Denis Kramer

Oscillations in Gas Channels Part I. The Forgotten Player in Impedance Spectroscopy in PEFCs

Our experimental results shown here disprove that finite diffusion can generally be assumed in ac impedance models for H-2/air-polymer electrolyte fuel cells (PEFCs) to account for the diffusive transport of oxygen through the gas diffusion layer (GDL) toward the air electrode. It is shown that the amplitude of the oxygen concentration oscillation created as a consequence of superimposed ac current at the air electrode is not zero at the channel/GDL interface but extends into the gas channels, at least below modulation frequencies of f(mod)=10 Hz. By this, sinusoidal oxygen-concentration oscillations within the cathode gas channels are excited locally along the flow field. Due to the forced air convection in the cathode flow-field channels, a coupling via the gas phase occurs downstream of the flow field. The coupling strongly affects the local and by this the overall impedance response of the cell and evokes the formation of a low-frequency arc in H-2/air-PEFC impedance spectra. Based on the experimental results, a qualitative model is presented explaining the local impedance response of a segmented 200 cm(2) H-2/air PEFC

Oscillations in Gas Channels II. Unraveling the Characteristics of the Low Frequency Loop in Air-Fed PEFC Impedance Spectra

The effect of oxygen depletion along the cathode flow channels on the local impedance response of a polymer electrolyte fuel cell (PEFC) operated on air and pure hydrogen was investigated using a novel experimental approach. The method combines the use of sectioned electrodes and local ac measurements in PEFCs. The results shown here give experimental proof that oxygen concentration oscillations in the cathode gas channels generated as a consequence of ac current flow evoke the formation of a low frequency capacitive loop in local H-2/air-PEFC impedance spectra in downstream parts of the flow field. The loop shows positive or negative real parts at low frequencies depending on the air stoichiometry. The loop is not observed in the local spectrum when the ac current is applied locally and, consequently, the impact of upstream processes on the local impedance response is excluded. A mechanistic description of the processes occurring during ac measurements in H-2/air-PEFCs was developed and validated by experiments. The results show that processes occurring along the flow channels of a PEFC cannot be excluded from the interpretation of PEFC impedance spectra even at rather high air stoichiometries and are in fact the most important phenomena at low modulation frequencies (f(mod)< 10 Hz).

Electrocatalytic performance of fuel cell reactions at low catalyst loading and high mass transport

An alternative approach to the rotating disk electrode (RDE) for characterising fuel cell electrocatalysts is presented. The approach combines high mass transport with a flat, uniform, and homogeneous catalyst deposition process, well suited for studying intrinsic catalyst properties at realistic operating conditions of a polymer electrolyte fuel cell (PEFC). Uniform catalyst layers were produced with loadings as low as 0.16 μgPt cm(-2) and thicknesses as low as 200 nm. Such ultra thin catalyst layers are considered advantageous to minimize internal resistances and mass transport limitations. Geometric current densities as high as 5.7 A cm(-2)Geo were experimentally achieved at a loading of 10.15 μgPt cm(-2) for the hydrogen oxidation reaction (HOR) at room temperature, which is three orders of magnitude higher than current densities achievable with the RDE. Modelling of the associated diffusion field suggests that such high performance is enabled by fast lateral diffusion within the electrode. The electrodes operate over a wide potential range with insignificant mass transport losses, allowing the study of the ORR at high overpotentials. Electrodes produced a specific current density of 31 ± 9 mA cm(-2)Spec at a potential of 0.65 V vs. RHE for the oxygen reduction reaction (ORR) and 600 ± 60 mA cm(-2)Spec for the peak potential of the HOR. The mass activity of a commercial 60 wt% Pt/C catalyst towards the ORR was found to exceed a range of literature PEFC mass activities across the entire potential range. The HOR also revealed fine structure in the limiting current range and an asymptotic current decay for potentials above 0.36 V. These characteristics are not visible with techniques limited by mass transport in aqueous media such as the RDE.

Analysis of gas diffusion layer and flow-field design in a PEMFC using neutron radiography

A carbon-cloth gas diffusion layer (GDL) displays better performance than a carbon-paper GDL under humidified conditions. A straight flow field displays better performance than a serpentine flow field. To investigate these phenomena, neutron radiography was used to compare the amount of liquid water that accumulated in test fuel cells. It was found that a larger amount of water accumulated in a carbon-cloth GDL than in a carbon-paper GDL. From the viewpoint of cell performance, the carbon-cloth GDL was less influenced by the accumulated water than the carbon-paper GDL. It is assumed that the broader pore distribution of a carbon-cloth GDL creates oxygen-diffusion paths even if water accumulates in the GDL. With a serpentine flow field, water accumulated in the corner and the gas bypassed the flow field. These phenomena are the main causes of performance deterioration with a serpentine flow field.

Visible-light photocatalysis on C-doped ZnO derived from polymer-assisted pyrolysis†

C-doped ZnO with a large surface area was prepared via F127-assisted pyrolysis at 500 °C and used for visible-light-responsive photocatalytic water purification. The band structure of the C-doped ZnO was investigated using valance band XPS and DFT simulation. The C-doped ZnO possessed enhanced absorption of UV and visible light, though it showed lower visible-light-responsive photocatalytic activity than ZnO because of significant recombination of photogenerated charge carriers arising from overloaded C-dopant and oxygen vacancies.

