Fuel overpotentials

One factor contributing to the inefficiency of a fuel ceU is poor performance of the positive electrode. This accounts for overpotentials of 300—400 mV in low temperature fuel ceUs. An electrocatalyst that is capable of oxygen reduction at lower overpotentials would benefit the overall efficiency of the fuel ceU. Despite extensive efforts expended on electrocatalysis studies of oxygen reduction in fuel ceU electrolytes, platinum-based metals are stiU the best electrocatalysts for low temperature fuel ceUs. 

Fuel cell stack voltage varies with external load. During low current operation, the cathode s activation overpotential slows the reaction, and this reduces the voltage. At high power, there is a limitation on how quickly the various fluids can enter and... 

The extent to which anode polarization affects the catalytic properties of the Ni surface for the methane-steam reforming reaction via NEMCA is of considerable practical interest. In a recent investigation62 a 70 wt% Ni-YSZ cermet was used at temperatures 800° to 900°C with low steam to methane ratios, i.e., 0.2 to 0.35. At 900°C the anode characteristics were i<>=0.2 mA/cm2, Oa=2 and ac=1.5. Under these conditions spontaneously generated currents were of the order of 60 mA/cm2 and catalyst overpotentials were as high as 250 mV. It was found that the rate of CH4 consumption due to the reforming reaction increases with increasing catalyst potential, i.e., the reaction exhibits overall electrophobic NEMCA behaviour with a 0.13. Measured A and p values were of the order of 12 and 2 respectively.62 These results show that NEMCA can play an important role in anode performance even when the anode-solid electrolyte interface is non-polarizable (high Io values) as is the case in fuel cell applications. 

In practice the situation is less favorable due to losses associated with overpotentials in the cell and the resistance of the membrane. Overpotential is an electrochemical term that, basically, can be seen as the usual potential energy barriers for the various steps of the reactions. Therefore, the practical efficiency of a fuel cell is around 40-60 %. For comparison, the Carnot efficiency of a modern turbine used to generate electricity is of order of 50 %. It is important to realize, though, that the efficiency of Carnot engines is in practice limited by thermodynamics, while that of fuel cells is largely set by material properties, which may be improved. 

This is considerably higher than that of an H2-O2 fuel cell (i.e., 83%). However, under normal operating conditions, at a current density j, the electrode potentials deviate from their equilibrium values as a result of large overpotentials, r, at both electrodes (Fig. 5) ... 

A significant steady-state population of reduced surface sites is generated by the cathodic overpotential, as set by the fuel cell load. 

Nprskov JK, Rossmeisl J, Logadottir A, Lindqvist L, Kitchin JR, Bligaard T, Jonsson H. 2004. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J Phys Chem B 108 17886-17892. 

Poisoning of platinum fuel cell catalysts by CO is undoubtedly one of the most severe problems in fuel cell anode catalysis. As shown in Fig. 6.1, CO is a strongly bonded intermediate in methanol (and ethanol) oxidation. It is also a side product in the reformation of hydrocarbons to hydrogen and carbon dioxide, and as such blocks platinum sites for hydrogen oxidation. Not surprisingly, CO electrooxidation is one of the most intensively smdied electrocatalytic reactions, and there is a continued search for CO-tolerant anode materials that are able to either bind CO weakly but still oxidize hydrogen, or that oxidize CO at significantly reduced overpotential. 

When pure hydrogen is used as the fuel, the overpotential for the hydrogen oxidation reaction (HOR) at the Pt anode is negligibly small. 

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 ... 

Ambient temperature catalysis of O2 reduction at low overpotentials is a challenge in development of conventional proton exchange membrane fuel cells (pol5mer electrolyte membrane fuel cells, PEMFCs) [Ralph and Hogarth, 2002]. In this chapter, we discuss two classes of enz5mes that catalyze the complete reduction of O2 to H2O multi-copper oxidases and heme iron-containing quinol oxidases. 

Enzymes are efficient catalysts for cathodic and anodic reactions relevant to fuel cell electrocatalysis in terms of overpotential, active site activity, and substrate/reaction specificity. This means that design constraints (e.g., fuel containment and anode-cathode separation) are relaxed, and very simple devices that may take up ambient fuel or oxidant from their environment are possible. While operation is generally confined to conditions close to ambient temperature, pressure, and pH, and power densities over about 10 mW cm are rarely achieved, enzyme fuel cells may be particularly useM in niche environments, for example scavenging trace H2 released into air, or sugar and O2 from blood. Thus, trace or unusual fuels become viable for energy production. 

Fig. 23. (a) Experimental IR-free overpotentials in MCFC-based separator. Cell performance 0.25% C02 Feed. All curves calculated [32] (b) C02 production scheme using molten carbonate fuel cell stack. 

The presence of a small amount of water vapor (up to pH20/pH2 = -0.03) in fuel reduces anode overpotential. For anode-supported cells, the use of pore formers is important to tailor the shrinkage during cofiring and to create adequate porosity for better performance. The difference in cell power output could differ by as much as 100% for cells as porosity changes from -30 to -50%. 

Wen C, Kato R, Fukunaga H, Ishitani H, and Yamada K. The overpotential of nickel/ yttria-stabilized zirconia cermet anodes used in solid oxide fuel cells. J Electrochem Soc 2000 147 2076-2080. 

Initially, both electrodes are at equilibrium. Since the anode has accumulated electrons and the cathode has depleted electrons, electrons begin to flow from electrode from the anode to the cathode. The thermodynamic driving force for the electron flow is the electrode potential difference, which for the fuel cell reaction is 1.23 Y at standard conditions. In addition to electron flow, H + ions produced at the anode diffuse through the bulk solution and react at the cathode. The reaction is able to continue as long as H2 is fed at the anode and 02 at the cathode. Hence, the cell is not at equilibrium. The shift in electrode potential from equilibrium is called the overpotential (>/). 

Useful work (electrical energy) is obtained from a fuel cell only when a reasonable current is drawn, but the actual cell potential is decreased from its equilibrium potential because of irreversible losses as shown in Figure 2-2". Several sources contribute to irreversible losses in a practical fuel cell. The losses, which are often called polarization, overpotential, or overvoltage (ri), originate primarily from three sources (1) activation polarization (r act), (2) ohmic polarization (rjohm), and (3) concentration polarization (ricoiic)- These losses result in a cell voltage (V) for a fuel cell that is less than its ideal potential, E (V = E - Losses). 

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