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Electrode degradation in proton exchange membrane fuel cells
KTH, Skolan för kemivetenskap (CHE), Kemiteknik, Tillämpad elektrokemi.ORCID-id: 0000-0002-1626-1067
2013 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
Abstract [en]

The topic of this thesis is the degradation of fuel cell electrodes in proton exchange membrane fuel cells (PEMFCs). In particular, the degradation associated with localized fuel starvation, which is often encountered during start-ups and shut-downs (SUs/SDs) of PEMFCs. At SU/SD, O2 and H2 usually coexist in the anode compartment. This situation forces the opposite electrode, i.e. the cathode, to very high potentials, resulting in the corrosion of the carbon supporting the catalyst, referred to as carbon corrosion. The aim of this thesis has been to develop methods, materials and strategies to address the issues associated to carbon corrosion in PEMFC.The extent of catalyst degradation is commonly evaluated determining the electrochemically active surface area (ECSA) of fuel cell electrode. Therefore, it was considered important to study the effect of RH, temperature and type of accelerated degradation test (ADT) on the ECSA. Low RH decreases the ECSA of the electrode, attributed to re-structuring the ionomer and loss of contact with the catalyst.In the search for more durable supports, we evaluated different accelerated degradation tests (ADTs) for carbon corrosion. Potentiostatic holds at 1.2 V vs. RHE were found to be too mild. Potentiostatic holds at 1.4 V vs. RHE were found to induce a large degree of reversibility, also attributed to ionomer re-structuring. Triangle-wave potential cycling was found to irreversibly degrade the electrode within a reasonable amount of time, closely simulating SU/SD conditions.Corrosion of carbon-based supports not only degrades the catalyst by lowering the ECSA, but also has a profound effect on the electrode morphology. Decreased electrode porosity, increased agglomerate size and ionomer enrichment all contribute to the degradation of the mass-transport properties of the cathode. Graphitized carbon fibers were found to be 5 times more corrosion resistant than conventional carbons, primarily attributed to their lower surface area. Furthermore, fibers were found to better maintain the integrity of the electrode morphology, generally showing less degradation of the mass-transport losses. Different system strategies for shut-down were evaluated. Not doing anything to the fuel cell during shut-downs is detrimental for the fuel cell. O2 consumption with a load and H2 purge of the cathode were found to give around 100 times lower degradation rates compared to not doing anything and almost 10 times lower degradation rate than a simple air purge of the anode. Finally, in-situ measurements of contact resistance showed that the contact resistance between GDL and BPP is highly dynamic and changes with operating conditions.

Abstract [sv]

Denna doktorsavhandling behandlar degraderingen av polymerelektrolytbränslecellselektroder. polymerelektrolytbränslecellselektroder. Den handlar särskilt om nedbrytningen av elektroden kopplad till en degraderingsmekanism som heter ”localized fuel starvation” oftast närvarande vid uppstart och nedstängning av bränslecellen. Vid start och stopp kan syrgas och vätgas förekomma samtidigt i anoden. Detta leder till väldigt höga elektrodpotentialer i katoden. Resultatet av detta är att kolbaserade katalysatorbärare korroderar och att bränslecellens livslängd förkortas. Målet med avhandlingen har varit att utveckla metoder, material och strategier för att både öka förståelsen av denna degraderingsmekanism och för att maximera katalysatorbärarens livslängd.Ett vanligt tillvägagångsätt för att bestämma graden av katalysatorns degradering är genom mätning av den elektrokemiskt aktiva ytan hos bränslecellselektroderna. I denna avhandling har dessutom effekten av temperatur och relativ fukthalt studerats. Låga fukthalter minskar den aktiva ytan hos elektroden, vilket sannolikt orsakas av en omstrukturering av jonomeren och av kontaktförlust mellan jonomer och katalysator.Olika accelererade degraderingstester för kolkorrosion har använts. Potentiostatiska tester vid 1.2 V mot RHE visade sig vara för milda. Potentiostatiska tester vid 1.4 V mot RHE visade sig däremot medföra en hög grad av reversibilitet, som också den tros vara orsakad av en omstrukturering av jonomeren. Cykling av elektrodpotentialen degraderade istället elektroden irreversibelt, inom rimlig tid och kunde väldigt nära simulera förhållandena vid uppstart och nedstängning.Korrosionen av katalysatorbäraren medför degradering av katalysatorn och har också en stor inverkan på elektrodens morfologi. En minskad elektrodporositet, en ökad agglomeratstorlek och en anrikning av jonomeren gör att elektrodens masstransportegenskaper försämras. Grafitiska kolfibrer visade sig vara mer resistenta mot kolkorrosion än konventionella kol, främst p.g.a. deras låga ytarea. Grafitiska kolfibrer visade också en förmåga att bättre bibehålla elektrodens morfologi efter accelererade tester, vilket resulterade i lägre masstransportförluster.Olika systemstrategier för nedstängning jämfördes. Att inte göra något under nedstängning är mycket skadligt för bränslecellen. Förbrukning av syre med en last och spolning av katoden med vätgas visade 100 gånger lägre degraderingshastighet av bränslecellsprestanda jämfört med att inte göra något alls och 10 gånger lägre degraderingshastighet jämfört med spolning av anoden med luft. In-situ kontaktresistansmätningar visade att kontaktresistansen mellan bipolära plattor och GDL är dynamisk och kan ändras beroende på driftförhållandena.

