Catalyst layer operation performance

This section provides a comprehensive overview of recent efforts in physical theory, molecular modeling, and performance modeling of CLs in PEFCs. Our major focus will be on state-of-the-art CLs that contain Pt nanoparticle electrocatalysts, a porous carbonaceous substrate, and an embedded network of interconnected ionomer domains as the main constituents. The section starts with a general discussion of structure and processes in catalyst layers and how they transpire in the evaluation of performance. Thereafter, aspects related to self-organization phenomena in catalyst layer inks during fabrication will be discussed. These phenomena determine the effective properties for transport and electrocatalytic activity. Finally, physical models of catalyst layer operation will be reviewed that relate structure, processes, and operating conditions to performance. 

At macroscopic level, the overall relations between structure and performance are strongly affected by the formation of liquid water. Solution of such a model that accounts for these effects provides full relations among structure, properties, and performance, which in turn allow predicting architectures of materials and operating conditions that optimize fuel cell operation. For stationary operation at the macroscopic device level, one can establish material balance equations on the basis of fundamental conservation laws. The general ingredients of a so-called "macrohomogeneous model" of catalyst layer operation include ... 

At high anodic overpotentials, methanol oxidation reaction exhibits strongly non-Tafel behavior owing to finite and potential-independent rate of methanol adsorption on catalyst surface [244]. The equations of Section 8.2.3 can be modified to take into account the non-Tafel kinetics of methanol oxidation. The results reveal an interesting regime of the anode catalyst layer operation featuring a variable thickness of the current-generating domain [245]. The experimental verification of this effect, however, has not yet been performed. 

There is more to catalyst layer operation than electrocatalysis, a lot more The design of fuel cell electrodes with high performance, long lifetime, and low cost is about embedding the catalyst, usually the most expensive and least stable material in the cell, into a porous composite host medium. It turns out that material selection and structural design of the host medium is as important as that of the catalyst material itself. 

The two-step strategy in the physical modeling of catalyst layer operation is depicted in Figure 3.5. The first step relates structure to the physical properties of the layer, considered as an effective medium. The second step relates these effective properties to electrochemical performance. Relations between structure and performance are complicated by the formation of liquid water, affecting effective properties and performance. Solutions for such a model provide relations between structure, properties, and performance. These relations allow predictions of architectures of materials and operating conditions that optimize catalyst layer and fuel cell operation to be made. 

This chapter is devoted entirely to performance models of conventional catalyst layers (type I electrodes), which rely on reactant supply by gas diffusion. It introduces the general modeling framework and employs it to discuss the basic principles of catalyst layer operation. Structure-based models of CCL rationalize distinct regimes of performance, which are discernible in polarization curves. If provided with basic input data on structure and properties, catalyst layer models reproduce PEFC polarization curves. Consistency between model predictions and experimental data will be evaluated. Beyond polarization curves, performance models provide detailed maps or shapes of reaction rate distributions. In this way, the model-based analysis allows vital conclusions about an optimal design of catalyst layers with maximal catalyst utilization and minimal transport losses to be drawn. 

The transient response of DMFC is inherently slower and consequently the performance is worse than that of the hydrogen fuel cell, since the electrochemical oxidation kinetics of methanol are inherently slower due to intermediates formed during methanol oxidation [3]. Since the methanol solution should penetrate a diffusion layer toward the anode catalyst layer for oxidation, it is inevitable for the DMFC to experience the hi mass transport resistance. The carbon dioxide produced as the result of the oxidation reaction of methanol could also partly block the narrow flow path to be more difScult for the methanol to diflhise toward the catalyst. All these resistances and limitations can alter the cell characteristics and the power output when the cell is operated under variable load conditions. Especially when the DMFC stack is considered, the fluid dynamics inside the fuel cell stack is more complicated and so the transient stack performance could be more dependent of the variable load conditions. 

One of the critical issues with regard to low temperamre fuel cells is the gradual loss of performance due to the degradation of the cathode catalyst layer under the harsh operating conditions, which mainly consist of two aspects electrochemical surface area (ECA) loss of the carbon-supported Pt nanoparticles and corrosion of the carbon support itself. Extensive studies of cathode catalyst layer degradation in phosphoric acid fuel cells (PAECs) have shown that ECA loss is mainly caused by three mechanisms ... 

