Polymer electrolyte fuel cells (PEFCs) have emerged as a promising renewable emission-free technology to solve the worldwide increasing demand for clean and efficient energy conversion. Despite large efforts in academia and automotive industry, the commercialization of PEFC vehicles still remains a great challenge. Critical issues are high material costs, insufficient catalytic activity as well as longterm durability. Especially due to the sluggish kinetics of the oxygen reduction reaction (ORR), high Pt loadings on the cathode are still necessary which leads to elevated costs.
Alloys of Pt with other less precious metals (Co, Ni, Fe, Cu, etc.) show improved ORR activities compared to pure Pt catalysts. However, state-of-the-art carbon-supported catalysts suffer from severe Pt and carbon corrosion during the standard operation of PEFCs, affecting their reliability and long-term efficiency.
Multimetallic aerogels constitute excellent candidates to overcome these issues. Due to their large open pores and high inner surface areas combined with electrical conductivity, they are ideal for applications in electrocatalysis. In addition, they can be employed without any catalyst support. Therefore, the fabrication of bimetallic Pt-M (M=Ni, Cu, Co, Fe) aerogels for applications in fuel cell catalysis was the focus of this thesis.
Based on a previously published synthesis for Pt–Pd aerogels, a facile one-step procedure at ambient conditions in aqueous solution was developed. Bimetallic aerogels with nanochain diameters of as small as 4 nm and Brunauer-Emmett-Teller (BET) surface areas of up to 60 m2/g could be obtained.
Extensive structure analysis of Pt–Ni and Pt–Cu aerogels by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy (STEM-EDX) and electrochemical techniques showed that both metals were predominantly present in their metallic state and formed homogeneous alloys. However, metal (hydr)oxide byproducts were observed in aerogels with higher contents of non-precious metal (>25 %). Moreover, electronic and geometric structures were similar to those of carbon-supported Pt alloy catalysts.
As a result, ORR activites were comparable, too. A threefold improvement in surface-specific activity over Pt/C catalysts was achieved. The mass-specific activites met or exceeded the U.S. Department of Energy (DOE) target for automotive PEFC applications. Furthermore, a direct correlation between non-precious metal content in the alloy and ORR activity was discovered. Aerogels with nonprecious metal contents >25% turned out to be susceptible to dealloying in acid leaching experiments, but there was no indication for the formation of extended surface structures like Pt-skeletons.
A Pt3Ni aerogel was successfully employed as the cathode catalyst layer in a differential fuel cell (1 cm2), which is a crucial step towards technical application. This was the first time an unsupported metallic aerogel was implemented in a PEFC. Accelerated stress tests that are usually applied to investigate the support stability of fuel cell catalysts revealed the excellent stability of Pt3Ni alloyed aerogels. In summary, the Pt alloy aerogels prepared in the context of this work have proven to be highly active oxygen reduction catalysts with remarkable stability.
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa:de:qucosa:30377 |
| Date | 29 May 2017 |
| Creators | Kühn, Laura |
| Contributors | Eychmüller, Alexander, Schmidt, Thomas Justus, Technische Universität Dresden |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | doc-type:doctoralThesis, info:eu-repo/semantics/doctoralThesis, doc-type:Text |
| Rights | info:eu-repo/semantics/openAccess |
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