Fuel cells environment

Ju X, M Hecht, RA Galhotra, WP Ela, EA Betterton, RG Arnold, AE Saez (2006) Destruction of gas-phase trichloroethylene in a modified fuel cell. Environ Sci Technol 40 612-617. 

Summing up this section, we would like to note that understanding size effects in electrocatalysis requires the application of appropriate model systems that on the one hand represent the intrinsic properties of supported metal nanoparticles, such as small size and interaction with their support, and on the other allow straightforward separation between kinetic, ohmic, and mass transport (internal and external) losses and control of readsorption effects. This requirement is met, for example, by metal particles and nanoparticle arrays on flat nonporous supports. Their investigation allows unambiguous access to reaction kinetics and control of catalyst structure. However, in order to understand how catalysts will behave in the fuel cell environment, these studies must be complemented with GDE and MEA tests to account for the presence of aqueous electrolyte in model experiments. 

The major requirement for a reliable hydrogen sensor operation in the fuel cell environment is in 100% condensing humidity Most of the fuel cells have abundant humidity and the sensor needs to operate continuously in humid environments. In some cases, the hydrogen sensor can also be operated at very low temperatures (as low as —40°C). The fuel cells regularly have a cold start, when operated from a very low ambient temperature the sensor needs to attain ambient temperature quickly (<30 s) and continue operation well below ambient temperature before the fuel cell itself reaches the ambient temperature. 

A final issue that faces this class of catalysts is stability in the fuel cell environment. Deactivation of materials in a fuel cell environment has been shown to be minimal in some studies,31,137 and severe in others.128,142 More active catalysts seem more susceptible to deactivation. Deactivation has been linked to the formation of peroxide and the loss of metal from the catalyst.128 On the other hand, demetallization has also been observed in pyrolyzed samples that did not lose activity with time.84 Another possible mode of deactivation could be due to the oxidation of the carbon surface. However, it seems reasonable that a complete understanding of the deactivation mechanism would first require a well-developed understanding of the active site. 

Wholly aromatic polymers are thought to be one of the more promising routes to high performance PEMs because of their availability, processability, wide variety of chemical compositions, and anticipated stability in the fuel cell environment. Specifically, poly(arylene ether) materials such as poly-(arylene ether ether ketone) (PEEK), poly(arylene ether sulfone), and their derivatives are the focus of many investigations, and the synthesis of these materials has been widely reported.This family of copolymers is attractive for use in PEMs because of their well-known oxidative and hydrolytic stability under harsh conditions and because many different chemical structures, including partially fluorinated materials, are possible, as shown in Figure 8. Introduction of active proton exchange sites to poly-(arylene ether) s has been accomplished by both a polymer postmodification approach and direct co-... 

Collection of in situ XAS data using a single cell fuel cell avoids problems associated with bubble formation found in liquid electrolytes as well as questions regarding the influence of adsorption of ions from the supporting electrolyte. However, the in situ study of membrane electrode assemblies (MEAs) in a fuel cell environment using transmission... 

XAS has been successfully employed in the characterization of a number of catalysts used in low temperature fuel cells. Analysis of the XANES region has enabled determination of the oxidation state of metal atoms in the catalyst or, in the case of Pt, the d band vacancy per atom, while analysis of the EXAFS has proved to be a valuable structural tool. However, the principal advantage of XAS is that it can be used in situ, in a flooded half-cell or true fuel cell environment. While the number of publications has been limited thus far, the increased availability of synchrotron radiation sources, improvements in beam lines brought about by the development of third generation sources, and the development of more readily used analysis software should increase the accessibility of the method. It is hoped that this review will enable the nonexpert to understand both the power and limitations of XAS in characterizing fuel cell electrocatalysts. 

