High-performance catalyst layers

In contrast to sulfonated materials, novel metal oxide catalysts are also apphcable for sugar hydrolysis. Water-tolerant sohd adds, such as layered HNbMoOg [55, 151], HTaMoOg [54], mesoporous Nb-W oxides [61], andTa-W oxides [62], showed high activity for ceUobiose hydrolysis, a unit of cellulose. The high performance of layered oxides is attributed to facile intercalation of ceUobiose into the interlayer... 

Unfortunately, while catalyst components and structures in low-temperature MEAs have attracted considerable attention, optimization of high-temperature catalyst layer structures and components seems little studied. Lobato et al. [83] investigated the effect of the catalytic ink preparation method on the performance of HT-PEMFCs. They employed two methods for catalyst layer preparation the solution method and the colloid method. In the solution method, catalyst ink was prepared by mixing the catalyst (20% Pt/C) and PBl solution (5% PBl in dimethylacetamide). In the colloid method, acetone was added to the mixture of catalyst and PBI solution, which made the PBI form a colloid suspended in the solvent. They found that electrodes prepared by the solution method showed better performances at 150 °C and 175 °C, and that the electrodes prepared by die colloid method gave a better performance at 125 °C. This is probably due to differences in catalyst layer structure (see Section 18.2.7). 

In the literature, few studies have focused on performance improvement and mitigation of high-temperature catalyst layers. For LT-PEMFCs, materials used in the catalyst layer preparation are commercially available. For HT-PEMFCs, materials are not only different from those in LT-PEMFCs but also differ from study to study. For example, in PBI membrane-based MEAs, Pt/C catalyst and PBI ionomer were used in the catalyst layer [80-83]. However, in a CSH2PO4 membrane-based catalyst layer, no ionomer was used [22]. It is expected that improvement and mitigation of a high-temperature catalyst layer should depend on the materials used, and the catalyst layer structures should be optimized according to the materials employed. 

The replacement of vanadia-based catalysts in the reduction of NOx with ammonia is of interest due to the toxicity of vanadium. Tentative investigations on the use of noble metals in the NO + NH3 reaction have been nicely reviewed by Bosch and Janssen [85], More recently, Seker et al. [86] did not completely succeed on Pt/Al203 with a significant formation of N20 according to the temperature and the water composition. Moreover, 25 ppm S02 has a detrimental effect on the selectivity with selectivity towards the oxidation of NH3 into NO enhanced above 300°C. Supported copper-based catalysts have shown to exhibit excellent activity for NOx abatement. Recently Suarez et al and Blanco et al. [87,88] reported high performances of Cu0/Ni0-Al203 monolithic catalysts with NO/NOz = 1 at low temperature. Different oxidic copper species have been previously identified in those catalytic systems with Cu2+, copper aluminate and CuO species [89], Subsequent additions of Ni2+ in octahedral sites of subsurface layers induce a redistribution of Cu2+ with a surface copper enrichment. Such redistribution... 

Mitsubishi Electric Corporation investigated alloyed catalysts, processes to produce thinner electrolytes, and increases in utilization of the catalyst layer (20). These improvements resulted in an initial atmospheric performance of 0.65 mV at 300 mA/cm or 0.195 W/cm, which is higher than the IFC performance mentioned above (presented in Table 5-2 for comparison). Note that this performance was obtained on small 100 cm cells and may not yet have been demonstrated with full-scale cells in stacks. Approaches to increase life are to use series fuel gas flow in the stack to alleviate corrosion, provide well-balanced micro-pore size reservoirs to avoid electrolyte flooding, and use a high corrosion resistant carbon support for the cathode catalyst. These improvements have resulted in the lowest PAFC degradation rate publicly acknowledged, 2 mV/1000 hours for 10,000 hours at 200 to 250 mA/cm in a short stack with 3600 cm area cells. 

With both approaches, it is key to establish the current regions where samples are under kinetic control to allow the correct comparison. Many reported comparisons of catalysfs in MEA sfrucfures point to differences in performance, which are attributed to intrinsic catalyst differences when it is clear that differences are due to mass fransport effects because of catalyst layer structure. To help overcome these difficulties, it is recommended that, for catalyst evaluation, pure reactants be used (e.g., O2 instead of air) and at relatively high stoichiometries. Use of current-voltage curves should be corrected for elecfrolyte or membrane resistances and Tafel analysis used to identify fhe kinefically confrolled current regions. 

General Motors has assessed the required activity of a catalyst that costs less compared to the current state-of-the-art Pt activity based on these con-straints. i Assuming that the catalyst layer thickness could be increased to MOO pm from the currently used 10 pm, GM has calculated that the minimum volume activity (i.e., Acm ) for a cathode catalyst that costs less should be at least 10% of the current Pt activity. In reality, this seems rather generous, given the recent trend to reduce catalyst layer thicknesses to optimize high-current performances. The DoE has developed a series of volume activity targets for nonprecious metal catalysts, with the 10% of Pt activity target (300 Acm 3 at 0.8 V, H2/O2) necessary by 2015. 

Although the majority of authors who have investigated CNTs as supports for Pt and PtRu particles claim higher activity or performance compared to conventional catalysts, it is not clear why these enhancement arise. It seems unlikely that the CNTs provide any electronic enhancement to Pt(Ru) reactivity, so it is likely that CNTs provide benefits for catalyst layer structure. Part of this may be related to surface area because CNTs can have relatively high surface areas and are often compared to XC72 supported catalysts that have only a moderate surface area ( 250 m g ). Given the current high expense of these materials ( 10 kgr ), further benefits of their use need to be identified before fhey can be practically considered as candidates for fuel cell catalyst supports. 

Although the sputter deposition technique can provide a cheap and directly controlled deposition method, the performance of PEM fuel cells with sputtered CLs is still inferior to that of conventional ink-based fuel cells. In addition, other issues arise related to the physical properties of sputtered catalyst layers, such as low lateral electrical conductivity of the thin metallic films [96,108]. Furthermore, the smaller particle size of sputter-deposited Ft can hinder water transport because of the high resistance to water transport in a thick, dense, sputtered Ft layer [108]. Currently, the sputter deposition method is not considered an economically viable alternative for large-scale electrode fabrication [82] and further research is underway to improve methods. 

The experimental optimization of Nafion ionomer loading within a catalyst layer has attracted widespread attention in the fuel cell community, mainly due to its critical role in dictating the reaction sites and mass transport of reactants and products [15,128-134]. Nafion ionomer is a key component in the CL, helping to increase the three-phase reaction sites and platinum utilization to retain moisture, as well as to prevent membrane dehydration, especially at low current densities. Optimal Nafion content in the electrode is necessary to achieve high performance. 

In order to make catalyst layers with high platinum utilization and better performance, we need to determine how various factors affect Pt utilization. Although this objective has been receiving more attention, we have not achieved a fundamental understanding of the relationships of composition, structure, effective properties, and fuel cell performance—a fact that may limit the optimal design and fabrication of CLs. 

Equations (6.59)-(6.61) represent a highly simplified scheme for evaluating various catalyst layer designs. Refinements of this crude framework for evaluating catalyst layer performance should address all transport limitations, account for water accumulation, and include two- and three-dimensional effects. 

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