Catalyst layer porous electrodes

A fuel cell consists of an ion-conducting membrane (electrolyte) and two porous catalyst layers (electrodes) in contact with the membrane on either side. The hydrogen oxidation reaction at the anode of the fuel cell yields electrons, which are transported through an external circuit to reach the cathode. At the cathode, electrons are consumed in the oxygen reduction reaction. The circuit is completed by permeation of ions through the membrane. 

Figure 15.3 Simulated effectiveness factor for porous carbon electrode as a function of the exchange current density jo and DCo for Ip] = 0.4 V for a 10wt% Pt/C catalyst layer with 7= 10, A = 140m g p = 2gcm, Nafion volume fraction 0.6, thickness p,m, and ionic conductivity 0.05 Scm See the text for details. (Reproduced from Gloaguen et al. [1994], with kind permission from Springer Science and Business Media.)...

As it follows from Table 5, many catalysts contain metallic platinum. We have developed bi-layer porous hydrophobic air electrodes, which do not contain platinum metals, are active and can be cycled [24, 25] (Figures 4-6). These bifunctional catalysts are pyrolized Co - macrocyclic compounds. Said catalyst has high catalytic activity for the oxygen reduction and also features acceptable stability, however its activity for the oxygen evolution is not high enough. 

The next set of models treats the catalyst layers using the complete simple porous-electrode modeling approach described above. Thus, the catalyst layers have a finite thickness, and all of the variables are determined as per Table 1 with a length scale of the catalyst layer. While some of these models assume that the gas-phase reactant concentration is uniform in the catalyst layers,most allow for diffusion to occur in the gas phase. 

The final simple macrohomogeneous porous-electrode models are the ones that are more akin to thin-film models. In these models, the same approach is taken, but instead of gas diffusion in the catalyst layer, the reactant gas dissolves in the electrolyte and moves by diffusion and reaction. The... 

Figure 11. Tafel plot of flooded porous-electrode simulation results for the cathode at three different values of xp = 2.2nFIfQ 2 02, z=dbK. The z coordinate ranges from 0 (catalyst layer/membrane interface) to L (catalyst layer/diffusion medium interface), the dimensionless overpotential is defined as // = —o FIRT r]oRR, - ), and the ORR rate constant is defined as A = hFFq 2 (Reproduced with permission from ref 36. Copyright 1998 The Electrochemical Society, Inc.)...

The species diffusivity, varies in different subregions of a PEFC depending on the specific physical phase of component k. In flow channels and porous electrodes, species k exists in the gaseous phase and thus the diffusion coefficient corresponds with that in gas, whereas species k is dissolved in the membrane phase within the catalyst layers and the membrane and thus assumes the value corresponding to dissolved species, usually a few orders of magnitude lower than that in gas. The diffusive transport in gas can be described by molecular diffusion and Knudsen diffusion. The latter mechanism occurs when the pore size becomes comparable to the mean free path of gas, so that molecule-to-wall collision takes place instead of molecule-to-molecule collision in ordinary diffusion. The Knudsen diffusion coefficient can be computed according to the kinetic theory of gases as follows... 

In the proton-emitting membrane or proton electrolyte membrane (PEM) design, the membrane electrode assembly consists of the anode and cathode, which are provided with a very thin layer of catalyst, bonded to either side of the proton exchange membrane. With the help of the catalyst, the H2 at the anode splits into a proton and an electron, while Oz enters at the cathode. On the inside of the porous anode is a thin platinum catalyst layer. When H2 reaches this layer, it separates into protons (H2 ions) and electrons. One of the reasons why the cost of fuel cells is still high is because the cost of the platinum catalyst is rising. One ounce of platinum cost 361 in 1999 and increased to 1,521 in 2007. 

In a fuel cell, chemical energy is converted into electrical energy. For instance, in an H2-02 fuel cell (Fig. 13.4), porous electrodes and catalyst layers are separated by a SPE membrane (e.g. Nation 117). 

