Anodic mass transport losses

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. 

Electrode materials play an important role in the performance (power output) and cost of bacterial fuel cells. This problem was the topic of two review papers. In a review by Rismani-Yazdi et al. (2008), some aspects of cathodic limitations (ohmic and mass transport losses, substrate crossover, etc.), are discussed. In a review by Zhou et al. (2011), recent progress in anode and cathode and filling materials as three-dimensional electrodes for microbial fuel cells (MFCs) has been reviewed systematically, resulting in comprehensive insights into the characteristics, options, modifications, and evaluations of the electrode materials and their effects on various actual wastewater treatments. Some existing problems of electrode materials in current MFCs are summarized, and the outlook for future development is also suggested. 

In region 111, for convenience, both dry anode and cathode cases are shown to peak at the same location, although this depends on the individual conditions and is not necessarily the case. Following the maximum local current, there is a downward trend resulting from local flooding or gas-phase mass transport losses at the electrode(s). This peak and downward trend will only occur if a reactant starvation condition (via flooding or high utilization) is reached. 

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 ... 

Mass transport within the electrodes is of particular importance in determining the reflection of the porous media structure on the fuel cell performance. In fact, the main results of mass transport limitation is that the reactant concentrations (H2 and CO for the anode, and O2 for the cathode) at the reaction zone are lower than in the gas channel. When applying Equations (3.40) and (3.42), the result is that the lower the concentration of the reactants, the lower the calculated cell performance. The loss of voltage due to the mass transport of the gas within the electrodes is also referred to as concentration overpotential. Simplified approaches for determining concentration overpotential include the calculation of a limiting current, i.e. the maximum current obtainable due to mass transport limitation (cf. Appendix A3.2). 

Figure 3.3.7 Theoretical (dashed dotted) and real (solid) cell voltage (V) - current density (I) performance characteristics of a fuel cell. Overpotentials are responsible for the difference between theoretical and real performance and cause efficiency losses. They split into (i) activation polarization overpotentials at anode and cathode due to slow chemical kinetics, (ii) ohmic polarization overpotential due to ohmic voltage losses along the circuit, and (iii) concentration polarization overpotentials due to mass-transport limitations. The activation overpotentials of the cathode are typically the largest contribution to the total overvoltage.

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