Schökel, Alexander (2015)
Ruthenium dissolution in direct methanol fuel cells.
Technische Universität Darmstadt
Dissertation, Erstveröffentlichung
Kurzbeschreibung (Abstract)
The lifetime of a direct methanol fuel cell (DMFC) is mostly determined by the degradation of its active component, the membrane electrode assembly (MEA). Besides degradation of the proton conducting membrane, the aging of the electrodes and especially the catalysts therein is the major limiting factor. One of the catalyst degradation mechanisms is ruthenium dissolution. This work is the first extensive study on the dissolution, migration and deposition of ruthenium in a DMFC single cell during early operation, i.e. between first start-up of the cell till approx. 100 h of operation. To analyze the dissolution process it is necessary to track the trace amounts of ruthenium being dissolved and transported through the MEA. For this task x-ray fluorescence spectroscopy (XRF), x-ray absorption spectroscopy (XAS), inductively coupled plasma mass spectrometry (ICP-MS) and cyclic voltammetry (CV) were used. The characterization of the catalysts itself was carried out by x-ray powder diffraction (XRD) and x-ray photoelectron spectroscopy (XPS). Fuel cell tests were explicitly not including any extreme operation conditions, such as fuel starvation or accelerated aging protocols. Each DMFC test was run at one specific potential for the duration of the test. After operation the cells were disassembled, the MEA removed, dried and cathode and anode catalysts removed from the membrane to be analyzed separately. Two different MEA fabrication techniques, wet spray coating and dry decal transfer, were used to produce MEAs. The fabrication techniques are compared in respect to their influence on ruthenium dissolution. It is shown, that the crystalline fraction of the commercial platinum-ruthenium on carbon anode catalyst and platinum on carbon cathode catalyst does not change under the operation conditions investigated. The mean lattice parameters of the platinum and platinum-ruthenium catalysts are 3.916 and 3.866, respectively, as determined by XRD measurements. Both values are in good agreement with the lattice parameters reported in literature. Also the XPS measurements do not show any significant change in the catalyst composition after operation in the DMFC. XAS measurements gave evidence that a transfer of ruthenium already takes place during fabrication of the MEA. While XAS could only be used for qualitative analysis of the samples, XRF and complementary ICP-MS analyses provided quantitative measurements for the migrated ruthenium. Even though it was expected that the wet spray coating technique causes a higher amount of ruthenium to migrate onto the cathode side, the Ru transfer of both techniques in the order of 0.02 wt%. It is important to note, that this transfer happened during fabrication and before the MEA was even assembled inside a DMFC. After cell assembly and start of DMFC operation a fast dissolution process transfers an additional 0.2 wt% ruthenium onto the cathode side. Here the fabrication technique seems to influence the ruthenium crossover. The sprayed MEAs show a significantly higher Ru transfer of about 0.3 wt% during the first 2 h of operation. Over the next 100 h of cell operation of the decal MEAs at open circuit conditions another 0.3 wt% ruthenium are transferred by a presumably slower process. It can be assumed that 4 there are two sources of ruthenium feeding these two processes. Highly soluble ruthenium species like hydroxides could by the source for the fast dissolution process, while the slower process is fed by harder to dissolve oxides. ICP-MS analyses of different solvents after leaching experiments using the platinum-ruthenium catalyst show that both water and methanol can dissolve low amounts of ruthenium from the catalyst. In contrast formic acid, which is also present in DMFCs as a product of an incomplete methanol oxidation side reaction, has the capability to dissolve significant amounts of ruthenium and even to attack platinum. Consequently, formation of formic acid inside the DMFC and ruthenium dissolution may be closely correlated.
