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Determination of Kinetic Parameters for the Oxygen Reduction Reaction on Platinum in an AEMFC
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0003-0897-7249
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0002-1923-8479
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry. COMSOL AB, SE-11140 Stockholm, Sweden..ORCID iD: 0000-0001-9627-1902
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0002-2268-5042
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2021 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 168, no 12, p. 124501-, article id 124501Article in journal (Refereed) Published
Abstract [en]

To promote the development of anion exchange membrane fuel cells (AEMFC), an understanding of the oxygen reduction reaction (ORR) kinetics in porous gas diffusion electrodes is essential. In this work, experimental polarisation curves for electrodes with different platinum catalyst loadings and oxygen partial pressures at the cathode are fitted to a physics-based porous electrode model in the voltage range from open circuit voltage (OCV) to 0.7 V. Polarisation curves measured with different anode catalyst loadings, and hydrogen partial pressures, were used to verify the model. The reactions are described using a two-step Tafel-Volmer pathway at the anode and concentration-dependent Butler-Volmer kinetics at the cathode. A good fit to experimental data in the kinetic region is obtained with an exchange current density of 1.0.10(-8)Acm(-2), a first order dependency on oxygen partial pressure, and a charge transfer coefficient of 0.8 for the ORR. For lower oxygen partial pressure, hydrogen crossover is needed to explain the downward shift of the polarisation curves in the kinetic region. In the experimental data, the polarisation curves show an apparent limiting current density at lower hydrogen partial pressures, explained by the lower rate of the Tafel step at these conditions.

Place, publisher, year, edition, pages
The Electrochemical Society , 2021. Vol. 168, no 12, p. 124501-, article id 124501
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-306530DOI: 10.1149/1945-7111/ac38f8ISI: 000728124400001Scopus ID: 2-s2.0-85122583697OAI: oai:DiVA.org:kth-306530DiVA, id: diva2:1622722
Note

QC 20211223

Available from: 2021-12-23 Created: 2021-12-23 Last updated: 2022-11-18Bibliographically approved
In thesis
1. Limiting processes in anion-exchange membrane fuel cells
Open this publication in new window or tab >>Limiting processes in anion-exchange membrane fuel cells
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Fuel cells allow for converting chemical energy stored in hydrogen into electrical energy, with only heat and water as by-products. In a sustainable energy society, hydrogen may play an important role due to its ability to act both as an energy carrier and as a valuable chemical in the process industry. The main remaining obstacles for widely available commercial fuel cells are durability and cost. One way to potentially decrease the cost is to change the fuel cell environment to an alternative chemistry by replacing the proton-exchange membrane (PEM) with an anion-exchange membrane (AEM). This thesis studies the anode reaction, the cathode reaction and water transport in an anion-exchange membrane fuel cell (AEMFC), to investigate where its performance limitations lies in the system. Electrochemical characterisation techniques together with physics-based modelling have been utilised.

The results from the study of the anode, shows that the hydrogen reaction proceeds through the Tafel-Volmer pathway, with the Tafel step starting to limit the reaction as the anode overpotential increases. Combining the anode model with a Butler-Volmer expression for the cathode reaction made it possible to model a H2:O2 fuel cell. Comparing the losses from the different processes in the fuel cell shows that the cathode is still the main contributor, but that the anode contribution cannot be neglected when predicting the fuel cell performance. Low ionic conductivity in the electrode was also identified as responsible for part of the overall resistances, leading to uneven current distribution in the catalyst layers and bad utilisation of the catalytic material.

Investigating the water transport properties of AEMs showed that not only electroosmotic drag and diffusion, but also an absorption/desorption step between gas phase and membrane phase, are necessary to get a model that can explain the experimental observations. The choice of gas diffusion layers (GDLs) used on the anode and cathode was found to be of similar importance on the water transport as doubling the membrane thickness, showing that not only the membrane is important for water transport. Under most realistic conditions, the risk of local dry-out in a cell was found to be low, as water readily diffuses from the high humidity side of the membrane to the low humidity side.

Abstract [sv]

Bränsleceller gör det möjligt att konvertera kemisk energi lagrad i vätgas till elektrisk energi, med endast värme och vatten som biprodukter. I ett hållbart energisamhälle kan vätgas spela en viktig roll tack vare sin förmåga att agera både som energibärare och som en värdefull kemikalie i industrin. De sista hindren innan bränsleceller kan bli brett tillgängliga kommersiellt är deras livslängd och kostnad. Ett sätt att minimera kostnaden är att byta till en annan bränslecellskemi, genom att ersätta det protonledande membranet med ett anjonledande membran. Denna avhandling syftar till att undersöka begränsningar i anjonledande membranbränsleceller som hämmar utvecklingen och kommersialiseringen av dessa bränsleceller. Fokus i deolika delstudierna har varit på anoden, katoden, och vattentransporten i det anjonledande membranet.

Resultaten från undersökning av vätgaselektroden visade att reaktionen följer en Tafel-Volmer mekanism, i vilken Tafelsteget börjar begränsa hastigheten när överpotentialen på anoden ökar. Genom att kombinera anodmodellen med ett Butler-Volmer-uttryck för katodreaktionen så var det möjligt att modellera en H2:O2 bränslecell. Från en jämförelse av förlusterna från de olika processerna i bränslecellen kan vi dra slutsatsen att katoden fortfarande dominerar, men att hänsyn också måste tas till anodförlusterna om bränslecellens prestanda ska förutsägas. Låg jonledningsförmåga i elektroderna identifierades också som orsak för en del av förlusterna, vilket leder till ojämn strömfördelning i katalysatorskikten och begränsad utnyttjandegrad av katalysatormaterialet.

Undersökningar av vattentransportegenskaperna av anjonledande membran visade att inte bara elektroosmotisk diffusionsmotstånd och diffusion, utan också ett absorption-desorptions-steg mellan gasfasen och membranfasen bör inkluderas för att få en rimlig modell av vattentransporten. Att välja en lämplig kombination med avseende på hydrofobicitet av gasdiffusionsskikt visade sig vara lika avgörande som att dubbla membrantjockleken, vilket visar att inte bara permeabiliteten i membranet spelar roll för vattentransporten. Under de flesta realistiska förhållandena är risken för lokal uttorkning av elektroderna liten, tack vare att vatten snabbt kan diffundera från sidan med hög fuktighet till sidan med låg fuktighet.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2022. p. 60
Series
TRITA-CBH-FOU ; 2022:58
Keywords
anion-exchange membrane fuel cell, hydrogen oxidation reaction, oxygen reduction reaction, water transport, physics-based modelling
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-321600 (URN)978-91-8040-417-4 (ISBN)
Public defence
2022-12-16, D2, Lindstedtsvägen 5, via Zoom: https://kth-se.zoom.us/meeting/register/u5UrcOmqrTMoH9IQlT682yjBTuzuwVUylXBJ, Stockholm, 14:00 (English)
Opponent
Supervisors
Funder
Swedish Foundation for Strategic Research, EM16–0060Swedish Foundation for Strategic Research, ARC19–0026Swedish Energy Agency, P41397-1StandUp
Note

QC 2022-11-21

Available from: 2022-11-21 Created: 2022-11-18 Last updated: 2022-11-21Bibliographically approved

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Grimler, HenrikCarlson, AnnikaEkström, HenrikLagergren, CarinaWreland Lindström, RakelLindbergh, Göran

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