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Quantifying water transport in anion exchange membrane fuel cells
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0003-4770-9554
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.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.
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2019 (English)In: International journal of hydrogen energy, ISSN 0360-3199, E-ISSN 1879-3487, Vol. 44, no 10, p. 4930-4939Article in journal (Refereed) Published
Abstract [en]

Sufficient water transport through the membrane is necessary for a well-performing anion exchange membrane fuel cell (AEMFC). In this study, the water flux through a membrane electrode assembly (MEA), using a Tokuyama A201 membrane, is quantified using humidity sensors at the in- and outlet on both sides of the MEA. Experiments performed in humidified inert gas at both sides of the MEA or with liquid water at one side shows that the aggregation state of water has a large impact on the transport properties. The water fluxes are shown to be approximately three times larger for a membrane in contact with liquid water compared to vaporous. Further, the flux during fuel cell operation is investigated and shows that the transport rate of water in the membrane is affected by an applied current. The water vapor content increases on both the anode and cathode side of the AEMFC for all investigated current densities. Through modeling, an apparent water drag coefficient is determined to −0.64, indicating that the current-induced transport of water occurs in the opposite direction to the transport of hydroxide ions. These results implicate that flooding, on one or both electrodes, is a larger concern than dry-out in an AEMFC.

Place, publisher, year, edition, pages
Elsevier, 2019. Vol. 44, no 10, p. 4930-4939
Keywords [en]
Anion exchange membrane fuel cell, Fuel cells, Relative humidity sensor, Water transport model
National Category
Energy Systems
Identifiers
URN: urn:nbn:se:kth:diva-244325DOI: 10.1016/j.ijhydene.2018.12.185ISI: 000459837700036Scopus ID: 2-s2.0-85060083256OAI: oai:DiVA.org:kth-244325DiVA, id: diva2:1294014
Note

QC 20190306

Available from: 2019-03-06 Created: 2019-03-06 Last updated: 2024-08-15Bibliographically approved
In thesis
1. Electrochemical evaluation of new materials in polymer electrolyte fuel cells
Open this publication in new window or tab >>Electrochemical evaluation of new materials in polymer electrolyte fuel cells
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Polymer electrolyte fuel cells (PEFC) convert the chemical energy in hydrogen to electrical energy and heat, with the only exhaust being water. Fuel cells are considered key in achieving a sustainable energy sector. The main obstacles to wide scale commercialization are cost and durability. The aim of this thesis is to evaluate new materials for PEFC to potentially lower cost and increase durability. To lower the amount of expensive platinum catalyst in the fuel cell, the activities of Pt-rare earth metal (REM) alloy catalysts have been tested. To improve the lifetime of the carbon support, the carbon corrosion properties of multi walled carbon nanotubes have been evaluated. To reduce the overall cost of fuel cell stacks, carbon coated and metal coated bipolar plates have been tested. To increase the performance and lifetime of anion exchange membranes, the water transport has been studied.

The results show that the Pt-REM catalysts had at least two times higher specific activity than pure platinum, and even higher activities should be obtainable if the surface structures are further refined.

Multi-walled carbon nanotubes had lower carbon corrosion than conventional carbon Vulcan XC-72. However, once severely corroded their porous structure collapsed, causing major performance losses.

The carbon coated metallic bipolar plates showed no significant increase of internal contact resistance (ICR) by cycling, suggesting that these coatings are stable in fuel cells. The NiMo- and NiMoP coated bipolar plates showed low ICR, however, presence of the coated bipolar plates caused secondary harmful effects on the polymer membrane and ionomer.

Considering the water transport through anion exchange membranes it was found that most membranes showed very similar water transport properties, with more water detected at both the anode and cathode when a current was applied. The most significant factor governing the water transport properties was the membrane thickness, with thicker membranes reducing the backflow of water from anode to cathode.

The results indicate that all of the new tested materials have the capability to improve the lifetime and reduce cost and thereby improve the overall performance of PEFC.

Abstract [sv]

Polymerelektrolytbränsleceller (PEFC) omvandlar den kemiskt bundna energin i vätgas till elektrisk energi och värme, med endast vatten som utsläpp. Bränsleceller ses som en viktig del i att skapa en hållbar energisektor. Det största hindret för kommersialisering är kostnaden och den begränsande livslängden. Syftet med denna avhandling är att utvärdera nya material som skulle kunna sänka kostnaden och öka hållbarheten av PEFC. För att minska mängden dyr platinakatalysator i bränslecellen har aktiviteten av legerade katalysatorer av platina och sällsynta jordartsmetaller testats. För att öka livslängden av bränslecellen har kolkorrosionsegenskaperna av flerväggade kolnanorör (MWCNT) utvärderats. För att kunna minska den totala kostnaden på bränslecellsstacken har kol- och metallbelagda bipolära plattor undersökts. För att öka livslängden och öka prestandan av anjonledande membran har vattentransportegenskaperna av dessa membran studerats.

