Fuel proton conductivity

The concept of the reversed fuel cell, as shown schematically, consists of two parts. One is the already discussed direct oxidation fuel cell. The other consists of an electrochemical cell consisting of a membrane electrode assembly where the anode comprises Pt/C (or related) catalysts and the cathode, various metal catalysts on carbon. The membrane used is the new proton-conducting PEM-type membrane we developed, which minimizes crossover. 

Polymer Electrolyte Fuel Cell. The electrolyte in a PEFC is an ion-exchange (qv) membrane, a fluorinated sulfonic acid polymer, which is a proton conductor (see Membrane technology). The only Hquid present in this fuel cell is the product water thus corrosion problems are minimal. Water management in the membrane is critical for efficient performance. The fuel cell must operate under conditions where the by-product water does not evaporate faster than it is produced because the membrane must be hydrated to maintain acceptable proton conductivity. Because of the limitation on the operating temperature, usually less than 120°C, H2-rich gas having Htde or no (

Ren, X. Springer, T. E. and Gottesfeld, S. (1998). Direct Methanol Fuel Cell Transport Properties of the Polymer Electrolyte Membrane and Cell Performance. Vol. 98-27. Proc. 2nd International Symposium on Proton Conducting Membrane Euel Cells. Pennington, NJ Electrochemical Society. 

For last few years, extensive studies have been carried out on proton conducting inorganic/organic hybrid membranes prepared by sol-gel process for PEMFC operating with either hydrogen or methanol as a fuel [23]. A major motivation for this intense interest on hybrid membranes is high cost, limitation in cell operation temperature, and methanol cross-... 

S. R. Narayanan, A. Kindler, B. Jeffries-Nakamura, W. Chun, H. Frank, M. Smart, S. Surampudi, and G. Halpert, in Proc. of the First International Symposium on Proton Conducting Membrane Fuel Cells, Ed. by S. Gottesfield, G. Halpert, and A. R. Landgrebe, The Electrochemical Society, Pennington, NJ, PV 95-23, 1995, pp. 261-266. 

Electrolytes for Electrochromic Devices Liquids are generally used as electrolytes in electrochemical research, but they are not well suited for practical devices (such as electrochromic displays, fuel cells, etc.) because of problems with evaporation and leakage. For this reason, solid electrolytes with single-ion conductivity are commonly used (e.g., Nafion membranes with proton conductivity. In contrast to fuel cells in electrochromic devices, current densities are much lower, so for the latter application, a high conductivity value is not a necessary requirement for the electrolyte. 

The PEMFCs require expensive polymer membrane (e.g., Nation ), and operate at a low temperature (e.g., 80°C). Although low temperature reduced the cost of material, the heat generated at low temperatures is more difficult to remove. Alternate proton conducting membranes (e.g., inorganic polymer composites) that will operate at a high temperature (e.g., 200°C) are required. The expensive platinum catalyst used for electrochemical reactions can be poisoned by even trace amounts of carbon monoxide in the hydrogen fuel stream. Hence, a more tolerant catalyst material needs to be developed. 

The main components of a PEM fuel cell are the flow channels, gas diffusion layers, catalyst layers, and the electrolyte membrane. The respective electrodes are attached on opposing sides of the electrolyte membrane. Both electrodes are covered with diffusion layers, and the flow channels/current collectors. The flow channels collect current from the electrodes while providing the fuel or oxidant with access to the electrodes. The gas diffusion layer allows gases to diffuse to the electro-catalysts and provides electrical contact throughout the catalyst layers. Within the anode catalyst layer, the fuel (typically H2) is oxidized to produce electrons and protons. The electrons travel through an external circuit to produce electricity, while the protons pass through the proton conducting electrolyte membrane. Within the cathode catalyst layer, the electrons and protons recombine with the oxidant (usually 02) to produce water. 

PEM Proton-exchange-membrane fuel cell (Polymer-electrolyte-membrane fuel cell) Proton- conducting polymer membrane (e.g., Nafion ) H+ (proton) 50-80 mW (Laptop) 50 kW (Ballard) modular up to 200 kW 25-=45% Immediate Road vehicles, stationary electricity generation, heat and electricity co-generation, submarines, space travel... 

Direct-methanol fuel cell Proton- conducting polymer membrane H+ (proton) 80-100... 

The effect of annealing temperatures (65 - 250 °C) and blend composition of Nafion 117, solution-cast Nafion , poly(vinyl alcohol) (PVA) and Nafion /PVAblend membranes for application to the direct methanol fuel cell is reported in [148], These authors have found that a Nafion /PVAblend membrane at 5 wt% PVA (annealed at 230 °C) show a similar proton conductivity of that found to Nafion 117, but with a three times lower methanol permeability compared to Nafion 117. They also found that for Nafion /PVA (50 wt% PVA) blend membranes, the methanol permeability decreases by approximately one order of magnitude, whilst the proton conductivity remained relatively constant, with increasing annealing temperature. The Nafion /PVA blend membrane at 5 wt% PVA and 230 °C annealing temperature had a similar proton conductivity, but three times lower methanol permeability compared to unannealed Nafion 117 (benchmark in PEM fuel cells). 

