Mécanismes de vieillissement des électrocatalyseurs de pile à combustible de type PEMFC

Ce travail de thèse s'inscrit dans le cadre de la durabilité des PEMFC et s'intéresse plus particulièrement à la dégradation des électrocatalyseurs de type Pt/C qui sont utilisés dans leurs électrodes. L'objectif visé était la détermination des mécanismes responsables de leur dégradation, par combinaison d'expériences d'électrochimie en cellule à trois électrodes, de microscopie électronique en transmission et à balayage, et de spectrométrie de masse (DEMS). Dans un premier temps nous avons mis en évidence que les méthodes de caractérisation employées peuvent influencer les dégradations observées. Ainsi, la morphologie des nanocatalyseurs Pt/C peut-être altérée par l'observation MET elle même, comme d'ailleurs par la séquence de mesures par CO-stripping.This thesis is part of the durability of PEMFC and is particularly interested in the degradation of electrocatalysts of type Pt / C that are used within their electrodes. The objective was to determine mechanisms responsible for their degradation, by combining experiments in electrochemical cell with three electrodes, transmission electron microscopy and scanning, and mass spectrometry (DEMS). Initially we have shown that the characterization methods used can influence the degradation observed. Thus, the morphology of Pt nanocatalysts / C may be altered by the TEM observation itself, as does the sequence of measurements by CO-stripping.SAVOIE-SCD - Bib.électronique (730659901) / SudocGRENOBLE1/INP-Bib.électronique (384210012) / SudocGRENOBLE2/3-Bib.électronique (384219901) / SudocSudocFranceF

Influence of carbon aerogel texture on PEMFC performances

International audienceTo improve Proton Exchange Membrane Fuel Cells (PEMFC), it is necessary to understand the phenomena occurring in operating conditions. The objective of this study is to determine how carbon support architecture can impact PEMFC performances, particularly diffusive limitations. In this context, as they have a controllable texture, carbon aerogels were used as catalyst supports in PEM fuel cell cathodes. Three carbon aerogels with different morphologies were synthesized. Fuel cell measurements show that the carbon support architecture has a significant impact on diffusive limitations. Moreover, they confirm that Nafion® loading must be optimized in order to preserve the catalytic layers architecture. This work finally highlights the impact of the catalytic layers architecture on the PEMFC performances

Synthesis of Highly Porous Catalytic Layers for Polymer Electrolyte Fuel Cell Based on Carbon Aerogels

International audienceRecent studies of the PEMFC catalytic layer electrocatalystsupport showed that high surface area carbon blacks cannot beused efficiently (1) because they have necessarily small primarypores that yield high diffusion limitation for the oxygenreduction reaction (ORR). In the present paper, we firstsynthesized and characterized carbon aerogels which exhibit highsurface area, high porous volume and adjustable pore-sizedistribution. In that way, they enable to decouple betweensurface area and porosity, while they are also promisingelectrocatalyst supports (2). Second, we elaborated newcatalytic layers made from 2 different carbon aerogels with 2different Nafion loadings. Finally, we characterized thestructure of such catalytic layers, and evaluated their activitytowards the oxygen reduction reaction (ORR). Finally, anappropriate catalyst support should display large pore-size andhigh surface area in order to reduce the PEMFC cathode platinumloadings without loosing activity, following the reduction ofoxygen diffusion limitation

Comparison of platinum deposit methods on carbon aerogels used in Proton Exchange. Membrane Fuel Cells (PEMFC)

International audienceWith the rarefaction and price increase of fossil fuels along with the consequences of greenhouse effect, many challenges have to be taken up. Consequently, a strong research effort is devoted to cleaner energy converters like fuel cells. In the car industry, Proton Exchange Membrane Fuel Cells (PEMFC) are chosen by a majority. But, remaining problems must be solved before a development at a large scale, among which: reducing the costs and increasing the power density and durability. Costs reduction mostly implies both diminishing the platinum quantity required for the oxygen reduction reaction at the cathode and increasing its activity. For these reasons, researches are devoted to the impact study of various methods of platinum deposit on the performances of new electrocatalysts and to the understanding of phenomena occurring in fuel cells

Elaboration and characterizations of platinum nanoparticles supported on cellulose-based carbon aerogel

International audienceThis work investigates the deposition of Pt nanoparticles onto carbon aerogels (CA), derived from microcrystalline cellulose. Nanoparticles are synthesised via impregnating the CA with H2PtCl6 followed by reduction either under H2 at 300 C or in a basic NaBH4 solution. H2 reduction yields uniform Pt nanoparticles (average diameter < 2nm) dispersed over the CA surface as revealed by Transmission electron microscopy (TEM). Larger agglomerates can be seen in TEM images of NaBH4 reduced samples, which is confirmed by powder X-ray diffraction (XRD). A rotating disk electrode was employed to analyse the electrochemical properties of the Pt nanoparticles. The active area of the platinum nanoparticles was evaluated using hydrogen adsorption/desorption cyclic voltammetry and CO stripping measurements. The oxygen reduction reaction was also studied to (i) obtain the kinetic parameters of oxygen reduction for the Pt/CA materials and (ii) compare them with commercial Pt/Carbon Black

Nanoporous silver for electrocatalysis application in alkaline fuel cells

Self-supporting porous silver foils with an average pore size < 100 nm were produced from a crystalline silver-based ternary alloy as a precursor by removing second phases present in the silver matrix. The final Ag-based porous foil shows good mechanical properties when comparing to its previous amorphous analogues. Its activity for direct electrochemical oxidation of ammonia-borane (AB), a fuel of interest for direct liquid fuel cells, has been investigated in alkaline media. The material exhibits promising electrochemical properties in long-term operation; indeed, material composition and nanostructure remain similar after 15,000 cyclic-voltammetries between − 0.3 and 0.5 V vs. RHE in a 0.1 M NaOH + 5 mM AB solution thermostated at 25 °C. Nanoporous materials, and in particular nanoporous silver, can therefore represent a relevant choice as anode in direct ammonia-borane fuel cell

Durability of carbon-supported nanostructured electrocatalysts in alkaline environments: more noble is not necessarily more stable!

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Apport des matériaux fluorés à la filière hydrogène : catalyseurs et électrodes de PEMFC

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Tailoring membranes

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Durability of carbon-supported nanostructured electrocatalysts in alkaline environments: more noble is not necessarily more stable!

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