Resultaten visar att de legerade katalysatorerna hade mer än två gånger högre elektrokemisk aktivitet än ren platina. Ännu högre elektrokemiska aktiviteter bör kunna erhållas om ytstrukturen kan förbättra ytterligare.

För MWCNT var kolkorrosionen lägre än för de konventionella kolpartiklarna av Vulcan XC-72. Efter mycket korrosion, kollapsade dock den porösa strukturen, vilket ledde till stora förluster i prestanda.

De kolbelagda bipolära plattorna uppvisade inga signifikanta ändringar i kontaktmotstånd (ICR) efter de elektrokemiska testerna. Detta betyder att de är stabila i bränsleceller. De NiMo- och NiMoP-belagda bipolära plattorna hade låga ICR-värden, dock ledde beläggningens närvaro till försämringar av membran- och elektrodegenskaper.

Alla testade anjonledande membran uppvisade liknande vattentransportegenskaper, med ökning av vatten på både anoden och katoden under drift. Membranens tjocklek visade sig ha störst påverkan på vattentransporten. Med tjockare membran detekterades mindre vatten på katoden, vilket betyder att tillbakaflödet av vatten hämmas av membranets tjocklek.

Sammanfattningsvis visar resultaten att alla nya testade material i alla fall till viss del kan lösa problemen med den höga kostnaden och korta livslängden och därmed öka den totala prestandan av PEFC.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2019. p. 66
Series
TRITA-CBH-FOU ; 2019:50
Keywords
Fuel cell, Pt-REM, Alloy catalyst, Multi walled carbon nanotubes, Bipolar plates, Water transport, Bränslecell, Pt-REM, Legerad katalysator, Flerväggade kolnanorör, Bipolära plattor, Vattentransport
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-261102 (URN)978-91-7873-326-2 (ISBN)
Public defence
2019-11-05, F3, Lindstedtsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 2019-10-04

Available from: 2019-10-04 Created: 2019-10-03 Last updated: 2022-06-26Bibliographically approved
2. Electrochemical properties of alternative polymer electrolytes in fuel cells
Open this publication in new window or tab >>Electrochemical properties of alternative polymer electrolytes in fuel cells
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Fuel cells, using hydrogen as energy carrier, allow chemically‑stored energy to be utilized for many applications, including balancing the electrical grid and the propulsion of vehicles. To make the fuel cell technology more accessible and promote a sustainable energy society, this thesis focuses on alternative polymer electrolytes, as they can potentially lead to a lower cost and a more environmentally‑friendly fuel cell. The main subject is anion exchange membrane fuel cells (AEMFCs), for which the importance of gas diffusion electrode morphology and platinum electrode reactions are investigated. Properties of the membrane such as water flux during operation are evaluated. Furthermore, novel polymer electrolytes are studied: variations of poly(phenylene oxide)‑based membranes in AEMFCs; and cellulose‑based membranes in a proton exchange membrane fuel cell (PEMFC).

 

The AEMFC results show that the performance is dependent on the electrode morphology. Electrochemical experiments in a hydrogen/hydrogen cell combined with modelling show that the hydrogen oxidation reaction proceeds through the Tafel‑Volmer reaction pathway on platinum. Application of the model in a hydrogen/oxygen cell shows that the cathode has the slowest reaction rate. During operation, the water flux through the membrane is directed from the anode where water is produced to the cathode where it is consumed. This leads to an increase in water content at both electrodes, which implies that electrode flooding is more likely than dry‑out during operation. The effect of membrane thickness on water flux is shown to be larger than the effect of polymer structure for several different types of poly(phenylene oxide)‑based membranes. The comparison of these polymers also indicates that a high conductivity, for the relative humidity achieved in a fuel cell, promotes increased performance. Finally, the study of cellulose-based membranes in a PEMFC shows that cellulose as a renewable, natural polymer has promising properties, such as stable conductivity for relative humidities above 65 % and a low gas permeability.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2019. p. 59
Series
TRITA-CBH-FOU ; 2019:64
Keywords
fuel cell, anion exchange membrane, proton exchange membrane, electrode morphology, hydrogen oxidation reaction, water transport, poly(phenylene oxide), cellulose, bränslecell, anjonledande membran, protonledande membran, elektrodstruktur, vätgasoxidation, vattentransport, poly(fenylenoxid), cellulosa
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-263095 (URN)978-91-7873-365-1 (ISBN)
Public defence
2019-11-29, F3, Lindstedtsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2019-10-29 Created: 2019-10-29 Last updated: 2022-06-26Bibliographically approved
3. 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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Eriksson, BjörnGrimler, HenrikCarlson, AnnikaEkström, HenrikWreland Lindström, RakelLindbergh, GöranLagergren, Carina

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