DAFCs

THERMODYNAMICS AND KINETICS OF REACTIONS IN A DAFC ETHANOL OXIDATION... 

The large-scale spread of DAFCs is closely related to the development of efficient anodic and cathodic materials, characterized by very fast electrochemical kinetics, stability at the high current densities in alkaline environments and modest cost. This objective requires cathodes without noble metals and anodes with very low amounts of noble metals. In order to improve the cheapness and sustainability of the processes described above, the most accepted opinion is the possibility of using solar light by means of the introduction of Ti02, pure or doped, into the electrode material formulation. Figure 4.15 shows a typical laboratory-scale photoelectrocatalytic reactor. 

Figure 16. UV-visible absorption spectra of A-S-D triad (solid line) and DAFc (dashed line) in 10 (tM ethanol solutions.

A UV-visible absorption spectrum of a 10 (J.M ethanol solution of a model compound (DAFc in Fig. 5) for the D moiety is shown together with that of the A-S-D triad in Fig. 16. The absorption bands between 200 and 300 nm can be clearly seen for DAFc. Qualitatively, absorption spectra for A-S-D triads in the LB films and in the 10 pM ethanol solution are similar. It is interesting to note, however, that the relative intensities of the acylated perylene band around 450 nm against the 200-300 nm UV absorption bands are different between the LB films and the ethanol solution. This difference can be attributed to orientation of the perylene moiety in the LB films in the same way as in the antenna LB films reported previously [38]. 

In recent decades, direct alcohol fuel cells (DAFCs) have been extensively studied and considered as possible power sources for portable electronic devices and vehicles in the near future. The application of methanol is limited due to its high volatility and toxicity, although it is relatively easily oxidized to CO2 and protons. So other short chain organic chemicals especially ethanol, ethylene glycol, propanol, and dimethyl... 

C. Lamy, E. M. Belgsir, and J.-M. Leger, Electrocatalytic oxidation of aliphatic alcohols Application to the direct alcohol fuel cell (DAFC), J. Appl. Electrochem. 31, 799-809 (2001). 

DMFCs and direct ethanol fuel cells (DEFCs) are based on the proton exchange membrane fuel cell (PEM FC), where hydrogen is replaced by the alcohol, so that both the principles of the PEMFC and the direct alcohol fuel cell (DAFC), in which the alcohol reacts directly at the fuel cell anode without any reforming process, will be discussed in this chapter. Then, because of the low operating temperatures of these fuel cells working in an acidic environment (due to the protonic membrane), the activation of the alcohol oxidation by convenient catalysts (usually containing platinum) is still a severe problem, which will be discussed in the context of electrocatalysis. One way to overcome this problem is to use an alkaline membrane (conducting, e.g., by the hydroxyl anion, OH ), in which medium the kinetics of the electrochemical reactions involved are faster than in an acidic medium, and then to develop the solid alkaline membrane fuel cell (SAMFC). 

The principles of the fuel cell are illustrated in Figure 1.1. The electrochemical cell consists of two electrodes, an anode and a cathode, which are electron conductors, separated by an electrolyte [e.g. a proton exchange membrane (PEM) in a PEMFC or in a DAFC], which is an ion conductor (as the result of proton migration and diffusion inside the PEM). An elementary electrochemical cell converts directly the chemical... 

Oxidation of Alcohols in a Direct Alcohol Fuel Cell The electrocatalytic oxidation of an alcohol (methanol, ethanol, etc.) in a direct alcohol fuel cell (DAFC) will avoid the presence of a heavy and bulky reformer, which is particularly convenient for applications to transportation and portable electronics. However, the reaction mechanism of alcohol oxidation is much more complicated, involving multi-electron transfer with many steps and reaction intermediates. As an example, the complete oxidation of methanol to carbon dioxide ... 

In addition, in a DAFC, the proton exchange membrane is not completely alcohol tight, so that some alcohol leakage to the cathodic compartment will lead to a mixed potential with the oxygen electrode. This mixed potential will decrease further the cell voltage by about 0.1-0.2 V. It turns out that new electrocatalysts insensitive to the presence of alcohols are needed for the DAFC. 

Hydrogen is a secondary fuel and, like electricity, is an energy carrier. It is the most electroactive fuel for fuel cells operating at low and intermediate temperatures. Methanol and ethanol are the most electroactive alcohol fuels, and, when they are electro-oxidized directly at the fuel cell anode (instead of being transformed in a hydrogen-rich gas in a fuel processor), the fuel cell is called a DAFC either a DMFC (with methanol) or a DEFC (with ethanol). 

In addition to hydrogen as a fuel, methanol or ethanol can be directly converted into electricity in a DAFC, the great progress of which resulted from the use of a proton exchange membrane acting both as an electrolyte (instead of the aqueous electrolytes previously used) and as a separator preventing the mixing of fuel and oxidant. A DAFC can work at moderate temperatures (30-50 °C) for portable applications, but now the tendency is to look for new membranes that are less permeable to alcohol and... 

The last three fuel cells (PEMFC, DAFC and SAMFC) are low-temperature fuel cells. In this chapter, the discussion will be focused on these fuel cells, particularly the PEMFC and the DAFC, since they can accommodate biomass fuels, either after fuel processing to obtain reformate hydrogen or directly with bioethanol. 

Die Auswaschzeit zwischen den einzelnen Proben muli so bemessen sein, dafc die vorhergehende Analyse das Ergebnis der Folgeananlyse nicht be-einflufit. 

In this chapter, after recalling the working principles and the different kinds of fuel cells, the discussion will be focused on low-temperature fuel cells (AFC, PEMFC, and DAFC), in which several kinds of carbon materials are used (catalyst support, gas-diffusion layer [GDL], bipolar plates [BP], etc.). Then some possible applications in different areas will be presented. Finally the materials used in fuel cells, particularly carbon materials, will be discussed according to the aimed applications. To read more details on the use of carbon in fuel cell technology, see the review paper on The role of carbon in fuel cell technology recently published by Dicks [6],... 

For low-temperature fuel cells (AFC, PEMFC, and DAFC) carbon is mainly used... 

The bipolar flow-field plate is the main hardware component of the PEMFC and of the DAFC. This has to fulfill several requirements, namely... 

In low-temperature fuel cells (AFC, PEMFC, DAFC, etc.), carbon materials are important since they are involved in the fabrication of BP, GDL, and CL. It appears that no other materials can replace carbon with the same properties (good electronic conductivity, good thermal and chemical stabilities, and low cost). But much work is needed to optimize carbon materials for fuel cell applications and to ensure that they meet the performance targets for conductivity, physical properties, and lifetime within operating stacks. 

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