Catalyst/polymer electrolyte

Pt/Ru Catalyst Polymer Pt Catalyst Porous Gas Layer Electrolyte Layer Diffusion Membrane Electrode... 

As can be seen from Eigure 11b, the output voltage of a fuel cell decreases as the electrical load is increased. The theoretical polarization voltage of 1.23 V/cell (at no load) is not actually realized owing to various losses. Typically, soHd polymer electrolyte fuel cells operate at 0.75 V/cell under peak load conditions or at about a 60% efficiency. The efficiency of a fuel cell is a function of such variables as catalyst material, operating temperature, reactant pressure, and current density. At low current densities efficiencies as high as 75% are achievable. 

The concept of a promoter can also be extended to the case of substances which enhance the performance of an electrocatalyst by accelerating the rate of an electrocatalytic reaction. This can be quite important for the performance, e.g., of low temperature (polymer electrolyte membrane, PEM) fuel cells where poisoning of the anodic Pt electrocatalyst (reaction 1.7) by trace amounts of strongly adsorbed CO poses a serious problem. Such a promoter which when added to the Pt electrocatalyst would accelerate the desired reaction (1.5 or 1.7) could be termed an electrocatalytic promoter, or electropromoter, but this concept will not be dealt with in the present book, where the term promoter will always be used for substances which enhance the performance of a catalyst. 

The experimental setup is shown in Figure 9.23. The Pt-black catalyst film also served as the working electrode in a Nafion 117 solid polymer electrolyte cell. The Pt-covered side of the Nafion 117 membrane was exposed to the flowing H2-02 mixture and the other side was in contact with a 0.1 M KOH aqueous solution with an immersed Pt counterelectrode. The Pt catalyst-working electrode potential, Urhe (=Uwr)> was measured with respect to a reversible reference H2 electrode (RHE) via a Luggin capillary in contact with the Pt-free side of the Nafion membrane. 

Electro-catalysts which have various metal contents have been applied to the polymer electrolyte membrane fuel cell(PEMFC). For the PEMFCs, Pt based noble metals have been widely used. In case the pure hydrogen is supplied as anode fuel, the platinum only electrocatalysts show the best activity in PEMFC. But the severe activity degradation can occur even by ppm level CO containing fuels, i.e. hydrocarbon reformates[l-3]. To enhance the resistivity to the CO poison of electro-catalysts, various kinds of alloy catalysts have been suggested. Among them, Pt-Ru alloy catalyst has been considered one of the best catalyst in the aspect of CO tolerance[l-3]. 

Design parameters of the anode catalyst for the polymer electrolyte membrane fiiel cells were investigated in the aspect of active metal size and inter-metal distances. Various kinds of catalysts were prepared by using pretreated Ketjenblacks as support materials. The prepared electro-catalysts have the morphology such as the sizes of active metal are in the range from 2.0 to 2.8nm and the inter-metal distances are 5.0 to 14.2nm. The electro-catalysts were evaluated as an electrode of PEMFC. In Fig. 1, it looked as if there was a correlation between inter-metal distances and cell performance, i.e. the larger inter-metal distances are related to the inferior cell performance. 

We have already referred to the Mo/Ru/S Chevrel phases and related catalysts which have long been under investigation for their oxygen reduction properties. Reeve et al. [19] evaluated the methanol tolerance, along with oxygen reduction activity, of a range of transition metal sulfide electrocatalysts, in a liquid-feed solid-polymer-electrolyte DMFC. The catalysts were prepared in high surface area by direct synthesis onto various surface-functionalized carbon blacks. The intrinsic... 

Dodolet JP, Cote R, Faubert G, Denes G, Guay D, Bertrand P (1998) Iron catalysts prepared by high-temperature pyrolysis of tetraphenylporphyrins adsorbed on carbon black for oxygen reduction in polymer electrolyte fuel cells. Electrochim Acta 43 341-353... 

Incorporation into a Polymer Layer In recent years a new electrode type is investigated which represents a layer of conducting polymer (such as polyaniline) into which a metal catalyst is incorporated by chemical or electrochemical deposition. In some cases the specific catalytic activity of the platinum crystallites incorporated into the polymer layer was found to be higher than that of ordinary dispersed platinum, probably because of special structural features of the platinum crystallites produced within the polymer matrix. A variant of this approach is that of incorporating the disperse catalyst directly into the surface layer of a solid polymer electrolyte. 

Polymer electrolyte fuel cells (PEFCs) have attracted great interest as a primary power source for electric vehicles or residential co-generation systems. However, both the anode and cathode of PEFCs usually require platinum or its alloys as the catalyst, which have high activity at low operating temperatures (<100 °C). For large-scale commercialization, it is very important to reduce the amount of Pt used in fuel cells for reasons of cost and limited supply. 

