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Demonstrating the absence of metal ion contamination in operando PEM fuel cells utilizing unmodified stainless steel bipolar plates
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0002-7919-8835
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0003-4770-9554
Alleima, Strateg Res, SE-81181 Sandviken, Sweden..
SSAB EMEA AB, Prod Dev, S-78184 Borlänge, Sweden..
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2023 (English)In: Applied Energy, ISSN 0306-2619, E-ISSN 1872-9118, Vol. 349, article id 121669Article in journal (Refereed) Published
Abstract [en]

Using stainless steel as material for bipolar plates (BPPs) in proton exchange membrane fuel cells (PEMFCs) carries a perceived risk of corrosion and subsequent metal ion contamination of the membrane electrode as-sembly (MEA). However, assessments in literature on this hazard to PEMFC systems have been based on ex-situ corrosion studies, where general assumptions made on the BPP environment might not be a correct simulation of real on-site conditions. In this contribution, uncoated BPPs from stainless steel grades 304 L, 316 L and 904 L were subjected to in-situ hybrid endurance/stress testing to simulate realistic conditions in operating fuel cell systems and re-evaluate the need of additional corrosion protection. A post analysis of the plates showed no signs of surface dissolution on any of the tested samples and the concentration of iron in the MEA averaged 7 to 10 ppm for uncoated samples and 7 to 11 ppm for coated and graphitic reference tests, displaying a negligible amount of trace metals compared to critical thresholds found in literature. Contact resistance values were stable for all samples and observable changes in cell performance and voltage degradation was confirmed to be un-related to the presence of uncoated bipolar plates. The combined effects of decoupling of bipolar plate surface potentials from electrode potentials and operational control of stable gas flow compositions to sustain stainless steel surface passivation, were identified as explanation for the experimentally observed corrosion resistance of uncoated stainless steel plates in PEMFCs.

Place, publisher, year, edition, pages
Elsevier BV , 2023. Vol. 349, article id 121669
Keywords [en]
Proton exchange membrane fuel cell, Bipolar plate, Corrosion mechanism, Stainless steel passivation, Ionic decoupling
National Category
Energy Engineering
Identifiers
URN: urn:nbn:se:kth:diva-335165DOI: 10.1016/j.apenergy.2023.121669ISI: 001047409400001Scopus ID: 2-s2.0-85166186043OAI: oai:DiVA.org:kth-335165DiVA, id: diva2:1793964
Note

QC 20230904

Available from: 2023-09-04 Created: 2023-09-04 Last updated: 2024-08-23Bibliographically approved
In thesis
1. Electrochemical characterization of materials for next generation polymer electrolyte fuel cells
Open this publication in new window or tab >>Electrochemical characterization of materials for next generation polymer electrolyte fuel cells
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Polymer electrolyte fuel cells occupy a key position in implementing the hydrogen economy on a global scale. However, assessments of cost, availability and sustainability of materials currently used to manufacture state-of-the-art fuel cell stacks have given cause for concern. Platinum and platinum-group metals are prohibitively expensive and of low abundance. The benchmark ion-conductive polymer NafionTM and related perfluorosulfonic acid-based polymers are difficult to synthesize and environmentally persistent to extreme degrees. Graphitic and carbon composite bipolar plates are unsuitable for mass production and have low recycling potential. In the compiled works, alternative materials were evaluated both for the acidic and alkaline variations of polymer electrolyte fuel cells. Electrochemical characterization was carried out in single cell tests with a focus on finding the limitations in terms of ohmic, charge transfer and transport resistances in the cell, through polarization and impedance measurements.

Carbon coated stainless steel bipolar plates were tested operando in a proton exchange membrane fuel cell (PEMFC) under realistic conditions based on the New European Drive Cycle. Observed trace metal contamination of the MEA was linked to metal dissolution from coating defects caused by manufacturing (Paper I). A theoretical understanding of observed metal dissolution was confirmed experimentally and a concept for preventing metal dissolution was developed for PEMFC bipolar plates (Paper II). The developed concept was extended to uncoated stainless steel bipolar plates and tested successfully for three stainless steel types in operando PEMFC (Paper III)

Anion exchange polymers based on poly(arylene piperidinium) (PAP) were tested as both membranes and ionomers in a comparative study with a commercial reference material, showing higher performance and the significance of ionomer-carbon support interactions (Paper IV). PAP-based ionomers with varying ion exchange capacities were studied to optimize electrodes in anion exchange membrane fuel cells (AEMFC). A combination of high ion exchange capacity ionomer on both cathode and anode was best performing, linked to small water transport resistance in cathode and increased kinetic contribution of the anode HOR (Paper V). The effects of modifying the catalyst layer through the introduction of crosslinked PAP particles were studied in operando AEMFCs. A positive impact on charge transfer and diffusion resistances in electrodes containing particles could be observed. (Paper VI).

