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Ammonia contamination of a proton exchange membrane fuel cell
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0002-1626-1067
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0001-9203-9313
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.
2018 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 165, no 3, p. F189-F197Article in journal (Refereed) Published
Abstract [en]

Reformate hydrogen from biogas is an attractive fuel alternative for energy conversion in PEM fuel cells. However, in the reformate traces of ammonia may be found, e.g. if the biogas is produced from agricultural resources. In this investigation the effect of ammonia in the fuel gas, on each part of the fuel cell, is studied by cyclic voltammetry, electrochemical impedance spectroscopy (EIS), symmetrical hydrogen cell (H2|H2)- and real fuel cell operation. A considerable degradation in performance is observed by introducing 200 ppm ammonia. The results show that ammonia not only affects the polymer electrolyte membrane but also the oxygen reduction reaction (ORR) and catalyst ionomer in both electrodes, whereas the hydrogen oxidation reaction (HOR) is the worst affected. In the short-term, the performance is reversible if running the cell on neat hydrogen after ammonia exposure, but this does not apply for long-term exposure. A mitigation method with air bleed is tested but gives no improvement of the performance.

Place, publisher, year, edition, pages
Electrochemical Society, 2018. Vol. 165, no 3, p. F189-F197
National Category
Other Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-225020DOI: 10.1149/2.0761803jesISI: 000431790700083Scopus ID: 2-s2.0-85043771326OAI: oai:DiVA.org:kth-225020DiVA, id: diva2:1193902
Funder
StandUp
Note

QC 20180328

Available from: 2018-03-28 Created: 2018-03-28 Last updated: 2024-03-15Bibliographically approved
In thesis
1. On Gas Contaminants, and Bipolar Plates in Proton Exchange Membrane Fuel Cells
Open this publication in new window or tab >>On Gas Contaminants, and Bipolar Plates in Proton Exchange Membrane Fuel Cells
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The proton exchange membrane (PEM) fuel cell is an electrochemical device that converts chemical energy into electrical energy through two electrocatalytic reactions. The most common catalyst used is platinum on carbon (Pt/C), which has shown the best performance in the fuel cell until now. However, the drawback of this catalyst is that it does not tolerate impurities, and both hydrogen and oxygen may carry small amounts of impurities depending on the production sources. The purpose of this thesis is to understand the effect of two impurities that are less investigated, i.e., ammonia, which may accompany the hydrogen rich reformates from renewable sources, and nitrogen dioxide, which may come from air pollution. The mechanism of contamination and an adequate recovery method for the respective contaminant are studied. Additionally, electroplated bipolar plates with Ni-Mo and Ni-Mo-P coatings were tested as alternatives to stainless steel and carbon materials.

The results show that ammonia not only provokes changes in the polymer membrane but also in the oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR) and catalyst ionomer in both electrodes. The extent of performance recovery after the contamination depends on the concentration used and the exposure time. In contrast, nitrogen dioxide affects the catalyst in the electrode directly; the contamination is related to side reactions that are produced on the catalyst’s surface. However, NO2 is not attached strongly to the catalyst and it is possible to restore the performance by using clean air. The time the recovery process takes depends on the potential applied and the air flow.

Finally, the evaluation of electroplated Ni-Mo and Ni-Mo-P on stainless steel by ex situ and in situ studies shows that these coatings reduce the internal contact resistance (ICR) and the corrosion rate of the stainless steel considerably. However, the in situ experiments show that phosphorus addition to the coating does not improve the fuel cell performance; thus, the Ni-Mo alloy is found to be a promising choice for electroplating stainless steel bipolar plates.

Abstract [sv]

Polymerelektrolytbränslecellen är en elektrokemisk enhet som omvandlar den kemiskt bundna energin i ett bränsle till elektrisk energi genom två elektrokatalytiska reaktioner. Den vanligaste katalysatorn som används är Pt/C som hittills också har visat bäst prestanda i bränslecellen. Nackdelen med denna katalysator är dock att den inte tolererar föroreningar. Både vätgas och syrgas kan innehålla små mängder av föroreningar beroende på ursprung. Syftet med denna avhandling är att förstå effekten på cellens prestanda av två olika föroreningar som är mindre undersökta: Ammoniak som kan medfölja vid reformering av förnybara råvaror till vätgas, och kvävedioxid som kan komma från luftföroreningar. Mekanismer för förorening av cellen och en adekvat återhämtningsmetod för respektive förorening har studerats. Dessutom, bipolära plattor av rostfritt stål elektrokemiskt belagda med Ni-Mo eller Ni-Mo-P, undersökts som ett alternativ till rent rostfritt stål- och grafit.

Resultaten visar att ammoniak inte bara åstadkommer förändringar i polymermembranet utan också i syrereduktionsreaktionen (ORR), väteoxidationsreaktionen (HOR) och jonomeren i de båda elektroderna. Till vilken grad som försämrad prestanda efter förorening kan återhämtas, beror både på koncentrationen av ammoniak och exponeringstid. När det gäller kvävedioxid så påverkar en bara elektrodens katalysator där försämringen av elektroden är relaterad till sidoreaktioner som sker på katalysatorytan. NO2 är dock inte starkt bunden till katalysatorn och det är möjligt att återhämta prestandan med bara ren luft. Tiden som återhämtningsprocessen tar beror på cellpotentialen och luftflödet.

Utvärderingen av elektropläterade skikt av Ni-Mo och Ni-Mo-P på rostfritt stål, som gjorts genom mätningar ex-situ och in-situ, visar att dessa beläggningar avsevärt minskar det interna kontaktmotståndet (ICR) och korrosionen av rostfritt stål. In-situ-experimenten visar att tillsatsen av  fosfor i beläggningen inte förbättrar bränslecellens prestanda, men att legering av Ni-Mo är ett lovande material att använda vid elektroplätering av skyddande skikt på bipolära plattor av rostfritt stål.

Place, publisher, year, edition, pages
Stockholm: Kungliga Tekniska högskolan, 2019. p. 58
Series
TRITA-CBH-FOU ; 2019:6
Keywords
PEM fuel cell, contaminants, ammonia, nitrogen dioxide, degradation, recovery, bipolar plates, electroplating, Ni-Mo, Ni-Mo-P, internal contact resistance, PEM bränslecell, föroreningar, ammoniak, kvävedioxid, degradering, återhämtning, bipolära plattor, elektroplätering, Ni-Mo, Ni-Mo-P, interna kontaktmotståndet
National Category
Other Chemical Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-241911 (URN)978-91-7873-092-6 (ISBN)
Public defence
2019-02-28, F3, Lindstedtsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20190128

Available from: 2019-01-28 Created: 2019-01-25 Last updated: 2022-06-26Bibliographically approved

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Gomez, Yasna AcevedoOyarce, AlejandroLindbergh, GöranLagergren, Carina

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