Neergat N, Sbukla AK, Gandhi KS. 2001. Platinum-based alloys as oxygen-reduction catalysts for solid-polymer-electrolyte direct methanol fuel cells. J Appl Electrochem 31 373-378. 

Watanabe M, Igarashi H, Fujino T. 1999. Design of CO tolerant anode catalysts for polymer electrolyte fuel cell. Electrochemistry 67 1194-1196. 

Behm RJ, Jusys Z. 2006. The potential of model studies for the understanding of catalyst poisoning and temperature effects in polymer electrolyte fuel cell reaction. J Power Sources 154 327-342. 

Diemant T, Hager T, Hosier HE, Rauscher H, Behm RJ. 2003. Hydrogen adsorption and coadsorption with CO on well-defined himetallic PtRu surfaces—A model study on the CO tolerance of himetallic PtRu anode catalysts in low temperature polymer electrolyte fuel cells. Surf Sci 541 137. 

Paulus UA, Veziridis V, Schnyder B, Kuhnke M, Scherer GG, Wokaun A. 2003. Fundamental investigation of catalyst utilization at the electrode/solid polymer electrolyte interface. Part I. Development of a model system. J Electroanal Chem 541 77-91. 

In the following chapter examples of XPS investigations of practical electrode materials will be presented. Most of these examples originate from research on advanced solid polymer electrolyte cells performed in the author s laboratory concerning the performance of Ru/Ir mixed oxide anode and cathode catalysts for 02 and H2 evolution. In addition the application of XPS investigations in other important fields of electrochemistry like metal underpotential deposition on Pt and oxide formation on noble metals will be discussed. 

Muhamad, E.N., Takeguchi, T., Wang, G., Anzai, Y., and Ueda, W. (2009) Electrochemical characteristics of Pd anode catalyst modified with Ti02 nanoparticles in polymer electrolyte fuel cell. Journal of the Electrochemical Society, 156 (1), B32-B37. 

Wilson, M. S. and Gottesfeld, S., Thin film catalyst layers for polymer electrolyte fuel cell electrodes, J. Appl. Electrochem., 22, 1, 1992. 

Carbon is unique among chemical elements since it exists in different forms and microtextures transforming it into a very attractive material that is widely used in a broad range of electrochemical applications. Carbon exists in various allotropic forms due to its valency, with the most well-known being carbon black, diamond, fullerenes, graphene and carbon nanotubes. This review is divided into four sections. In the first two sections the structure, electronic and electrochemical properties of carbon are presented along with their applications. The last two sections deal with the use of carbon in polymer electrolyte fuel cells (PEFCs) as catalyst support and oxygen reduction reaction (ORR) electrocatalyst. 

There has been an accelerated interest in polymer electrolyte fuel cells within the last few years, which has led to improvements in both cost and performance. Development has reached the point where motive power applications appear achievable at an acceptable cost for commercial markets. Noticeable accomplishments in the technology, which have been published, have been made at Ballard Power Systems. PEFC operation at ambient pressure has been validated for over 25,000 hours with a six-cell stack without forced air flow, humidification, or active cooling (17). Complete fuel cell systems have been demonstrated for a number of transportation applications including public transit buses and passenger automobiles. Recent development has focused on cost reduction and high volume manufacture for the catalyst, membranes, and bipolar plates. 

A. LaConti, G. Smarz, F. Sribnik, "New Membrane-Catalyst for Solid Polymer Electrolyte Systems," Final Report prepared by Electro-Chem Products, Hamilton Standard for Los Alamos National Laboratory under Contract No. 9-X53-D6272-1, 1986. 

Antoine et al. [28] inveshgated the gradient across the CL and found that the Pt utilization was dependent on the CL porosity. In a nonporous CL, catalyst utilization was increased through the preferential locahon of Pt close to the gas diffusion layer in a porous CL, catalyst utilization efficiency was increased through the preferential location of Pt close to the polymer electrolyte membrane. In PEM fuel cells, fhe CL has a porous structure, and better performance is expected if higher Pf loading is used af preferential locahons close to the membrane/catalyst layer interface. 

Numerous efforfs have been made to improve existing fhin-film catalysts in order to prepare a CL with low Pt loading and high Pt utilization without sacrificing electiode performance. In fhin-film CL fabrication, fhe most common method is to prepare catalyst ink by mixing the Pt/C agglomerates with a solubilized polymer electrolyte such as Nation ionomer and then to apply this ink on a porous support or membrane using various methods. In this case, the CL always contains some inactive catalyst sites not available for fuel cell reactions because the electrochemical reaction is located only at the interface between the polymer electrolyte and the Pt catalyst where there is reactant access. 

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