Typ des Eintrags: | Dissertation | ||||
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Erschienen: | 2015 | ||||
Autor(en): | Schökel, Alexander | ||||
Art des Eintrags: | Erstveröffentlichung | ||||
Titel: | Ruthenium dissolution in direct methanol fuel cells | ||||
Sprache: | Englisch | ||||
Referenten: | Roth, Prof. Dr. Christina ; Ensinger, Prof. Dr. Wolfgang | ||||
Publikationsjahr: | 2015 | ||||
Datum der mündlichen Prüfung: | 6 März 2015 | ||||
URL / URN: | http://tuprints.ulb.tu-darmstadt.de/4454 | ||||
Kurzbeschreibung (Abstract): | The lifetime of a direct methanol fuel cell (DMFC) is mostly determined by the degradation of its active component, the membrane electrode assembly (MEA). Besides degradation of the proton conducting membrane, the aging of the electrodes and especially the catalysts therein is the major limiting factor. One of the catalyst degradation mechanisms is ruthenium dissolution. This work is the first extensive study on the dissolution, migration and deposition of ruthenium in a DMFC single cell during early operation, i.e. between first start-up of the cell till approx. 100 h of operation. To analyze the dissolution process it is necessary to track the trace amounts of ruthenium being dissolved and transported through the MEA. For this task x-ray fluorescence spectroscopy (XRF), x-ray absorption spectroscopy (XAS), inductively coupled plasma mass spectrometry (ICP-MS) and cyclic voltammetry (CV) were used. The characterization of the catalysts itself was carried out by x-ray powder diffraction (XRD) and x-ray photoelectron spectroscopy (XPS). Fuel cell tests were explicitly not including any extreme operation conditions, such as fuel starvation or accelerated aging protocols. Each DMFC test was run at one specific potential for the duration of the test. After operation the cells were disassembled, the MEA removed, dried and cathode and anode catalysts removed from the membrane to be analyzed separately. Two different MEA fabrication techniques, wet spray coating and dry decal transfer, were used to produce MEAs. The fabrication techniques are compared in respect to their influence on ruthenium dissolution. It is shown, that the crystalline fraction of the commercial platinum-ruthenium on carbon anode catalyst and platinum on carbon cathode catalyst does not change under the operation conditions investigated. The mean lattice parameters of the platinum and platinum-ruthenium catalysts are 3.916 and 3.866, respectively, as determined by XRD measurements. Both values are in good agreement with the lattice parameters reported in literature. Also the XPS measurements do not show any significant change in the catalyst composition after operation in the DMFC. XAS measurements gave evidence that a transfer of ruthenium already takes place during fabrication of the MEA. While XAS could only be used for qualitative analysis of the samples, XRF and complementary ICP-MS analyses provided quantitative measurements for the migrated ruthenium. Even though it was expected that the wet spray coating technique causes a higher amount of ruthenium to migrate onto the cathode side, the Ru transfer of both techniques in the order of 0.02 wt%. It is important to note, that this transfer happened during fabrication and before the MEA was even assembled inside a DMFC. After cell assembly and start of DMFC operation a fast dissolution process transfers an additional 0.2 wt% ruthenium onto the cathode side. Here the fabrication technique seems to influence the ruthenium crossover. The sprayed MEAs show a significantly higher Ru transfer of about 0.3 wt% during the first 2 h of operation. Over the next 100 h of cell operation of the decal MEAs at open circuit conditions another 0.3 wt% ruthenium are transferred by a presumably slower process. It can be assumed that 4 there are two sources of ruthenium feeding these two processes. Highly soluble ruthenium species like hydroxides could by the source for the fast dissolution process, while the slower process is fed by harder to dissolve oxides. ICP-MS analyses of different solvents after leaching experiments using the platinum-ruthenium catalyst show that both water and methanol can dissolve low amounts of ruthenium from the catalyst. In contrast formic acid, which is also present in DMFCs as a product of an incomplete methanol oxidation side reaction, has the capability to dissolve significant amounts of ruthenium and even to attack platinum. Consequently, formation of formic acid inside the DMFC and ruthenium dissolution may be closely correlated. |
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URN: | urn:nbn:de:tuda-tuprints-44540 | ||||
Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 500 Naturwissenschaften 600 Technik, Medizin, angewandte Wissenschaften > 620 Ingenieurwissenschaften und Maschinenbau |
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Fachbereich(e)/-gebiet(e): | 11 Fachbereich Material- und Geowissenschaften 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft > Erneuerbare Energien |
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Hinterlegungsdatum: | 03 Mai 2015 19:55 | ||||
Letzte Änderung: | 03 Mai 2015 19:55 | ||||
PPN: | |||||
Referenten: | Roth, Prof. Dr. Christina ; Ensinger, Prof. Dr. Wolfgang | ||||
Datum der mündlichen Prüfung / Verteidigung / mdl. Prüfung: | 6 März 2015 | ||||
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