Ionomer membranes alloy

The electrolyte is a perfluorosulfonic acid ionomer, commercially available under the trade name of Nafion . It is in the form of a membrane about 0.17 mm (0.007 in) thick, and the electrodes are bonded directly onto the surface. The elec trodes contain veiy finely divided platinum or platinum alloys supported on carbon powder or fibers. The bipolar plates are made of graphite or metal. 

The stability and durability of Pt alloys, especially those involving a >d transition metal, are the major hurdles preventing them from commercial fuel cell applications. "" The transition metals in these alloys are not thermodynamically stable and may leach out in the acidic PEM fuel cell environment. Transition metal atoms at the surface of the alloy particles leach out faster than those under the surface of Pt atom layers." The metal cations of the leaching products can replace the protons of ionomers in the membrane and lead to reduced ionic conductivity, which in turn increases the resistance loss and activation overpotential loss. Gasteiger et al. showed that preleached Pt alloys displayed improved chemical stability and reduced ORR overpotential loss (in the mass transport region), but their long-term stability has not been demonstrated. " These alloys experienced rapid activity loss after a few hundred hours of fuel cell tests, which was attributed to changes in their surface composition and structure." ... 

A1) Applied and hot-pressed Pt /PTFE (A2) Electroless deposition of Pt on membrane (A3) Applied and hot-pressed Pt/C(or Pt)//ionomer within ionomer-impregnated carbon paper (A4) Alloy catalyst sputtered onto array of nanowhiskers and the catalyzed array embedded into the membrane surface (Bl) Pt/C//PTFE applied to substrate and impregnated with recast ionomer (B2) (Bl) + sputtered Pt layer (B3) Pt catalyst electrodeposited... 

The PE MFC has a solid ionomer membrane as the electrolyte, and a platinum, carbon-supported Pt or Pt-based alloy as the electrocatalyst. Within the cell, the fuel is oxidized at the anode and the oxidant reduced at the cathode. As the solid proton-exchange membrane (PEM) functions as both the cell electrolyte and separator, and the cell operates at a relatively low temperature, issues such as sealing, assembly, and handling are less complex than with other fuel cells. The P EM FC has also a number of other advantages, such as a high power density, a rapid low-temperature start-up, and zero emission. With highly promising prospects in both civil and military applications, PEMFCs represent an ideal future altemative power source for electric vehicles and submarines [6]. 

In a previous paper (2), the author described a method to dissolve the sulfonyl fluoride precursor form of a perfluorinated sulfonate ionomer. Commercially available forms of Nafion are supplied as activated membranes (i.e., saponified from the precursor to the ionic form), and near-quantitative reconstitution of the precursor functionality (such as RSOjF) must first be performed using a chemical reagent such as SF. f4) before dissolution in perhalogenated solvents is possible. Besides adding to the cost of membrane manufacture, SF. is extremely toxic and corrosive and must be handled in nickel alloy pressure equipment. Therefore, a method for dissolving perfluorinated ionomers directly would be more desirable. 

Even among the models that employ porous-electrode theory, there have been differences in how the various models choose to describe the electrode. For example, consider the catalyst layer in a state-of-the-art PEM fuel cell containing a supported-platinum-on-carbon (or platinum-alloy-on-carbon) catalyst, a polymeric membrane material, and, in some cases, a void volume. Whether this void volume is considered explicitly, or whether gas- and liquid-phase transport is simply described via permeability through the ionomer is one of the key differences between the various models. 

The loss of the alloyed non-noble metal does not always lead to a decrease of activity. As already mentioned, in some cases, an increase of activity was found, ascribed to as surface roughening or electrOTiic effects [61]. On the other hand, in other cases, the activity decreases because the beneficial effect on the electronic structure of Pt is lost. In any case, metal ions leaching from the catalyst will have a negative effect on the membrane and ionomer phase in the electrode. 

This reaction is currently unavoidable and appears to be favored at hot and dry operating conditions of the fuel cell. The peroxide decomposition forms reactive radials such as hydroxyl, OH, and peroxyl, OOH, that cause oxidative degradation of both the fuel cell membrane and catalyst support [67]. Both electrodes currently use Pt or Pt alloys to catalyze both the HOR and ORR reactions. The catalyst particles are typically supported on a high surface area, heat-treated carbon to both increase the effectiveness of the catalyst and to provide a path for the electrons to pass through to the external circuit via the gas diffusion media (which is typically also made of carbon) and the current collecting bipolar plates. In addition, the catalyst particles are coated in ionomer to facilitate proton transport however, the electrode structure must also be porous to facilitate reactant gas transport. A schematic of a typical PEM MEA is shown in Fig. 17.1. A boundary condition exists at the catalyst particle where protons from the ionomer, electrons from the electrically conducting Pt and carbon, and reactant gases meet. This is usually referred to as the three-phase boundary. The transport of reactants, electrons, and protons must be carefully balanced in terms of the properties, volume, and distribution of each media in order to optimize operation of the fuel cell. 

The main contaminants for the membrane are cationic species, such as metal ions, which may come from contaminated air and fuel streams when moisture is present, metal fuel cell components, balance-of-plant components, or nonmetal contaminated component materials. Other organic and inorganic materials can also contaminate the membrane, but the effects of these are less well documented. Component materials supplying contaminants may include the platinum catalyst or alloying metals, such as ruthenium or cobalt, which may leach out into the membrane the raw material source for the carbon materials (in the catalyst support, microporous layer, gas diffusion layer, or plate materials) may also have inherent metal or other chemical impurities and seal and gasketing materials, such as silicone, can decompose and contaminate the membrane. All of the membrane contaminants can also impact the ionomer materials present in the catalyst layers. 

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