Structural and compositional characterization of individual elements of a combinatorial library can be important for the initial validation of a particular combinatorial synthesis method. Many earlier reports on combinatorial synthesis and screening of electrocatalysts fall short of reporting the complete structural and compositional characterization of individual library elements of interest. The workflow described here includes catalyst characterization before and after screening, thereby establishing an activity-composition-structure-stability relationship for electrocatalysts. This can be relevant in light of the extreme conditions present in a conventional fuel cell environment. 

Liu, Z., Arnold, R.G., Betterton, E.A. and Smotkin, E. (2001) Reductive dehalogenation of gas-phase chlorinated solvents using a modified fuel cell. Environ. Sci. Technol 35,4320-4326. 

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." ... 

Bouwman et al. demonstrated that Pt can be used in the ionic form (Pt" and Pt") by dispersing it in a matrix of hydrous iron phosphate (FePO) via a sol-gel process (Pt-FePO)." The hydrous FePO possesses micropores of approximately 2 nm. It has 3 H2O molecules per Fe atom and is thought to also serve as a proton transport medium. The Pt-FePO catalyst exhibited a higher ORR activity than Pt/C catalysts. This catalyst was also found to be less sensitive to CO poisoning because CO did not adsorb onto the catalyst surface. The ORR catalytic activity was attributed to the adsorption and storage of oxygen on the FePO, presumably as Fe-hydroperoxides. However, these catalysts have poor electrical conductivity. There is no published data on the long-term stability of these catalysts in fuel cell environments. 

Samms, S.R., Wasmus, S., and Savinell, R.F., Thermal stability of proton conducting acid doped polybenzimidazole in simulated fuel cell environments, J. Electrochem. Soc., 143, 1225, 1996. 

Generally, the membrane under operation conditions should be considered inside the fuel cell environment. Works on simulation of water management within the whole cell or stack usually utilize a rather simplified picture of the membrane. The complementary objective of the model described in this section is, however, to reveal primarily the effects of water distribution across the membrane. Therefore, appropriate boundary conditions on the anode and cathode sides of the membrane are... 

In spite of the documented, relatively high chemical stability of poly(PFSA) membranes in the fuel-cell environment, recent extensive work looking into the origins of performance loss observed in PEFCs has revealed important mechanisms of degradation that apply to perfluorinated membranes (while being further amplified in nonperfluorinated membranes). An important mechanism of membrane... 

A large diffusion may be found also for composite materials, carbon, or metal based. In the first case different types of polymeric resins (thermoplastics, such as polypropylene, polyethylene, and PVDF, or thermosettings, such as epoxies and phenolics) are filled with carbonaceous powders (graphite or carbon blacks), to provide a material characterized by very high chemical stability in the fuel cell environment and satisfactory properties of electrical conductivity, but which cannot offer sufficient robustness at thickness lower than 2 mm. The metal composite plates are essentially based on combinations (sandwiches of different layers) of stainless steel, porous graphite, and polycarbonates, with the aim to exploit the characteristics of different materials. Their fabrication can be more complex but this is compensated by the possibility to incorporate other functional components, such as manifolds, seals, and cooling layers. 

Develop a low-cost metallic bipolar plate alloy that will form an electrically conductive and corrosion resistant nitride surface layer during thermal nitriding to enable use in a PEM fuel cell environment. 

The need addressed by this project is for a sensor to detect the presence of CO in the H2 produced from hydrocarbon feedstocks in reformers and used to power PEM fuel cells. Low-cost sensors are not available for measuring CO at 1-100 ppm levels in a fuel cell environment. The primary goal of this project is to develop a low-cost microelectronic gas sensor for detecting CO (1-100 ppm) in the fuel stream. The sensors must operate in hydrogen (30-75%), with carbon dioxide (CO2) (15%), CO (0-... 

P.H. Larsen and P.F. James, Chemical stability of Mg0/Ca0/Cr203-Al203-B203-phosphate glasses in solid oxide fuel cell environment. Journal of Materials Science, 33 (1998) 2499-2507. 

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