Shuang Ma Andersen

SiC nanocrystals as Pt catalyst supports for fuel cell applications

A robust catalyst support is pivotal to Proton Exchange Membrane Fuel Cells (PEMFCs) to overcome challenges such as catalyst support corrosion, low catalyst utilization and overall capital cost. SiC is a promising candidate material which could be applied as a catalyst support in PEMFCs. SiC nanocrystals are here synthesized using nano-porous carbon black (Vulcan® XC-72) as a template using two different reactions, which result in particle sizes in the ranges of 50–150 nm (SiC-SPR) and 25–35 nm (SiC-NS). Pt nano-catalysts of size 5–8 nm and 4–5 nm have successfully been uniformly deposited on the nanocrystals of SiC-SPR and SiC-NS by the polyol method. The SiC substrates are subjected to an acid treatment to introduce the surface groups, which help to anchor the Pt nano-catalysts. These SiC based catalysts have been found to have a higher electrochemical activity than commercially available Vulcan based catalysts (BASF & HISPEC). These promising results signal a new era of SiC based catalysts for fuel cell applications.

Oxygen reduction and methanol oxidation behaviour of SiC based Pt nanocatalysts for proton exchange membrane fuel cells

Research with proton exchange membrane fuel cells has demonstrated their potential as important providers of clean energy. The commercialization of this type of fuel cell needs a breakthrough in the electrocatalyst technology to reduce the relatively large amount of noble metal platinum used with the present carbon based substrates. We have recently examined suitably sized silicon carbide (SiC) particles as catalyst supports for fuel cells based on the stable chemical and mechanical properties of this material. In the present study, we have continued our work with studies of the oxygen reduction and methanol oxidation reactions of SiC supported catalysts and measured them against commercially available carbon based catalysts. The deconvolution of the hydrogen desorption signals in CV cycles shows a higher contribution of Pt (110) and Pt (111) peaks compared to Pt (100) for SiC based supports than for carbon based commercial catalysts, when HClO4 is used as an electrolyte. The Pt (110) and Pt (111) facets are shown to have higher electrochemical activities than Pt (100) facets. To the best of our knowledge, methanol oxidation studies and the comparison of peak deconvolutions of the H desorption region in CV cyclic studies are reported here for the first time for SiC based catalysts. The reaction kinetics for the oxygen reduction and for methanol oxidation with Pt/SiC are observed to be similar to the carbon based catalysts. The SiC based catalyst shows a higher specific surface activity than BASF (Pt/C) for methanol oxidation and oxygen reduction while the mass activity values are comparable.

Electrochemical Performance and Durability of Carbon Supported Pt Catalyst in Contact with Aqueous and Polymeric Proton Conductors

Significant differences in catalyst performance and durability are often observed between the use of a liquid electrolyte (e.g., sulfuric acid), and a solid polymer electrolyte (e.g., Nafion). To understand this phenomenon, we studied the electrochemical behavior of a commercially available carbon supported platinum catalyst in four different electrode structures: catalyst powder (CP), catalyst ionomer electrode (CIE), half membrane electrode assembly (HMEA), and full membrane electrode assembly (FMEA) in both ex situ and in situ experiments under a simulated start/stop cycle. We found that the catalyst performance and stability are very much influenced by the presence of the Nafion ionomers. The proton conducting phase provided by the ionomer and the self-assembled electrode structure render the catalysts a higher utilization and better stability. This is probably due to an enhanced dispersion, an improved proton-catalyst interface, the restriction of catalyst particle aggregation, and the improved stability of the ionomer phase especially after the lamination. Therefore, an innovative electrode HMEA design for ex-situ catalyst characterization is proposed. The electrode structure is identical to the one used in a real fuel cell, where the protons transport takes place solely through solid state proton conducting phase.

The Importance of Ion Selectivity of Perfluorinated Sulfonic Acid Membrane for the Performance of Proton Exchange Membrane Fuel Cells

Nafion 212 membrane was subjected to swelling–dehydration (SD) cycles, as a relevant operation condition for direct methanol fuel cells (DMFCs). The major degradation mechanism due to the treatment was found to be sulfonic group contamination with trace ion, rather than formation of sulfonic anhydride, which is a well-known degradation mechanism for Nafion® membranes under hydrothermal (HT) aging condition. The consequences of the degradation include decreasing water content, thickness, and surface fluoride and increasing resistance, dry weight, and a changed surface morphology. Ion selectivity of the sulfonic group was studied toward different fuel cell relevant conditions. It turned out that the sulfonic groups have much higher selectivity toward cations rather than neighbor sulfonic groups. Trace impurities in the liquid methanol feed in DMFC may therefore represent an important contamination source.

Environmentally and Industrially Friendly Recycling of Platinum Nanoparticles Through Electrochemical Dissolution-Electrodeposition in Acid-Free/Dilute Acidic Electrolytes

A process to recycle platinum from industrial waste, for example, spent catalysts from polymer fuel cells and electrolyzers, through potentiodynamic dissolution along with potentiostatic electrodeposition in dilute acidic/acid-free baths has been explored. During potentiodynamic dissolution, owing to Ostwald ripening, redeposition of the dissolved Pt species on source nanoparticles becomes significant, leading to lower overall dissolution efficiency. Alternatively, high concentrations of Pt-complexing agents (e.g., Cl- ) are required to stabilize dissolved species through complex formation. The present process overcomes those limitations by removing the dissolved Pt species continuously through electrodepositing them in the form of Pt0 on another electrode. Such a process significantly promotes the overall reaction kinetics, and an increase in dissolution rate by a factor of two or more has been observed in non-complexing electrolytes. The process may be implemented for environmentally and industrially friendly recycling of Pt in dilute acidic/acid-free baths, thus eliminating the additional steps such as electrolyte upconcentration and post-dissolution reduction of dissolved Pt species.

Zoom in Catalyst/Ionomer Interface in Polymer Electrolyte Membrane Fuel Cell Electrodes: Impact of Catalyst/Ionomer Dispersion Media/Solvent

Large-scale applications of polymer electrolyte membrane fuel cells (PEMFCs) are throttled primarily by high initial cost and durability issues of the electrodes, which essentially consist of the nanoparticulate catalysts (e.g., Pt) having accessibility to electrons (e-), protons (H+), and fuel/oxidant through catalyst support, polymer electrolyte ionomer, and porous gas diffusion layer, respectively. Hence, to achieve high electrode performance in terms of activity and/or durability, understanding and optimization of the catalyst/support and catalyst/ionomer interfaces are of significant importance. Present study demonstrates an alternative route to inspect the catalyst/ionomer interface through an accelerated stress test combined with electrochemical impedance spectroscopy. Various interfaces are created through catalyst inks prepared using commercial Pt/C catalyst powder dispersed in different solvents. Electrode degradation pattern turns out to be a very useful tool to interpret a catalyst/ionomer interface structure. Variations of interfacial impedance, electrochemical surface area (ECSA), and double layer capacitance with the number of potential cycles suggested significant impact of catalyst/ionomer interface on the catalyst performance. A quantification of the degradation mechanisms responsible for ECSA loss during AST was employed to further understand the correlations between the electrochemical performance of the electrodes and their catalyst/ionomer interface structures. The knowledge may be implied to further optimize the electrode structure and hence to advance the PEMFC technology.