sted, utgiver, år, opplag, sider
Stockholm: KTH Royal Institute of Technology, 2013. , s. 77
Serie
Trita-CHE-Report, ISSN 1654-1081 ; 2013:43
Emneord [en]
PEMFC; PEFC; Porous electrodes; Carbon corrosion; Carbon nanotubes; Carbon fibers; Polyhedral carbon nanofoams; Phosphonated hydrocarbon ionomer; Mass-transport losses; Electrode morphology; Electrode collapse; Start-up and shut-down; System strategies; Stainless steel; Bi-polar plates; In-situ contact resistance.
HSV kategori
Identifikatorer
URN: urn:nbn:se:kth:diva-133437ISBN: 978-91-7501-890-4 (tryckt)OAI: oai:DiVA.org:kth-133437DiVA, id: diva2:661230
Disputas
2013-11-22, Kollegisalen, Brinellvägen 8, plan 4, KTH, Stockholm, 10:00 (engelsk)
Opponent
Veileder
Merknad

QC 20131104

Tilgjengelig fra: 2013-11-04 Laget: 2013-11-01 Sist oppdatert: 2013-11-04bibliografisk kontrollert
Delarbeid
1. Active Area Determination of Porous Pt Electrodes Used in Polymer Electrolyte Fuel Cells: Temperature and Humidity Effects
Åpne denne publikasjonen i ny fane eller vindu >>Active Area Determination of Porous Pt Electrodes Used in Polymer Electrolyte Fuel Cells: Temperature and Humidity Effects
Vise andre…
2010 (engelsk)Inngår i: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 157, nr 12, s. B1795-B1801Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

This paper discusses the proper measure of the electrochemically active area (ECA)of carbon supported Pt catalyst in PEM fuel cells employing in situ cyclic voltammetry. The charges of the hydrogen underpotential deposition (Hupd) and CO stripping peak obtained in situ are compared, and the influence of operation temperature (25–80°C) and relative humidity (40%–90%) is discussed. The results show that the charges of the Hupd decrease with rising temperature, while the corresponding charges of the CO stripping peak are essentially independent of temperature, at least at high relative humidity. The unexpectedly small Hupd charges are explained by the significant overlap with the hydrogen evolution reaction in a fuel cell at elevated temperatures. According to our results, it is proposed that a more reliable value of Pt ECA is estimated from the CO stripping charge. However, with decreasing humidity the charges of both Hupd and CO stripping peaks decrease, which is probably an effect of increasing blockage of Pt active sites by hydrophobic domains in the electrode ionomer. Some implications of varying cell conditions on the estimated Pt ECA and its correlation with fuel cell activity are discussed in an example from a fuel cell degradation test.

Emneord
SINGLE-CRYSTAL SURFACES, CARBON-MONOXIDE, UNDERPOTENTIAL DEPOSITION, HYDROGEN ADSORPTION, MEMBRANE INTERFACE, PT(100) ELECTRODES, AQUEOUS H2SO4, CO OXIDATION, PLATINUM, ELECTROOXIDATION
HSV kategori
Identifikatorer
urn:nbn:se:kth:diva-25266 (URN)10.1149/1.3494220 (DOI)000283938300022 ()2-s2.0-78449298256 (Scopus ID)
Forskningsfinansiär
StandUp
Merknad

QC 20101014. Tidigare titel: Active Area Determination of Porous Pt Electrodes Used inPEM Fuel Cells: Temperature and Humidity Effects

