded by gas pores. Stefan-Maxwell equations were used to describe the multiphase transport occurring in both the GDL and the catalyst layer. The model predicted a high-frequency loop due to the charge transfer process and a low-frequency loop due to the combined effect of the gas-phase transport resistance and the charge transfer resistance when the cathode is at high current densities. 

As shown in Fig. 1.4 of Chapter 1, under a load, PEM fuel cell performance is determined by four voltage losses the voltage loss caused by mixed potential and hydrogen crossover, which is related to the Pt catalyst status and the membrane properties the activation loss, which is related to the electrode kinetics the ohmic loss, which is determined by ohmic resistance and the voltage loss caused by mass transfer, which is affected by the characteristics of the gas diffusion layer and catalyst layer. The voltage loss caused by mixed potential and hydrogen crossover will be discussed in detail in Chapter 7. The activation loss, ohmic loss, and mass transfer loss can be calculated from the charge transfer resistance, ohmic resistance, and mass transfer resistance, which can be determined by EIS measurement and simulation. 

In the ECM (Fig. 12.13), is the ohmic resistance of the solution electrolyte, while Ri and C (constant phase element, CPE), respectively, represent the ionic ohmic resistance and ionic capacitance in the catalyst layer the capacitance (Ci) was replaced by a CPE to more accurately reflect the porous electrode behavior [30]. R2 and C2 represent methanol oxidation charge transfer resistance and interfacial double layer capacitance, respectively, and R represents intermediate adsorbate resistance due to the increase in intermediate adsorbate coverage at the reaction site of the catalyst surface. An adsorbed intermediate, such as CO, can be oxidized to CO2 above a critical potential to result in an inductance, L [28]. The inductance of the instrument in the HF region was not pursued in this ECM. 

The charge transfer can be modeled by an equivalent electrical circuit, the most basic of which is illustrated in Figure 9.2. In the electrochemical circuit, there is an electrical resistance, an ionic resistance, and a charge transfer resistance that represent the losses associated with ion transfer through the catalyst and surface, the electrolyte, and across the double layer, respectively. 

Ethanol electro- oxidation/cyclic voltammetry, electrochemical impedance spectroscopy Pt and Pt/Ru NaOH solution Electrodeposition of noble metal on CuNi alloys Higher electrocatalytic activity is found for ethanol oxidation for the catalyst layer prepared from PTFE suspension of noble metal salts rather without PTFE suspension. The charge transfer resistance is greatly reduced in the Pt/Ru-modilied CuNi electrodes Gupta et al. (2004)... 

In the polarization curve, three parts can be observed kinetic, ohmic, and mass transfer. In the kinetic part, the cell voltage drop is due to the charge-transfer kinetics, i.e., the 02 reduction and H2 oxidation rate at the electrode surface, which is dominated by the kinetic I-rj equation (Equation 1.37). In the ohmic part, the cell voltage drop is mainly due to the internal resistance of the fuel cell, including electrolyte membrane resistance, catalyst layer resistance, and contact resistance. In the mass transfer part, the voltage drop is due to the transfer speed of H2 and 02 to the electrode surface. 

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