A.R. Landgrebe, S. Gottesfeld, First International Symposium on Proton Conducting Membrane Fuel Cells, Chicago, h. Proceedings Vol. 95-23, The Electrochemical Society, Inc., Pennington, N.J., 1995. 

To overcome these disadvantages, a thin-film CL technique was invented, which remains the most commonly used method in PEM fuel cells. Thin-film catalyst layers were initially used in the early 1990s by Los Alamos National Laboratory [6], Ballard, and Johnson-Matthey [7,8]. A thin-film catalyst layer is prepared from catalyst ink, consisting of uniformly distributed ionomer and catalyst. In these thin-film catalyst layers, the binding material is not PTFE but rather hydrophilic Nafion ionomer, which also provides proton conductive paths for the electrochemical reactions. It has been found that the presence of hydrophobic PTFE in thin catalyst layers was not beneficial to fuel cell performance [9]. 

Typically, Nation ionomer is the predominant additive in the catalyst layer. However, other types of CLs with various hygroscopic or proton conductor additives have also been developed for fuel cells operafed xmder low relative humidity (RH) and/or at elevated temperatures. Many studies have reported the use of hygroscopic y-Al203 [52] and silica [53,54] in the CE to improve the water retention capacity and make such CEs viable for operation af lower relative humidity and/or elevated temperature. Alternatively, proton conducting materials such as ZrP [55] or heteropoly acid HEA [56] have also been added... 

The fabrication of catalyst layers for PEM fuel cells involves maintaining a delicate balance between gas and water transport, and electron and proton conduction. The process of CL fabrication should be guided by both fuel cell performance and cost reduction. 

The catalyst layer is composed of multiple components, primarily Nafion ion-omer and carbon-supported catalyst particles. The composition governs the macro- and mesostructures of the CL, which in turn have a significant influence on the effective properties of the CL and consequently the overall fuel cell performance. There is a trade-off between ionomer and catalyst loadings for optimum performance. For example, increased Nafion ionomer confenf can improve proton conduction, but the porous channels for reactanf gas fransfer and water removal are reduced. On the other hand, increased Pt loading can enhance the electrochemical reaction rate, and also increase the catalyst layer thickness. 

Kreuer, K. D. 2001. On the development of proton conducting membranes for hydrogen and methanol fuel cells. Journal of Membrane Science 185 29-39. 

Aleksandrova, E., Hiesgen, R., Eberhard, D., Friedrich, K. A., Kaz, T. and Roduner, E. 2007. Proton conductivity study of a fuel cell membrane with nanoscale resolution. ChemPhysChem 8 519-522. 

Hiibner, G. and Roduner, E. 1999. EPR investigation of HO radical initiated degradation reactions of sulfonated aromatics as model compounds for fuel cell proton conducting membranes. Journal of Materials Chemistry 9 409- 18. 

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. 

Asano, N., Aoki, M., Suzuki, S., Miyatake, K., Uchida, H. and Watanabe, M. 2006. Aliphatic/aromatic polyimide ionomers as a proton conductive membrane for fuel cell applications. Journal of the American Chemical Society 128 1762-1769. 

Jeske, M., Soltmann, C., Ellenberg, C., Wilhelm, M., Koch, D. and Grathwohl, G. 2007. Proton conducting membranes for the high temperature-polymer electrolyte membrane-fuel cell (HT-PEMFC) based on functionalized polysiloxanes. 

Lavorgna, M., Mensitieri, G., Scherillo, G., Shaw, M. T., Swier, S. and Weiss, R. A. 2007. Polymer blend for fuel cells based on SPEKK Effect of cocontinuous morphology on water sorption and proton conductivity. Journal of Polymer Science Part B Polymer Physics 45 395-404. 

Miyake, N., Wainright, J. S. and Savinell, R. E 2001. Evaluation of a sol-gel derived Nafion/silica hybrid membrane for proton electrolyte membrane fuel cell applications. I. Proton conductivity and water content. Journal of the Electrochemical Society 148 A898-A904. 

Kreuer, K. D. 2005. Proton conduction in fuel cells. In Hydrogen transfer reactions, ed. J. T. Hynes, J. P. Klinman, H. H. Limbach and R. L. Schowen, 709-736. Weinheim, Germany Wiley-VCH. 

Allcock, H. R., Hofmann, M. A., Ambler, C. M., Lvov, S. N., Zhou, X. Y., Chalkova, E. and Weston, J. 2002. Phenyl phosphonic functionalized poly(aryloxyphosphanes) as proton-conducting membranes for direct methanol fuel cells. Journal of Membrane Science 201 47-54. 

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