A porous anode and cathode are attached to each surface of the membrane, forming a membrane-electrode assembly, similar to that employed in SPE fuel cells. Electrochemical reactions (electron transfer-l-hydrogenation) occur at the interfaces between the ion exchange membrane and electrochemically active layers of electrodes. Electrochemical reductive HDH occurred at the interfaces between the ion exchange membrane and the cathode catalyst layer when an electrical current is applied between the electrodes ... 

Air diffusion electrodes In fuel cells and in air-breathing batteries, a mesoporous carbon electrode is made up of two layers an outer layer composed of carbon powder and a hydrophobic (nonwettable) binder, typically PTFE. This enables the access of gas to the inner layer, where the binder is selected to be both a hydrophilic (wettable) and an ion-conducting ionomer, to support (rather than impair if the binder was nonconducting) the ionic conductivity of the porous electrode. The catalyst particles are dispersed in-between the carbon particles. Thus, a very tortuous interface between the two layers is formed. The reacting gas approaches this interface, forming three phase points of contact providing a high active surface area. See also - air electrode. 

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. 

When discussing the ionic conductivity of catalyst layers, one must mention the finite transmission-line equivalent circuit, which is widely used to model porous electrodes and was shown as Figure 4.33 in Chapter 4. For ease of discussion, the circuit is re-plotted here as Figure 6.23. 

To elucidate methanol crossover at the DMFC cathode, the active electrode surface of the cathode was divided into two separate parts one for oxygen reduction and the other for oxidation of crossover methanol. In this model, the methanol oxidation and oxygen reduction occur in parallel at different sites or pores because of the porous structure of the catalyst layer. The equivalent circuit for this model is presented in Figure 6.69. 

The MCFC membrane electrode assembly (MEA) comprises three layers a porous lithiated NiO cathode structure and a porous Ni/NiCr alloy anode structure, sandwiching an electrolyte matrix (see detail below). To a first approximation, the porous, p-type semiconductor, nickel oxide cathode structure is compatible with the air oxidant, and a good enough electrical conductor. The nickel anode structure, coated with a granular proprietary reform reaction catalyst, is compatible with natural gas fuel and reforming steam, and is an excellent electrical conductor. As usual, the oxygen is the actual cathode and the fuel the anode. Hence the phrase porous electrode structure . 

The presence of water is critical for operation but in current PEMFCs proper water management is a delicate issue and poor control can greatly reduce the efficiency of the device. An excess of water can flood the catalyst and porous transport layers impeding the transport of reactants and eventually drowning the fuel cell. At low water content, the polymer electrolyte membrane can become a poor conductor and the reactivity at the electrodes is affected. Local hot spots arising due to the inefficient operation result in early degradation of the cell. ... 

The heart of a fuel cell is the membrane electrode assembly (MEA). In the simplest form, the electrode component of the MEA would consist of a thin film containing a highly dispersed nanoparticle platinum catalyst. This catalyst layer is in good contact with the ionomeric membrane, which serves as the reactant gas separator and electrolyte in this cell. The membrane is about 25-100 p,m thick. The MEA then consists of an ionomeric membrane with thin catalyst layers bonded on each side. Porous and electrically conducting carbon paper/cloth current collectors act as gas distributors (Figure 27.1). Since ohmic losses occur within the ionomeric membrane, it is important to maximize the proton conductivity of the membrane, without sacrificing the mechanical and chemical stability. 

Fig. 42. Schematic of regions considered in PEFC air electrode modeling, including (from left to right) gas flow channel, gas-diffusion backing, and cathode catalyst layer. Oxygen is transported in the backing through the gas-phase component of a porous/tortuous medium and through the catalyst layer by diffusion through a condensed medium. The catalyst layer also transports protons and is assumed to have evenly distributed catalyst particles within its volume [100]. (Reprinted by permission of the Electrochemic Society).

A special kind of porous electrodes is gas diffusion electrodes which mostly have been used in fuel cells. A gas diffusion anode for hydrogen [68-73] may consist of three layers a metal current collector, a hydrophobic gas-porous layer, and a catalyst layer. The hydrophobic layer is often based on polytetrafluorethylene, which is made electric con-... 

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