In this work, N 2 adsorption was employed to investigate the effects of carbon support, platinum, and ionomer loading on the microstructure of polymer electrolyte membrane fuel cell catalyst layers (CLs). Brunauer-Emmett-Teller and t-plot analyses of adsorption isotherms and pore-size distributions were used to study the microstructure of carbon supports, platinum/carbon catalyst powders, and three-component platinum/carbon/ionomer CLs. Two types of carbon supports were chosen for the investigation: Ketjen Black and Vulcan XC-72. CLs with a range of Nafion ionomer loadings were studied in order to evaluate the effect of an ionomer on the CL microstructure. Regions of adsorption were differentiated into micropores associated with the carbon primary particles (<2 nm), mesopores ascribed to the void space inside agglomerates (2-20 nm), and meso-to macroporous space inside aggregates of agglomerates (>50 nm). Ketjen Black was found to possess a significant fraction of micropores, 25% of the total pore volume, in contrast to Vulcan XC-72, for which the corresponding fraction of micropores was 15% of the total pore volume. The microstructure of the carbon support was found to be a significant factor in the formation of the microstructure in the three-component CLs, serving as a rigid porous framework for distribution of platinum and the ionomer. It was found that platinum particle deposition on Ketjen Black occurs in, or at the mouth of, the support's micropores, thus affecting its effective microporosity, whereas platinum deposition on Vulcan XC-72 did not significantly affect the support's microstructure. The codeposition of ionomer in the CL strongly influenced its porosity, covering pores < 20 nm, which are ascribed to the pores within the primary carbon particles (pore sizes < 2 nm) and to the pores within agglomerates of the particles (pore sizes of 2-20 nm).
The effects of carbon microstructure and ionomer loading on water vapor sorption and retention in catalyst layers (CLs) of PEM fuel cells are investigated using dynamic vapor sorption. Catalyst layers based on Ketjen Black and Vulcan XC-72 carbon blacks, which possess distinctly different surface areas, pore volumes, and microporosities, are studied. It is found that pores <20 nm diameter facilitate water uptake by capillary condensation in the intermediate range of relative humidities. A broad pore size distribution (PSD) is found to enhance water retention in Ketjen Black-based CLs whereas the narrower mesoporous PSD of Vulcan CLs is shown to have an enhanced water repelling action. Water vapor sorption and retention properties of CLs are correlated to electrochemical properties and fuel cell performance. Water sorption enhances electrochemical properties such as the electrochemically active surface area (ESA), double layer capacitance and proton conductivity, particularly when the ionomer content is very low. The hydrophilic properties of a CL on the anode and the cathode are adjusted by choosing the PSD of carbon and the ionomer content. It is shown that a reduction of ionomer content on either cathode or anode of an MEA does not necessarily have a significant detrimental effect on the MEA performance compared to the standard 30 wt % ionomer MEA. Under operation in air and high relative humidity, a cathode with a narrow pore size distribution and low ionomer content is shown to be beneficial due to its low water retention properties. In dry operating conditions, adequate ionomer content on the cathode is crucial, whereas it can be reduced on the anode without a significant impact on fuel cell performance.
International audienceWe model and validate the effect of ionomer content and Pt nanoparticles on nanoporous structure of catalyst layers in polymer electrolyte fuel cells. By employing Pore network modeling technique and analytical solutions, we analyze and reproduce experimental N2-adsorption isotherms of carbon, Pt/ carbon and catalyst layers with various ionomer contents. The porous catalyst layer structures comprise of Ketjen Black carbon, Pt and Nafion ionomer. The experimental pore size distributions obtained by N2- adsorption are used as an input to generate porous media using the pore network approach. Subsequently, the simulated porous structures are used to produce simulated N2-adsorption isotherms, which are then compared to the experimentally measured isotherms. The results show a good agreement in the prediction of the effect of the ionomer content on the microstructure of catalyst layers. Moreover, the analysis of the isotherms confirms the hypothesis of ionomer distribution on the surface of agglomerates as well as the existence of different sorption regimes in primary and secondary pores of fuel cell catalyst layers
Fuel cell catalyst powders consisting of Pt metal catalyst deposited on three types of carbon supports were imaged using the electron tomography TEM technique. Electron tomograms were used to reconstruct 3D models of the carbon supports and catalyst particles. The 3D models served to visualize the catalyst powders and to calculate total surface areas, the interaction surface areas between the support and the catalyst, as well as catalyst particle size distribution. Results showed good agreement with other available experimental data.
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