Tilgjengelig fra: 2010-10-14 Laget: 2010-10-14 Sist oppdatert: 2017-12-12bibliografisk kontrollert
2. Performance of Phosphonated Hydrocarbon Ionomer in the Fuel Cell Cathode Catalyst Layer
Åpne denne publikasjonen i ny fane eller vindu >>Performance of Phosphonated Hydrocarbon Ionomer in the Fuel Cell Cathode Catalyst Layer
Vise andre…
2013 (engelsk)Inngår i: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 160, nr 3, s. F269-F277Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Inexpensive and environmentally friendly electrolyte polymers that can be operated at higher temperatures and drier conditions are highly interesting for PEM fuel cells for automotive, portable power and stationary electricity generation applications. In this study an ionomer based on polysulfone grafted with poly(vinylphosphonic acid) (PSUgPVPA) in the cathode Pt/C catalyst layer was electrochemically characterized and compared to Nafion. The performance at different levels of humidity at 80 degrees C was evaluated by polarization measurements, cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The results show that the performance of the PSUgPVPA-based cathode catalyst layer is comparable to that of Nafion-at 100% relative humidity (RH) but with some instabilities. However, at drier conditions significant losses of performance for the PSUgPVPA-based cathode was observed. This could be an effect of catalyst poisoning by the ionomer interfering with ORR. However, the concomitant decrease of the electrochemical surface area, double layer capacitance and increased imaginary impedance, indicate that the poorer performance at low humidity is mainly an effect of reduced catalyst wetting by the ionomer in combination with the decreased proton conduction in the ionomeric phase.

Emneord
Gas-Diffusion Electrodes, Mass-Transport Limitations, Proton-Exchange Membranes, Pefc Cathode, Poly(Vinylphosphonic Acid), Intermediate Temperature, Transient Techniques, Relative-Humidity, Protogenic Group, Side-Chains
HSV kategori
Identifikatorer
urn:nbn:se:kth:diva-119754 (URN)10.1149/2.046303jes (DOI)000315307500044 ()2-s2.0-84875455943 (Scopus ID)
Forskningsfinansiär
StandUp
Merknad

QC 20130322

Tilgjengelig fra: 2013-03-22 Laget: 2013-03-21 Sist oppdatert: 2017-12-06bibliografisk kontrollert
3. Graphitised Carbon Nanofibres as Catalyst Support for PEMFC
Åpne denne publikasjonen i ny fane eller vindu >>Graphitised Carbon Nanofibres as Catalyst Support for PEMFC
Vise andre…
2011 (engelsk)Inngår i: Fuel Cells, ISSN 1615-6846, E-ISSN 1615-6854, Vol. 11, nr 6, s. 715-725Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Graphitised carbon nanofibres (G-CNFs) show superior thermal stability and corrosion resistance in PEM fuel cell environment over traditional carbon black (CB) and carbon nanotube catalyst supports. However, G-CNFs have an inert surface with only very limited amount of surface defects for the anchorage of Pt catalyst nanoparticles. Modification of the fibre surface is therefore needed. In this study Pt nanoparticles have been deposited onto as-received and surface-modified G-CNFs. The surface modifications of the fibres comprise acid treatment and nitrogen doping by pyrolysis of a polyaniline (PANI) precursor. The modified surfaces were studied by FTIR and XPS and the electrochemical characterization, including long-term Pt stability tests, was performed using a low-temperature PEMFC single cell. The performance and stability of the G-CNF supported catalysts were compared with a CB supported catalyst and the effects of the different surface treatments were discussed. On the basis of these results, new membrane electrode assemblies (MEAs) were manufactured and tested also for carbon corrosion by in situ FTIR analysis of the cathode exhaust gases. It was observed that the G-CNFs showed 5?times lower carbon corrosion compared to CB based catalyst when potential reached 1.5?V versus RHE in simulated start/stop cycling.

sted, utgiver, år, opplag, sider
Wiley-Blackwell, 2011
Emneord
Carbon Corrosion, Carbon Nanofibres, Catalyst Stability, Catalyst Support, Proton Exchange Membrane Fuel Cell, Surface Modification
HSV kategori
Identifikatorer
urn:nbn:se:kth:diva-70040 (URN)10.1002/fuce.201000180 (DOI)000298317200002 ()2-s2.0-84055212712 (Scopus ID)
Forskningsfinansiär
StandUp
Merknad

QC 20120130

Tilgjengelig fra: 2012-01-30 Laget: 2012-01-30 Sist oppdatert: 2017-12-08bibliografisk kontrollert
4. The Electrochemical Response of a Corroded PEMFC Cathode: Mass-transport at low RH
Åpne denne publikasjonen i ny fane eller vindu >>The Electrochemical Response of a Corroded PEMFC Cathode: Mass-transport at low RH
(engelsk)Manuskript (preprint) (Annet vitenskapelig)
HSV kategori
Identifikatorer
urn:nbn:se:kth:diva-133451 (URN)
Forskningsfinansiär
StandUp
Merknad

