Dissolution and migration of platinum due to start/stop degradation and increased cathode potentials were studied for commercial membrane electrode assemblies (MEA). The chosen conditions closely mimic real situations in automotive operation. In start/stop tests, we observed a strongly enhanced platinum dissolution due to the dynamic interplay of repeated cell start‐up and consecutive normal fuel cell operation, which is related to platinum oxidation (start‐up) and reduction (normal operation) cycles. Consequently, the performed test protocols distinguish between dynamic and static load profiles. Electrochemical investigations before and after degradation monitor the loss in cell performance. Since electron microscopy offers the unique possibility to unravel and distinguish degradation due to carbon corrosion and agglomeration or platinum dissolution, a focus was set on this method. For the start/stop MEA pronounced platinum dissolution accompanied by the formation of large platinum precipitations in the membrane was found. Carbon corrosion was also observed, but did not lead to a significantly reduced porosity and loss in platinum dispersion. In contrast, the MEA which was exposed to high constant potentials exhibited severe damage to the 3D cathode structure due to carbon corrosion. However, no pronounced platinum dissolution was observed and only few Pt precipitations were found in the membrane itself.

Membrane electrode assemblies (MEA) for fuel cells require optimization of their nanoscale organization to reach performance parameters, which include enhanced power density, increased catalyst utilization and reduced cost. We applied sprayed layer-by-layer assembly to produce a high activity MEA for H(2)/O(2) fuel cells from polyaniline fibers (PANI-F). This technique produces "fast-prepared" membranes with nanoscale structure, which allows to adequately address specific tuning of their porosity, platinum loading, electronic conductivity, and proton conductivity. Pt nanoparticles were attached to the PANI-F in a reaction of selective heterogeneous nucleation. After functionalization, Pt/PANI-F were assembled with Nafion. Microscopic investigation revealed that functionalized polyaniline fibers formed a highly porous yet tight network of interpenetrating conductors connected to the catalytic Pt particles. The Pt/PANI-F LBL ultrathin MEA demonstrated a power densitiy of 63 mW cm(-2) and yielded a Pt utilization of 437.5 W g(-1) Pt which is comparable to the traditional fuel cell using carbon black as Pt support. Moreover, the amount of Pt used in this work is almost 2 times lower than for usual carbon-supported Pt catalysts.

In this study, we explored thin films of nanofibrous functionalised conducting plasma polyaniline (pPANI) with platinum deposited by an atmospheric plasma deposition process for the potential design of anodes for hydrogen fuel cell applications. We observed that the incorporation of such a polymer, characterised by both electronic and ionic conductivity, associated with a catalyst in a 3D porous network, could lead to an increased probability of the three‐phase contact to occur. In this context, aniline was mixed with functionalised platinum nanoparticles and used as the precursor. The role of these functionalised nanoparticles was not only to act as the catalyst for fuel cell purposes, but also as nucleation sites promoting the formation of the nanofibrous pPANI thin film during the plasma polymerisation. The morphology of the thin film was analysed by scanning electron microscopy and the efficiency, in terms of energy conversion, was assessed in a single fuel cell test bench.

Sb‐doped SnO2 (ATO) is used as an alternative support material to replace carbon in the highly corrosive environment of a fuel cell cathode. Two ATO powders with different morphologies are decorated with Pt nanoparticles and afterwards used as the cathode catalyst. The commercial ATO powder exhibits crystallites in the nanometer range, while the home‐made ATO powder, which was synthesized by ultrasonic spray pyrolysis, consists of polycrystalline hollow spheres. The spheres have diameters in the micrometer range and are composed of individual nanocrystallites. The unusual morphology of the home‐made ATO offers nano‐ and microporosity at the same time and opens up new possibilities for the controlled design of electrode structures in low‐temperature polymer electrolyte fuel cells. Both materials are characterized by XRD, SEM, and TEM and tested in a single cell set‐up. While almost no current is gained from the membrane electrode assembly with the commercial ATO support, the cell with the home‐made ATO achieves a mediocre performance. This higher activity, however, is obtained with approximately half the Pt content compared to the catalyst with the commercial support. The different behaviours of both ATO powders can therefore mainly be attributed to differences in the specific support morphology.

The performance of a low temperature fuel cell is strongly correlated with parameters like the platinum particle size, platinum dispersion on the carbon support, and electronic and protonic conductivity in the catalyst layer as well as its porosity. These parameters can be controlled by a rational choice of the appropriate catalyst synthesis and carbon support. Only recently, particular attention has been given to the support morphology, as it plays an important role for the formation of the electrode structure. Due to their significantly different structure, mesoporous carbon microbeads (MCMBs) and multiwalled carbon nanotubes (MWCNTs) were used as supports and compared. Pt nanoparticles were decorated on these supports using the polyol method. Their size was varied by different heating times during the synthesis, and XRD, TEM, SEM, CV, and single cell tests used in their detailed characterization. A membrane-electrode assembly prepared with the MCMB did not show any activity in the fuel cell test, although the catalyst's electrochemical activity was almost similar to the MWCNT. This is assumed to be due to the very dense electrode structure formed by this support material, which does not allow for sufficient mass transport.

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The ethanol oxidation reaction is studied using X-ray absorption spectroscopy during chronoamperometric cell operation with a carbon-supported Pt catalyst. The analysis of the XANES region of the Pt L 3 edge by the Δμ-technique allows the coverage of the Pt surface with OH-, n-fold O-, and C-species to be determined. The current−voltage characteristics and the coverage is modeled by means of a multistep reaction mechanism based on a modified Butler−Volmer approach that additionally includes adsorbate−adsorbate lateral interactions. The model is validated against experimental current and surface coverage data over time. With the model, the importance of acetaldehyde formation via initial C α −H vs O−H bond cleavage is examined, the latter dominating at higher potentials on vacant sites remaining in the oxygen coverage coming from water activation.