Silver nanoparticles were used as catalyst material in the cathode of previously optimized membrane electrode assemblies in AEMFC. The results showed promising performance compared to platinum electrodes based on monetary and sustainability considerations, but also challenges regarding catalyst stability and detrimental silver-ionomer interactions. (Paper VII).

Abstract [sv]

Bränsleceller med polymerelektrolyt har en avgörande roll för implementering av vätgasekonomin globalt. Faktorer som kostnad, tillgänglighet och miljöpåverkan av material som för närvarande används i moderna bränsleceller är dock ett bekymmer. Platina och platinagruppmetaller är dyra och sällsynt förekommande. Den dominerande jonledande polymeren NafionTM och liknande perfluorsulfonsyra-baserade polymerer är krävande att syntetisera och svårnedbrytbara i naturen. Bipolära plattor av grafit och kolkomposit är olämpliga för massproduktion och har låg återvinningspotential. I avhandlingens sammanställda arbeten utvärderades alternativa material både för de sura (PEMFC) och de alkaliska (AEMFC) varianterna av polymerelektrolytbränsleceller. Elektrokemisk karakterisering med polarisations- och impedansmätningar genomfördes i enkelceller för att studera begränsningarna vad gäller laddningsöverföring samt ohmska och transportrelaterade förluster i cellen.

Kolbelagda bipolära plattor av rostfritt stål undersöktes in operando i en PEMFC under realistiska förhållanden baserade på en standardiserad europeisk driftcykel. Spår av metalljoner i cellkomponenterna observerades efter test och kopplades till metallupplösning från defekter orsakade vid tillverkningen (Paper I). Upplösningen visade sig bero på potentialgradienter som uppstod vid förändringar i gassammansättningen och kunde undvikas med bättre reglerade flöden (Paper II). Tre typer av rostfritt stål utan kolbeläggning jämfördes i operando PEMFC med belagda bipolära plattor Inte i något av fallen påvisades någon metalljonupplösning(Paper III).

Anjonbytarpolymerer baserade på poly(arylenpiperidinium) (PAP) undersöktes både som membran och jonomer. I en jämförande studie med ett kommersiellt Aemion-material visade PAP högre prestanda. Vidare visade studien att interaktionen mellan jonomer och bärarkol hade betydelse för prestandan (Paper IV). PAP-baserade jonomerer med varierande jonbyteskapacitet studerades för att optimera elektroder i AEMFC. En kombination med jonomer med hög jonbyteskapacitet på både katod och anod var bäst, och kopplad till litet vattentransportmotstånd i katoden och ökat kinetiskt bidrag från anodreaktionen (Paper V). Effekterna av att modifiera katalysatorskiktet genom införandet av tvärbundna PAP-partiklar studerades i operando AEMFCs. En positiv inverkan på laddningsöverföring och diffusionsmotstånd i elektroder som innehåller partiklar kunde observeras. (Paper VI). 

Slutligen användes silvernanopartiklar som katodkatalysator i AEMFC med elektroder optimerade med PAP. Resultaten visade lovande prestanda jämfört med platinaelektroder, utifrån kostnads- och hållbarhetsaspekter, men också utmaningar gällande katalysatorns stabilitet och interaktionen mellan silver och jonomer. (Paper VII).

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2023. p. 114
Series
TRITA-CBH-FOU ; 2023:59
Keywords
Polymer electrolyte fuel cells, PEMFC, AEMFC, bipolar plates, corrosion, poly(arylene piperidinium), ionomer, electrode structure, silver nanoparticles, oxygen reduction reaction, Polymerelektrolytbränsleceller, PEMFC, AEMFC, bipolära plattor, korrosion, poly(arylenpiperidinium), jonomer, elektrodstruktur, silvernanopartiklar, syrgasreduktionsreaktion
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-340853 (URN)978-91-8040-794-6 (ISBN)
Public defence
2024-01-26, F3 (Flodis), Lindstedtsvägen 26, KTH, https://kth-se.zoom.us/meeting/register/u5wlcOGuqTwiGNXzKR_gDsNo2rokLVn_pyFk, Stockholm, 10:00 (English)
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Note

QC 20231218

Available from: 2023-12-18 Created: 2023-12-15 Last updated: 2024-01-15Bibliographically approved

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Novalin, TimonEriksson, BjörnLagergren, CarinaLindbergh, GöranWreland Lindström, Rakel

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