Mass transport PEMFC

For isolating the overpotential of the working electrode, it is common practice to admit hydrogen to the counter-electrode (the anode in a PEMFC the cathode in a direct methanol fuel cell, DMFC) and create a so-called dynamic reference electrode. Furthermore, the overpotential comprises losses associated with sluggish electrochemical kinetics, as well as a concentration polarization related to hindered mass transport ... 

Oxidation of Adsorbed CO The electro-oxidation of CO has been extensively studied given its importance as a model electrochemical reaction and its relevance to the development of CO-tolerant anodes for PEMFCs and efficient anodes for DMFCs. In this section, we focus on the oxidation of a COads monolayer and do not cover continuous oxidation of CO dissolved in electrolyte. An invaluable advantage of COads electro-oxidation as a model reaction is that it does not involve diffusion in the electrolyte bulk, and thus is not subject to the problems associated with mass transport corrections and desorption/readsorption processes. 

In a PEMFC, the power density and efficiency are limited by three major factors (1) the ohmic overpotential mainly due to the membrane resistance, (2) the activation overpotential due to slow oxygen reduchon reaction at the electrode/membrane interface, and (3) the concentration overpotential due to mass-transport limitations of oxygen to the electrode surfaced Studies of the solubility and concentration of oxygen in different perfluorinated membrane materials show that the oxygen solubility is enhanced in the fluorocarbon (hydrophobic)-rich zones and hence increases with the hydrophobicity of the membrane. The diffusion coefficient is directly related to the water content of the membrane and is thereby enhanced in membranes containing high water content the result indicates that the aqueous phase is predominantly involved in the diffusion pathway. ... 

The EOD coefficient, is the ratio of the water flux through the membrane to the proton flux in the absence of a water concentration gradient. As r/d,3g increases with increasing current density during PEMFC operation, the level of dehydration increases at the anode and normally exceeds the ability of the PEM to use back diffusion to the anode to achieve balanced water content in the membrane. In addition, accumulation of water at the cathode leads to flooding and concomitant mass transport losses in the PEMFC due to the reduced diffusion rate of O2 reaching the cathode. 

In PEMFCs, Ralph et al. [86] tested a Ballard Mark V single cell with two different DLs a carbon cloth (Zoltek PWB-3) and a carbon fiber paper (Toray TGP-090) all the other operating conditions stayed the same for bofh cases. It was observed that the carbon cloth demonstrated a distinct advantage over the CFP at high current densities (>600 mA/cm ), while at low current densities both DLs performed similarly. If was claimed fhaf this was because the CC material enhanced mass transport properties and improved the water management within the cell due to its porosity and hydrophobicity. 

Electrocatalysts One of the positive features of the supported electrocatalyst is that stable particle sizes in PAFCs and PEMFCs of the order of 2-3 nm can be achieved. These particles are in contact with the electrolyte, and since mass transport of the reactants occurs by spherical diffusion of low concentrations of the fuel-cell reactants (hydrogen and oxygen) through the electrolyte to the ultrafine electrocatalyst particles, the problems connected with diffusional limiting currents are minimized. There has to be good contact between the electrocatalyst particles and the carbon support to minimize ohmic losses and between the supported electrocatalysts and the electrolyte for the proton transport to the electrocatalyst particles and for the subsequent oxygen reduction reaction. This electrolyte network, in contact with the supported electrocatalyst in the active layer of the electrodes, has to be continuous up to the interface of the active layer with the electrolyte layer to minimize ohmic losses. 

Figure 5.1 Schematic of a PEMFC. The cathode and anode reactions are given for a hydrogen PEMFC and a DMFC. At high current density or liquid water saturation of the GDL, the shading of the catalyst layer by the rib area causes mass transport limitation.

PEMFCs must have the ability to survive and start up from sub-freezing temperatures, also called cold start, to be deployed successfully in automobiles. Under freezing environmental conditions, water produced has a tendency to freeze in open pores in the catalyst layer and GDL, rather than being removed from the fuel cell, thus creating mass transport limitations that eventually result in the shutdown of PEFC operation. Figure 31.11 shows the accumulation of solid water in a fuel cell in sub-freezing operation detected by neutron imaging [34]. 

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