In addition to Nafion-based catalyst layers, additional types have been developed, including CLs with different ion exchange capacities (lECs) [57,58] or with other hydrocarbon-type ionomers such as sulfonated poly(ether ether ketone) [58-60], sulfonated polysulfone [61,62], sulfonated polyether ionomers [63], and borosiloxane electrolytes [64], as well as sulfonated polyimide [65]. These nonfluorinated polymer materials have been targeted to reduce cost and/or increase operating temperature. Unfortunately, such CLs still encounter problems with low Pt utilization, flooding, and inferior performance compared wifh convenfional Nafion-based CLs. 

Separation of the individual contributors can provide useful information about performance optimization for fuel cells, helping to optimize MEA components, including catalyst layers (e.g., catalyst loading, Nafion content, and PTFE content), gas diffusion layers, and membranes. It assists in the down-selection of catalysts, composite structure, and MEA fabrication methods. It also helps in selecting the most appropriate operating conditions, including humidification, temperature, back-pressure, and reactant flow rates. 

To increase fundamental knowledge about ionic resistance, it is important to develop a methodology to experimentally isolate the contributions of the various cell components. Electrochemical impedance spectroscopy has been widely used by Pickup s research group to study the capacitance and ion conductivity of fuel cell catalyst layers [24-27] they performed impedance experiments under a nitrogen atmosphere, which simplified the impedance response of the electrode. Saab et al. [28] also presented a method to extract ohmic resistance, CL electrolyte resistance, and double-layer capacitance from impedance spectra using both the H2/02 and H2/N2 feed gases. In this section, we will focus on the work by Pickup et al. on using EIS to obtain ionic conductivity information from operational catalyst layers. 

Figure 3.51. Single PEM fuel cell performance. Current-voltage relationship (open symbols) and implied power density (filled symbols), are shown for different operational temperatures in the range of 45-90°C, for a cell with a catalyst layer with incorporated PTFE (polytetrafluoroethene) to reduce water flooding, a low loading of a carbon-supported Pt catalyst layer (120 pg Pt cm ) and finally Nation intrusions. (From Z. Qi and A. Kaufman (2003). Low Pt loading high performance cathodes for PEM fuel cells. /. Power Sources 113,37-43. Used with permission from Elsevier.)...

In some earlier life tests performed by Wilson and co-workers, PEFCs utilizing thin-film platinum catalyst layers typically experienced a gradual performance loss over the first 500 to 1000 h of operation and then stabilized at about 70% of the original performance (here, performance is described in terms of the current density measured at 0.50 V, i.e., close to the maximum power output of the cell). In such life tests. 

The high theoretical efficiency of a fuel cell is substantially reduced by the finite rate of dynamic processes at various locations in the cell. Substantial efficiency losses at typical operating temperatures occur already in the anodic and cathodic catalyst layers due to the low intrinsic reaction rates of the oxygen reduction and, in the case of the DMFC, of the methanol oxidation reaction. (The catalytic oxidation of hydrogen with platinum catalysts is very fast and thus does not limit PEFC performance.) In addition, at low temperatures, turnover may be limited by noble metal catalyst poisoning due to sulfur... 

Optimum thickness. At fixed composition a phase diagram of the catalyst layer can be generated, which establishes a relation between the optimum thickness interval of the catalyst layer and the target current density jo (or jo interval) of fuel cell operation. The optimum compromise between kinetic losses and mass transport losses is realized in the intermediate regime. The existence of an upper limit on the thickness beyond which the performance would start to deteriorate is due to the concerted impact of oxygen and proton transport limitations, whereas considered separately each of the effects would only serve to define a minimal thickness. 

Physically, the reason for the dramatic difference between performances of cathode and anode active layers is the exchange current density ia at the anode the latter is 10 orders of magnitude higher than at the cathode [6]. Due to the large ia, the electrode potential r]a is small. The anode of PEFC, hence, operates in the linear regime, when both exponential terms in the Butler-Volmer equation can be expanded [178]. This leads to exponential variation of rja across the catalyst layer with the characteristic length (in the exponent)... 

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