QC 20160622

Tilgjengelig fra: 2013-11-04 Laget: 2013-11-04 Sist oppdatert: 2016-06-22bibliografisk kontrollert
5. Polyhedral Carbon Nanoforms as catalyst support in a Proton Exchange Membrance cathode
Åpne denne publikasjonen i ny fane eller vindu >>Polyhedral Carbon Nanoforms as catalyst support in a Proton Exchange Membrance cathode
Vise andre…
(engelsk)Manuskript (preprint) (Annet vitenskapelig)
HSV kategori
Identifikatorer
urn:nbn:se:kth:diva-133452 (URN)
Forskningsfinansiär
StandUp
Merknad

QS 2013

Tilgjengelig fra: 2013-11-04 Laget: 2013-11-04 Sist oppdatert: 2016-03-16bibliografisk kontrollert
6. Comparing shut-down strategies for proton exchange membrane fuel cells
Åpne denne publikasjonen i ny fane eller vindu >>Comparing shut-down strategies for proton exchange membrane fuel cells
Vise andre…
2014 (engelsk)Inngår i: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 254, s. 232-240Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Application of system strategies for mitigating carbon corrosion of the catalyst support in proton exchange fuel cells (PEMFCs) is a requirement for PEMFC systems, especially in the case of systems for transport application undergoing thousands of start-ups and shut-downs (SU/SD) during its lifetime. This study compares several of the most common shut-down strategies for 1100 cycles SU/SD cycles at 70 C and 80% RH using commercially available fuel cell components. Each cycle simulates a prolonged shut-down, i.e. finishing each cycle with air filled anode and cathode. Furthermore, all start-ups are unprotected, i.e. introducing the H2 rich gas into an air filled anode. Finally, each cycle also includes normal fuel cell operation at 0.5 A cm-2 using synthetic reformate/air. H2 purge of the cathode and O2 consumption using a load were found to be the most effective strategies. The degradation rate using the H2 purge strategy was 23 μV cycle-1 at 0.86 A cm-2 using H 2 and air at the anode and cathode, respectively. This degradation rate may be regarded as a generally low value, especially considering that this value also includes the degradation rate caused by unprotected start-ups.

Emneord
Carbon corrosion, Catalyst support, Proton exchange membrane fuel cell, Start-up and shut-down, System strategies
HSV kategori
Identifikatorer
urn:nbn:se:kth:diva-133453 (URN)10.1016/j.jpowsour.2013.12.058 (DOI)000332496300030 ()2-s2.0-84892760898 (Scopus ID)
Forskningsfinansiär
StandUp
Merknad

QC 20140305. Updated from manuscript to article in journal.

Tilgjengelig fra: 2013-11-04 Laget: 2013-11-04 Sist oppdatert: 2017-12-06bibliografisk kontrollert
7. Operating conditions affecting the contact resistance of bi-polar plates in proton exchange membrane fuel cells
Åpne denne publikasjonen i ny fane eller vindu >>Operating conditions affecting the contact resistance of bi-polar plates in proton exchange membrane fuel cells
Vise andre…
2013 (engelsk)Inngår i: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 231, s. 246-255Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Both ex-situ and in-situ measurements of contact resistance between gas diffusion layer (GDL) and bi-polar plate (BPP) were carried out using the same fuel cell hardware. Each BPP sample was submitted to ex-situ testing at room temperature, ex-situ testing in simulated fuel cell environment and in-situ testing, isolating the effect of specific operating conditions on the contact resistance. Increasing cell temperatures and relative humidity (RH) of the gases lowered the contact resistance. However, the presence of liquid water, measured as an increase in pressure drop over the cathode, affected the contact resistance negatively. High current density operation raises the temperature of the cell, but simultaneously increases the water content at the cathode, causing an increase of the contact resistance. In the case of uncoated steel 316L and gold-coated steel 316L, high current density operation for an extended period of time also caused a progressive deterioration of the contact resistance, which without this in-situ measurement could have been mistaken for other ohmic losses, e.g. increased membrane resistance due to metal ion poisoning.

Emneord
Bi-polar plate, Contact resistance, Durability, In-situ, PEM fuel cell, Stainless steel
HSV kategori
Identifikatorer
urn:nbn:se:kth:diva-119653 (URN)10.1016/j.jpowsour.2012.12.100 (DOI)000316036700032 ()2-s2.0-84872973902 (Scopus ID)
Forskningsfinansiär
Mistra - The Swedish Foundation for Strategic Environmental ResearchSwedish Research CouncilStandUp
Merknad

QC 20130320

Tilgjengelig fra: 2013-03-20 Laget: 2013-03-20 Sist oppdatert: 2017-12-06bibliografisk kontrollert

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