Materials 159 Direct methanol fuel cell

Lasch K, Hayn G, Jdrissen L, Garche J, Besenhardt O (2002) Mixed conducting catalyst support materials for the direct methanol fuel cell. J Power Sources 105 305-310... 

The Pt/Ru catalyst is the material of choice for the direct methanol fuel cell (DMFC) (and hydrogen reformate) fuel cell anodes, and its catalytic function needs to be completely understood. In the hrst approximation, as is now widely acknowledged, methanol decomposes on Pt sites of the Pt/Ru surface, producing chemisorbed CO that is transferred via surface motions to the active Pt/Ru sites to become oxidized to CO2... 

Despite the uncertainty regarding the exact nature of the active site for oxygen reduction, researchers have managed to produce catalysts based on heat-treated macrocycles with comparable activities to state-of-the-art platinum catalysts. In numerous cases researchers have shown activity close to or better than platinum catalysts.64,71,73,103,109 Since the active site for the ORR in these materials is not fully understood, there is still potential for breakthrough in their development. Another advantage of this class of materials that should be mentioned is their inactivity for methanol oxidation, which makes them better suited than platinum for use in direct methanol fuel cell cathodes where methanol crossover to the cathode can occur.68,102,104,122-124 While the long-term activity of heat treated materials is... 

K. Scott, W. M. Taama, and P. Argyropoulos. Material aspects of the liquid feed direct methanol fuel cell. Journal of Applied Electrochemistry 28 (1998) 1389-1397. 

Collins, J.A. 2001. Development of electrocatalyst materials for direct methanol fuel cells. Energy Marie Curie fellowship Conference, Profactor GmbH, Steyr, Austria, 16-19 May 2001. 

Polyphosphazene-based PEMs are potentially attractive materials for both hydrogen/air and direct methanol fuel cells because of their reported chemical and thermal stability and due to the ease of chemically attaching various side chains for ion exchange sites and polymer cross-linking onto the — P=N— polymer backbone. Polyphosphazenes were explored originally for use as elastomers and later as solvent-free solid polymer electrolytes in lithium batteries, and subsequently for proton exchange membranes. 

Allcock et al. also have investigated the use of phosphonated polyphosphazenes as potential membrane materials for use in direct methanol fuel cells (Figure A2) Membranes were found to have lEC values between 1.17 and 1.43 mequiv/g and proton conductivities between 10 and 10 S/cm. Methanol diffusion coefficients for these membranes were found to be at least 12 times lower than that for Nafion 117 and 6 times lower than that for a cross-linked sulfonated polyphosphazene membrane. 

The purpose of the present review is to summarize the current status of fundamental models for fuel cell engineering and indicate where this burgeoning field is heading. By choice, this review is limited to hydrogen/air polymer electrolyte fuel cells (PEFCs), direct methanol fuel cells (DMFCs), and solid oxide fuel cells (SOFCs). Also, the review does not include microscopic, first-principle modeling of fuel cell materials, such as proton conducting membranes and catalyst surfaces. For good overviews of the latter fields, the reader can turn to Kreuer, Paddison, and Koper, for example. 

There is increased interest in the use of Ru-based systems as catalysts for oxygen reduction in acidic media, because these systems have potential applications in practicable direct methanol fuel cell systems. The thermolysis of Ru3(CO)i2 has been studied to tailor the preparation of such materials [123-125]. The decarbon-ylation of carbon-supported catalysts prepared from Ru3(CO)i2 and W(CO)6, Mo(CO)is or Rh(CO)is in the presence of selenium has allowed the preparation of catalysts with enhanced activity towards oxygen reduction, when compared with the monometallic ruthenium-based catalyst [126],... 

Strasser, P., Gorer, S., Devenney, M., Electrochemical techniques for the discovery of new fuel-cell cathode materials. In Direct Methanol Fuel Cells, Vol. 4, Narayanan, S.G., Zawodzinski, T. (eds.), The Electrochemical Society Washington, 2001, p 191. 

Reddington et al. (66) reported the synthesis and screening of a 645-member discrete materials library L9 as a source of catalysts for the anode catalysis of direct methanol fuel cells (DMFCs), with the relevant goal of improving their properties as fuel cells for vehicles and other applications. The anode oxidation in DMFCs is reported in equation 1 (Fig. 11.12). At the time of the publication, state-of-the-art anode catalysts were either binary Pt-Ru alloys (67) or ternary Pt-Ru-Os alloys (68). A systematic exploration of ternary or higher order alloys as anode catalysts for DMFCs was not available, and predictive models to orient the efforts were also lacking. 

In this section, recent advances in the field of polymer electrolyte direct methanol fuel cells, i.e., PEFCs based on direct anodic oxidation of methanol are discussed. A schematic of such a ceU is shown in Fig. 48, together with the processes that take place in the cell. The DMFC has many facets, electrocatalysis materials and components which deserve a detailed treatment. The discussion here will be confined, however, to the very significant performance enhancement demostrated recently with polymer electrolyte DMFCs, and, as a result, to possible consideration of DMFCs as a nearer term technology. 

Zhong and co-workers [530] described recent results of an investigation of the electrocatal3dic oxidation of methanol using carbon-supported An and Au-Pt nanoparticle catalysts. The exploration of the bimetallic composition on carbon black support was aimed at modifying the catalytic properties for the methanol oxidation reaction at the anode in direct methanol fuel cells (DMFCs). An and Au-Pt nanoparticles of 2-3 nm sizes encapsulated in an organic monolayer were prepared, assembled on carbon black materials and treated thermally. The results have revealed that these Au-Pt nanoparticles catalysts are potentially viable candidates for use in fuel cells under a number of conditions [530],... 

The membrane shown in Fig. 4.10 was prepared using this three-dimensionally ordered macroporous polyimide obtained according to the above process with AMPS polymer. The proton conductivity and methanol permeability of the composite membrane are summarized in Table 4.2. The proton conductivity of the composite membrane was higher than that of Nafion and the methanol permeability of the composite membrane was slightly lower than that of Nafion . Both tendencies are good for membrane for direct methanol fuel cell. In this way, three-dimensionally ordered macroporous materials are suitable for matrix of soft proton conductive polymer with higher proton conductivity. 

MRS Spring Meeting, San Francisco, CA, April 2, 2002. Title System and Material Issues in Direct Methanol Fuel Cells B. S. Pivovar... 

In a fiirther series of experiments, phosphotungstic acid (PWA) was impregnated onto silica particles and the resulting material was loaded in the recast Nafion. As is well known, heteropolyacids (HPAs) have demonstrated suitable characteristics to be used as proton conductive materials in fuel cells [4-6]. Due to dissolution phenomena in water, however, previous experiments using solid heteropolyacid did not result in stable fuel cell performance [5]. To overcome this problem, resulting in a short lifetime of the fuel cell, experiments of blocking the HPA in a host material were carried out [7-9]. Thus, in this work the phosphotungstic acid-modified membrane was compared, in terms of performance, with the bare silica-recast Nafion membrane in direct methanol fuel cell at 145°C. 

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