Celtec-V A Polybenzimidazole-Based Membrane for the Direct Methanol Fuel Cell

Celtec-V is a proton exchange membrane based on polybenzimidazole (PBI) comprising an interpenetrating network of polyvinylphosphonic acid designed for application in the direct methanol fuel cell. The properties and fuel cell performance of Celtec-V are investigated and compared against a Nafion 117 standard. It is shown that with the PBI-based membrane, fuel cell performance can be sustained to higher methanol feed concentration at around half the methanol crossover rate. Above 1.0 M methanol, Celtec-V outperforms Nafion 117. Furthermore, lower water permeation is observed, with Celtec-V having an electro-osmotic drag coefficient of around 1 compared to a value of 4-5 for Nafion 117. Room for improvement is identified in the ohmic resistance of the membrane and the cathode-membrane interface, where higher losses are observed at increasing current density.

Materials for polymer electrolyte fuel cells

The commercial success of the polymer electrolyte fuel cell (PEFC) will to a large extent be determined by the nature, properties, functionality, and cost of the electrochemical sub-components used in the membrane electrode assembly (MEA). Materials research activities in Switzerland for the PEFC are being pursued at the Paul Scherrer Institut (Villigen AG) and the Swiss Federal Institute of Technology in Lausanne with different objectives. The radiation grafted proton exchange membrane developed at the Paul Scherrer Institut (PSI) has been brought to a near-product-like quality level with encouraging performance close to state-of-the-art materials and a life-time of several thousand hours. Furthermore, the membrane shows low methanol crossover in the direct methanol fuel cell. In addition, polyarylene block copolymer membranes have been investigated as an option for fluorine-free membranes. The electrocatalysis of Pt in acidic solution and in contact with a solid electrolyte, the development of new methanol oxidation and oxygen reduction catalysts, and co-sputtering of Pt and carbon as an alternative method for catalyst preparation are areas of fundamental research. More applied research is performed in the characterization of commercial electrodes in single cells, using standard as well as advanced diagnostic tools developed in-house. This article gives an overview over the research and development projects in Switzerland related to materials and components for the PEFC.

Oxygen Reduction Reaction at LaxCa1-xMnO3 Nanostructures: Interplay between A-site Segregation and B-site Valency

The mean activity of surface Mn sites at LaxCa1−xMnO3 nanostructures towards the oxygen reduction reaction (ORR) in alkaline solution is assessed as a function of the oxide composition. Highly active oxide nanoparticles were synthesised by an ionic liquid-based route, yielding phase-pure nanoparticles, across the entire range of compositions, with sizes between 20 and 35 nm. The bulk vs. surface composition and structure are investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). These techniques allow quantification of not only changes in the mean oxidation state of Mn as a function of x, but also the extent of A-site surface segregation. Both trends manifest themselves in the electrochemical responses associated with surface Mn sites in 0.1 M KOH solution. The characteristic redox signatures of Mn sites are used to estimate their effective surface number density. This parameter allows comparing, for the first time, the mean electrocatalytic activity of surface Mn sites as a function of the LaxCa1−xMnO3 composition. The ensemble of experimental data provides a consistent picture in which increasing electron density at the Mn sites leads to an increase in the ORR activity. We also demonstrate that normalisation of electrochemical activity by mass or specific surface area may result in inaccurate structure–activity correlations.

The stability of LaMnO3 surfaces: a hybrid exchange density functional theory study of an alkaline fuel cell catalyst

LaMnO3 is an inexpensive alternative to precious metals (e.g. platinum) as a catalyst for the oxygen reduction reaction in alkaline fuel cells. In fact, recent studies have shown that among a range of non-noble metal catalysts, LaMnO3 provides the highest catalytic activity. Despite this, very little is known about LaMnO3 in the alkaline fuel cells environment, where the orthorhombic structure is most stable. In order to understand the reactivity of orthorhombic LaMnO3 we must first understand the surface structure. Hence, we have carried out calculations on its electrostatically stable low index surfaces using hybrid-exchange density functional theory, as implemented in CRYSTAL09. For each surface studied the calculated structure and formation energy is discussed. Among the surfaces studied the (100) surface was found to be the most stable with a formation energy of 0.98 J m−2. The surface energies are rationalised in terms of the cleavage of Jahn–Teller distorted Mn–O bonds, the compensation of undercoordination for ions in the terminating layer and relaxation effects. Finally, the equilibrium morphology of orthorhombic LaMnO3 crystals is predicted, allowing us to speculate about likely surface reaction sites.

Electronic metal-support interaction enhanced oxygen reduction activity and stability of boron carbide supported platinum

Catalysing the reduction of oxygen in acidic media is a standing challenge. Although activity of platinum, the most active metal, can be substantially improved by alloying, alloy stability remains a concern. Here we report that platinum nanoparticles supported on graphite-rich boron carbide show a 50–100% increase in activity in acidic media and improved cycle stability compared to commercial carbon supported platinum nanoparticles. Transmission electron microscopy and x-ray absorption fine structure analysis confirm similar platinum nanoparticle shapes, sizes, lattice parameters, and cluster packing on both supports, while x-ray photoelectron and absorption spectroscopy demonstrate a change in electronic structure. This shows that purely electronic metal-support interactions can significantly improve oxygen reduction activity without inducing shape, alloying or strain effects and without compromising stability. Optimizing the electronic interaction between the catalyst and support is, therefore, a promising approach for advanced electrocatalysts where optimizing the catalytic nanoparticles themselves is constrained by other concerns.