Proton conduction stability

Fang, J., Guo, X., Harada, S., Watari, T., Tanaka, K., Kita, H. and Okamoto, K. 2002. Novel sulfonated polyimides as polyelectrolytes for fuel cell applications. 1. Synthesis, proton conductivity, and water stability of polyimides from 4,4 -diaminophenyl ether-2,2 -disulfonic acid. Macromolecules 35 9022-9028. 

For instance, the Dow experimental membrane and the recently introduced Hyflon Ion E83 membrane by Solvay-Solexis are "short side chain" (SSC) fluoropolymers, which exhibit increased water uptake, significantly enhanced proton conductivity, and better stability at T > 100°C due to higher glass transition temperatures in comparison to Nafion. The membrane morphology and the basic mechanisms of proton transport are, however, similar for all PFSA ionomers mentioned. The base polymer of Nation, depicted schematically in Figure 6.3, consists of a copolymer of tetrafluoro-ethylene, forming the backbone, and randomly attached pendant side chains of perfluorinated vinyl ethers, terminated by sulfonic acid head groups. °... 

Alberti et al. investigated the influence of relative humidity on proton conductivity and the thermal stability of Nafion 117 and compared their results with data they obtained for sulfonated poly(ether ether ketone) membranes over the broad, high temperature range 80—160 °C and RHs from 35 to 100%. The authors constructed a special cell used in conjunction with an impedance analyzer for this purpose. Data were collected at high temperatures within the context of reducing Pt catalyst CO poison-... 

Hydrated Acidic Polymers. Hydrated acidic polymers are, by far, the most commonly used separator materials for low-temperature fuel cells. Their typical nanoseparation (also see Section 1) leads to the formation of interpenetrating hydrophobic and hydrophilic domains the hydrophobic domain gives the membrane its morphological stability, whereas the hydrated hydrophilic domain facilitates the conduction of protons. Over the past few years, the understanding of the microstructure of these materials has been continuously growing, and this has been crucial for the improved understanding of the mechanism of proton conduction and the observed dependence of the conductivity on solvent (water and methanol) content and temperature. 

Figure 25. Proton conductivity of various oxides, as calculated from data on proton concentrations and mobilities, according to Norby and Larring (the type of dopant is not indicated see ref 187 for source data). The conductivity of oxides with a perovskite-type structure are shown by bold lines, and the conductivity of the oxide ion conductor YSZ (yttria-stabilized zirconia) is shown for comparison, (reproduced with the kind permission of Annual Reviews, http //www.AnnualReviews.org).

The actually developed PEMFCs have a Nafion membrane, which partially fulfills these requirements, since its thermal stability is limited to 100 °C and its proton conductivity decreases strongly at higher temperatures because of its dehydration. On the other hand, it is not completely tight to liquid fuels (such as alcohols). This becomes more important as the membrane is thin (a few tens of micrometers). Furthermore, its actual cost is too high (more than 500 m ), so that its use in a PEMFC for an electric car is not cost competitive. 

It has been reported (4,5) that solid electrolyte sensors using stabilized zirconia can detect reducible gases in ambient atmosphere by making use of an anomalous EMF which is unusually larger than is expected from the Nernst equation. However, these sensors should be operated in a temperature range above ca. 300°C mainly because the ionic conductivity of stabilized zirconia is too small at lower temperatures. On the other hand, solid state proton conductors such as antimonic acid (6,1), zirconium phosphate (8), and dodecamolybdo-phosphoric acid (9) are known to exhibit relatively high protonic conductivities at room temperature. We recently found that the electrochemical cell using these proton conductors could detect... 

Haile, S. M., Staneff, G., and Ryu, K. H. Non-stoichiometry, Grain Boundary Transport and Chemical Stability of Proton Conducting Perovskites, Journal of Materials Science, 36, 1149 (2001). 

In Chapter 10, the use of membranes for different applications are described. One of the possible membranes for hydrogen cleaning is an asymmetric membrane comprised of the dense end of a proton conduction perovskite such as BaCe0 95 Yb0 05O3 5 and a porous end to bring mechanical stability to the membrane. In this case, it is possible to take from the slurry, obtained by the acetate procedure, several drops to be released over a porous ceramic membrane, located in the spinning bar of a spin-coating machine. Thereafter, the assembly powder, thin film porous membrane is heated from room temperature up to 1573 K at a rate of 2K/min, kept at this temperature for 12 h, and then cooled at the same rate in order to get the perovskite end film over the porous membrane [50],... 

Nation ionomers are produced by copolymerization of a perfluorinated vinyl ether comonomer with tetrafluoroethylene resulting in the chemical structure shown in Figure 8.25 [162,166], This polymer and other related polymers consist of perfluorinated, hydrophobic, backbones that give chemical stability to the material. The material also contains sulfonated, hydrophilic, side groups that make hydration possible in the acidic regions, and also allow the transport of protons at low temperatures, since the higher limit of temperature is determined by the humidification of the membrane, since water is a sine qua non for conduction [166], The material exhibits a proton conductivity of 0.1 S/cm at 80°C [162], The membrane performance is then based on the hydrophilic character of the sulfonic acid groups, which allow proton transport when hydrated while the hydrophobic... 

Hydrogen-permselective silica membranes [8,10] can be, as well, synthesized by a particular application of solgel techniques [142,143], Additionally, hydrogen permselective asymmetric membranes composed of a dense ceramic of a proton-conducting perovskite over a porous support have been developed [40], However, some difficulties with respect to their stability is possible in certain reactive environments [121],... 

Figure 2 Properties in polyphosphazenes are determined hy (1) the backbone bonds that control the inherent flexibility of the polymer via their influence on bond torsional freedom, and also provide photo-and thermo-oxidative stahihty (2) the side groups control polymer solubility, reactivity, thermal stability, crystallinity, cross-linking, and (indirectly) polymer flexibility (3) free volume between the side groups affects polymer motion, solvent penetration, membrane behavior, and density (4) functional groups (usually introduced hy secondary reactions) affect soluhihty, biological behavior, proton conduction, cross-hnking, and many other properties...

Polyaniline (PANI) is a class of conductive polymer with good chemical and thermal stability. It contains various benzoid and quinoid fragments in different redox and protonation states linked through N atoms. The ratio of different fragments can be adjusted in a reversible manner by changing the electric potential and acidity for the fine-tuning of its electron and proton conductivities. The electron (hole) conductivity of a PANI material can be as high as -10 S/cm, whereas its proton conductivity can reach up to 10 S/cm . Various PANI materials have been... 

PBI (see chemical structure above) is a hydrocarbon membrane that has been commercially available for decades. Free PBI has a very low proton conductivity ( 10 S/cm) and is not suitable for PEM fuel cell applications. However, the proton conductivity can be greatly improved by doping PBI with acids such as phosphoric, sulfuric, nitric, hydrochloric, and perchloric acids. The PA-doped PBI membrane is the most popular one in PEM fuel cell applications because H3PO4 is a nonoxidative acid with very low vapor pressure at elevated temperature. Savinell et al. and Wainright et al. first demonstrated the use of PBI-PA for HT fuel cells in 1994.270 272 since then, there has been a significant amount of research on the PBI-based membrane because of its low cost and good thermal and chemical stabil-... 

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