Polymer catalyst layers

Thin catalyst layers on a GC rotating disk electrode (RDE) or a rotating ring-disk electrode (RRDE) serve for studies of ORR kinetics. In order to separate the kinetic current from the measured current j, Schmidt and co-workers [Schmidt et al., 1998b] corrected the latter for the influence of oxygen diffusion in the aqueous electrolyte and in the polymer film using the foUowing equation ... 

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

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. 

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. 

Xie, Z., Navessin, T, Shi, K., Chow, R., Wang, Q., Song, D., Andreaus, B., Eikerling, M., Liu, Z., and Holdcroft, S. Eunctionally graded cathode catalyst layers for polymer electrolyte fuel cells. Journal of the Electrochemical Society 2005 152 A1171-A1179. 

Kamarajugadda, S., and Mazumder, S. Numerical investigation of the effect of cathode catalyst layer structure and composition on polymer electrolyte membrane fuel cell performance. Journal of Power Sources 2008 183 629-642. Krishnan, L., Morris, E. A., and Eisman, G. A. Pt black polymer electrolyte-based membrane-based electrode revisited. Journal of the Electrochemical Society 2008 155 B869-B876. 

Cheng, X., Yi, B., Han, M., Zhang, J., Qiao, Y., and Yu, J. Investigation of platinum utilization and morphology in catalyst layer of polymer electrolyte fuel cells. Journal of Power Sources 1999 79 75-81. 

Kamarajugadda, S., and Mazumder, S. Numerical investigation of the effect of cathode catalyst layer structure and composition on polymer electrolyte membrane fuel cell performance. Journal of Power Sources 2008 183 629-642. 

Wang, G., Mukherjee, P P, and Wang, C. Y. Optimization of polymer electrolyte fuel cell cathode catalyst layers via direct numerical simulation modeling. Electrochimica Acta 2007 52 6367-6377. 

Passalacqua, E., Lufrano, F., Squadrito, G., Patti, A., and Giorgi, L. Nafion content in the catalyst layer of polymer electrolyte fuel cells Effects on structure and performance. Electrochimica Acta 2001 46 799-805. 

Figure 4.1 shows a schematic of a typical polymer electrolyte membrane fuel cell (PEMFC). A typical membrane electrode assembly (MEA) consists of a proton exchange membrane that is in contact with a cathode catalyst layer (CL) on one side and an anode CL on the other side they are sandwiched together between two diffusion layers (DLs). These layers are usually treated (coated) with a hydrophobic agent such as polytetrafluoroethylene (PTFE) in order to improve the water removal within the DL and the fuel cell. It is also common to have a catalyst-backing layer or microporous layer (MPL) between the CL and DL. Usually, bipolar plates with flow field (FF) channels are located on each side of the MFA in order to transport reactants to the... 

This chapter gives an overview of the state of affairs in physical theory and molecular modeling of materials for PEECs. The scope encompasses systems suitable for operation at T < 100°C that contain aqueous-based, proton-conducting polymer membranes and catalyst layers based on nanoparticles of Pt. 

The materials of greatest interest in view of fundamental understanding and design are the polymer electrolyte membrane and the catalyst layers. They fulfill key functions in the cell and at the same time offer the most compelling opportunities for innovation through design and integration of advanced materials. 

Diffusion medium properties for the PEFC system were most recently reviewed by Mathias et al. The primary purpose of a diffusion medium or gas diffusion layer (GDL) is to provide lateral current collection from the catalyst layer to the current collecting lands as well as uniform gas distribution to the catalyst layer through diffusion. It must also facilitate the transport of water out of the catalyst layer. The latter function is usually fulfilled by adding a coating of hydrophobic polymer such as poly(tet-rafluoroethylene) (PTFE) to the GDL. The hydrophobic polymer allows the excess water in the cathode catalyst layer to be expelled from the cell by gas flow in the channels, thereby alleviating flooding. It is known that the electric conductivity of GDL is... 

Divisek et al. presented a similar two-phase, two-dimensional model of DMFC. Two-phase flow and capillary effects in backing layers were considered using a quantitatively different but qualitatively similar function of capillary pressure vs liquid saturation. In practice, this capillary pressure function must be experimentally obtained for realistic DMFC backing materials in a methanol solution. Note that methanol in the anode solution significantly alters the interfacial tension characteristics. In addition, Divisek et al. developed detailed, multistep reaction models for both ORR and methanol oxidation as well as used the Stefan—Maxwell formulation for gas diffusion. Murgia et al. described a one-dimensional, two-phase, multicomponent steady-state model based on phenomenological transport equations for the catalyst layer, diffusion layer, and polymer membrane for a liquid-feed DMFC. 

The anode layer of polymer electrolyte membrane fuel cells typically includes a catalyst and a binder, often a dispersion of poly(tetraflu-oroethylene) or other hydrophobic polymers, and may also include a filler, e.g., acetylene black carbon. Anode layers may also contain a mixture of a catalyst, ionomer and binder. The presence of a ionomer in the catalyst layer effectively increases the electrochemically active surface area of the catalyst, which requires a ionically conductive pathway to the cathode catalyst to generate electric current (16). 

Figure 13.9 Schematic diagram of a polymer electrolyte fuel cell (A) gas manifolding, (B) porous graphite block, (C) active catalyst layer (dispersed Pt and Teflon binder), and (D) polymer electrolyte.

Water content affects many processes within a fuel cell and must be properly managed. Proton conductivity within the polymer electrolyte typically decreases dramatically with decreasing water content (especially for perfhiorinated membranes such as Nation ), while excessive liquid water in the catalyst layers (CLs) and gas diffusion layers (GDLs) results in flooding, which inhibits reactant access to the catalyst sites. Water management is complicated by several types of water transport, such as production of water from the cathode reaction, evaporation, and condensation at each electrode, osmotic drag of water molecules from anode to cathode by... 

Polymer electrolyte fuel cell (PEFC) is considered as one of the most promising power sources for futurist s hydrogen economy. As shown in Fig. 1, operation of a Nation-based PEFC is dictated by transport processes and electrochemical reactions at cat-alyst/polymer electrolyte interfaces and transport processes in the polymer electrolyte membrane (PEM), in the catalyst layers consisting of precious metal (Pt or Ru) catalysts on porous carbon support and polymer electrolyte clusters, in gas diffusion layers (GDLs), and in flow channels. Specifically, oxidants, fuel, and reaction products flow in channels of millimeter scale and diffuse in GDL with a structure of micrometer scale. Nation, a sulfonic acid tetrafluorethy-lene copolymer and the most commonly used polymer electrolyte, consists of nanoscale hydrophobic domains and proton conducting hydrophilic domains with a scale of 2-5 nm. The diffusivities of the reactants (02, H2, and methanol) and reaction products (water and C02) in Nation and proton conductivity of Nation strongly depend on the nanostructures and their responses to the presence of water. Polymer electrolyte clusters in the catalyst layers also play a critical... 

M. Eikerling and A. Komyshev, Modeling the performance of the cathode catalyst layer of polymer electrolyte fuel cells, J. Electroanal. Chem. 435 (1998) 98-106. 

Direct simulation of polymer electrolyte fuel cell catalyst layers, presentation of a systematic development of the direct numerical simulation... 

The MEA consists of a thin (10-200 pm) solid polymer electrolyte (a protonic membrane, such as Nation) on both sides of which are pasted the electrode structures (fuel anode and oxygen cathode) (Figure 9.5). The electrode structure comprises several layers the first layer made of carbon paper (or cloth) to strength the structure, on which are coated the GDL, and then the catalyst layer (CL), directly in contact with the protonic membrane (usually Nafion). 

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