Polymer electrolyte membrane hydrogen oxidation

The principle of the fuel cell was first demonstrated by Grove in 1839 [W. R. Grove, Phil. Mag. 14 (1839) 137]. Today, different schemes exist for utilizing hydrogen in electrochemical cells. We explain the two most important, namely the Polymer Electrolyte Membrane Fuel Cell (PEMFC) and the Solid Oxide Fuel Cell (SOFC). 

Figure 8.31. Principle of a Polymer Electrolyte Membrane (PEM) fuel cell. A Nation membrane sandwiched between electrodes separates hydrogen and oxygen. Hydrogen is oxidized into protons and electrons at the anode on the left. Electrons flow through the outer circuit, while protons diffuse through the...

Polymer electrolyte fuel cell (PEFC) is considered as one of the most promising power sources for futurist s hydrogen economy. As shown in Fig. 1, operation of a Nation-based PEFC is dictated by transport processes and electrochemical reactions at cat-alyst/polymer electrolyte interfaces and transport processes in the polymer electrolyte membrane (PEM), in the catalyst layers consisting of precious metal (Pt or Ru) catalysts on porous carbon support and polymer electrolyte clusters, in gas diffusion layers (GDLs), and in flow channels. Specifically, oxidants, fuel, and reaction products flow in channels of millimeter scale and diffuse in GDL with a structure of micrometer scale. Nation, a sulfonic acid tetrafluorethy-lene copolymer and the most commonly used polymer electrolyte, consists of nanoscale hydrophobic domains and proton conducting hydrophilic domains with a scale of 2-5 nm. The diffusivities of the reactants (02, H2, and methanol) and reaction products (water and C02) in Nation and proton conductivity of Nation strongly depend on the nanostructures and their responses to the presence of water. Polymer electrolyte clusters in the catalyst layers also play a critical... 

The best catalysts for the electrochemical oxidation and production of hydrogen are platinum metal and the hydrogenase enzymes. Both catalyze the reaction of two protons with two electrons to form H2, as shown in Equation 7.1. Because of its superior catalytic rates and overpotentials compared to other metals and because of its high stabihty compared to hydrogenase enzymes, platinum is currently used as the catalyst for both half reactions (the oxidation of H2 and the reduction of O2) in polymer electrolyte membrane (PEM) fuel cells, which have been proposed for automotive transportation [1]. However, the high cost of platinum provides a strong impetus for developing less expensive alternatives. 

The membrane in the polymer electrolyte fuel cell (PEFC) is a key component. Not by chance does the type of membrane brand the cell name - it is the most important component determining cell architecture and operation regime. Polymer electrolyte membranes are almost impermeable to gases, which is crucial for gas-feed cells, where hydrogen (or methanol) oxidation and oxygen reduction must take place at two separated electrodes. However, water can diffuse through the membrane and so can methanol. Parasitic transport of methanol (methanol crossover) severely impedes the performance of the direct methanol fuel cell (DMFC). 

There exist a variety of fuel cells. For practical reasons, fuel cells are classified by the type of electrolyte employed. The following names and abbreviations are frequently used in publications alkaline fuel cells (AFC), molten carbonate fuel cells (MCFC), phosphoric acid fuel cells (PAFC), solid oxide fuel cells (SOFC), and proton exchange membrane fuel cells (PEMFC). Among different types of fuel cells under development today, the PEMFC, also called polymer electrolyte membrane fuel cells (PEFC), is considered as a potential future power source due to its unique characteristics [1-3]. The PEMFC consists of an anode where hydrogen oxidation takes place, a cathode where oxygen reduction occurs, and an electrolyte membrane that permits the transfer of protons from anode to cathode. PEMFC operates at low temperature that allows rapid start-up. Furthermore, with the absence of corrosive cell constituents, the use of the exotic materials required in other fuel cell types is not required [4]. 

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