Fuel cells surface stability

O2 transport from the atmosphere to the surface of the catalyst present on the electrode surface. All these findings indicate that metallomacrocyclics are still interesting for O2 electroreduction and for possible applications in fuel cells. Longterm stability, which is one of the limiting factors, can be improved dramatically by heat treatment and this is discussed in detail in Chapter 3. 

As electrochemical reaction sites, CLs play an extremely important rote in the performance of fuel cell stacks. A CL mainly consists of catalyst, support and binder. The CL is usually coated on the surface of the GDL. Another method has the CL directly applied to the membrane (catalyst coated membrane, CCM). The selection of the components, the proper ratios of those components, the structure of the formed CL and the formation method of the CL are critical factors in the performance of a fuel cell. The stability of the fuel cell performance is directly related to the stabilities of the catalyst, binder and support in flie CL. Degradation of catalytic activity would be due to the agglomeration of the eatalyst particles and their detachment from the support, the degradation of the binder, and the oxidation and corrosion of the support, particularly at the cathode. Further improvement in CL performance is possible. The basic technical considerations include how to maximize the three-phase interface of the CL, how to stabilize the metal particles on the support, and how to reduce the degradation of the components in the CL. 

The surface characteristics of the plates can have a significant impact on the fuel cell performance, stability, and durability. Both highly hydrophilic and hydrophobic surfaces help water removal from the flow-fields. Liquid water tends to form a thin layer on highly hydrophilic surfaces. This increases the contact area between the gaseous exhaust and the liquid water and thus aids the evaporation and removal of water. On the other hand, when the plate surface is highly hydrophobic, liquid water droplets have a low affinity to the surface, and they can be readily blown out by the gaseous exhaust. 

This reaction is of great technological interest in the area of solid oxide fuel cells (SOFC) since it is catalyzed by the Ni surface of the Ni-stabilized Zr02 cermet used as the anode material in power-producing SOFC units.60,61 The ability of SOFC units to reform methane "internally", i.e. in the anode compartment, permits the direct use of methane or natural gas as the fuel, without a separate external reformer, and thus constitutes a significant advantage of SOFC in relation to low temperature fuel cells. 

For the support material of electro-catalysts in PEMFC, Vulcan XC72(Cabot) has been widely used. This carbon black has been successfully employed for the fuel cell applications for its good electric conductivity and high chemical/physical stability. But higher amount of active metals in the electro-catalysts, compared to the general purpose catalysts, make it difficult to control the metal size and the degree of distribution. This is mainly because of the restricted surface area of Vulcan XC72 carbon black. Thus complex and careM processes are necessary to get well dispersed fine active metal particles[4,5]. 

However, in the case of multimetallic catalysts, the problem of the stability of the surface layer is cmcial. Preferential dissolution of one metal is possible, leading to a modification of the nature and therefore the properties of the electrocatalyst. Changes in the size and crystal structure of nanoparticles are also possible, and should be checked. All these problems of ageing are crucial for applications in fuel cells. 

Second, sensors are often intended for a single use, or for usage over periods of one week or less, and enzymes are capable of excellent performance over these time scales, provided that they are maintained in a nfild environment at moderate temperature and with minimal physical stress. Stabilization of enzymes on conducting surfaces over longer periods of time presents a considerable challenge, since enzymes may be subject to denaturation or inactivation. In addition, the need to feed reactants to the biofuel cell means that convection and therefore viscous shear are often present in working fuel cells. Application of shear to a soft material such as a protein-based film can lead to accelerated degradation due to shear stress [Binyamin and Heller, 1999]. However, enzymes on surfaces have been demonstrated to be stable for several months (see below). 

The choice of immobilization strategy obviously depends on the enzyme, electrode surface, and fuel properties, and on whether a mediator is required, and a wide range of strategies have been employed. Some general examples are represented in Fig. 17.4. Key goals are to stabilize the enzyme under fuel cell operating conditions and to optimize both electron transfer and the efficiency of fuel/oxidant mass transport. Here, we highlight a few approaches that have been particularly useful in electrocatalysis directed towards fuel cell applications. 

A remaining crucial technological milestone to pass for an implanted device remains the stability of the biocatalytic fuel cell, which should be expressed in months or years rather than days or weeks. Recent reports on the use of BOD biocatalytic electrodes in serum have, for example, highlighted instabilities associated with the presence of 02, urate or metal ions [99, 100], and enzyme deactivation in its oxidized state [101]. Strategies to be considered include the use of new biocatalysts with improved thermal properties, or stability towards interferences and inhibitors, the use of nanostructured electrode surfaces and chemical coupling of films to such surfaces, to improve film stability, and the design of redox mediator libraries tailored towards both mediation and immobilization. 

The general requirements for an SOFC anode material include [1-3] good chemical and thermal stability during fuel cell fabrication and operation, high electronic conductivity under fuel cell operating conditions, excellent catalytic activity toward the oxidation of fuels, manageable mismatch in coefficient of thermal expansion (CTE) with adjacent cell components, sufficient mechanical strength and flexibility, ease of fabrication into desired microstructures (e.g., sufficient porosity and surface area), and low cost. Further, ionic conductivity would be beneficial to the extension of... 

A final issue that faces this class of catalysts is stability in the fuel cell environment. Deactivation of materials in a fuel cell environment has been shown to be minimal in some studies,31,137 and severe in others.128,142 More active catalysts seem more susceptible to deactivation. Deactivation has been linked to the formation of peroxide and the loss of metal from the catalyst.128 On the other hand, demetallization has also been observed in pyrolyzed samples that did not lose activity with time.84 Another possible mode of deactivation could be due to the oxidation of the carbon surface. However, it seems reasonable that a complete understanding of the deactivation mechanism would first require a well-developed understanding of the active site. 

A wide range of fhese materials has been investigated for fuel cell use, usually as supports for PfRu particles for DMFC testing (presumably due to the ease of experimenfafion). The fheoretically inerf surfaces of CNTs pose some difficulties for mefal cluster deposition because no sites exist for deposition or stabilization. Therefore, clusters fend to be deposited onto defecf and amorphous portions of samples (see Figure 1.18). 

---