Improved Fuel Cell Chemical Durability of an Heteropoly Acid Functionalized Perfluorinated Terpolymer-Perfluorosulfonic Acid Composite Membrane

Chul Oong Kim; Ivy Wu; Mei Chen Kuo; Dominic J. Carmosino; Ethan W. Bloom; Soenke Seifert; David A. Cullen; Phuc Ha; Matthew J. Lindell; Ruichun Jiang; Craig S. Gittleman; Michael A. Yandrasits; Andrew M. Herring

doi:10.1149/1945-7111/acb848

Improved Fuel Cell Chemical Durability of an Heteropoly Acid Functionalized Perfluorinated Terpolymer-Perfluorosulfonic Acid Composite Membrane

Chul Oong Kim, Ivy Wu, Mei Chen Kuo, Dominic J. Carmosino, Ethan W. Bloom, Soenke Seifert, David A. Cullen, Phuc Ha, Matthew J. Lindell, Ruichun Jiang, Craig S. Gittleman, Michael A. Yandrasits, Andrew M. Herring

Materials MicroAnalysis

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

Commercial proton exchange membrane heavy-duty fuel cell vehicles will require a five-fold increase in durability compared to current state-of-the art light-duty fuel cell vehicles. We describe a new composite membrane that incorporates silicotungstic heteroply acid (HPA), α-K₈SiW₁₁O₄₀▪13H₂O, a radical decomposition catalyst and when acid-exchanged can potentially conduct protons. The HPA was covalently bound to a terpolymer of tetrafluoroethylene, vinylidene fluoride, and sulfonyl fluoride containing monomer (1,1,2,2,3,3,4,4-octafluoro-4-((1,2,2-trifluorovinyl)oxy)butane-1-sulfonyl fluoride) by dehydrofluorination followed by addition of diethyl (4-hydroxyphenyl) phosphonate, giving a perfluorosulfonic acid-vinylidene fluoride-heteropoly acid (PFSA-VDF-HPA). A composite membrane was fabricated using a blend of the PFSA-VDF-HPA and the 800EW 3M perfluoro sulfonic acid polymer. The bottom liner-side of the membrane tended to have a higher proportion of HPA moieties compared to the air-side as gravity caused the higher mass density PFSA-VDF-HPA to settle. The composite membrane was shown to have less swelling, more hydrophobic properties, and higher crystallinity than the pure PFSA membrane. The proton conductivity of the membrane was 0.130 ± 0.03 S cm⁻¹ at 80 °C and 95% RH. Impressively, when the membrane with HPA-rich side was facing the anode, the membrane survived more than 800 h under accelerated stress test conditions of open-circuit voltage, 90 °C and 30% RH.

Original language	English
Article number	024505
Journal	Journal of the Electrochemical Society
Volume	170
Issue number	2
DOIs	https://doi.org/10.1149/1945-7111/acb848
State	Published - Feb 2023

Funding

This work was partially supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy under grant DE-EE0008821. This research used resources of the Colorado School of Mines Shared Instrument Facility (CSM SIF) and SEM instrument used for the imaging and specimen preparation was acquired through the support of the National Science Foundation (DMR-1828454). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Electron microscopy was conducted under the Million Mile Fuel Cell Truck (M2FCT) Consortium (〈https://millionmilefuelcelltruck.org〉), technology manager Greg Kleen, which is supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office. STEM-EDS was conducted as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. This work was partially supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy under grant DE-EE0008821. This research used resources of the Colorado School of Mines Shared Instrument Facility (CSM SIF) and SEM instrument used for the imaging and specimen preparation was acquired through the support of the National Science Foundation (DMR-1828454). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02–06CH11357. Electron microscopy was conducted under the Million Mile Fuel Cell Truck (M2FCT) Consortium (〈 https://millionmilefuelcelltruck.org 〉), technology manager Greg Kleen, which is supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office. STEM-EDS was conducted as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory.

Funders	Funder number
M2FCT
National Science Foundation	DMR-1828454
U.S. Department of Energy
Office of Science
Office of Energy Efficiency and Renewable Energy	DE-EE0008821
Argonne National Laboratory	DE-AC02–06CH11357
Oak Ridge National Laboratory
Hydrogen and Fuel Cell Technologies Office

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This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1149/1945-7111/acb848

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Kim, C. O., Wu, I., Kuo, M. C., Carmosino, D. J., Bloom, E. W., Seifert, S., Cullen, D. A., Ha, P., Lindell, M. J., Jiang, R., Gittleman, C. S., Yandrasits, M. A., & Herring, A. M. (2023). Improved Fuel Cell Chemical Durability of an Heteropoly Acid Functionalized Perfluorinated Terpolymer-Perfluorosulfonic Acid Composite Membrane. Journal of the Electrochemical Society, 170(2), Article 024505. https://doi.org/10.1149/1945-7111/acb848

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title = "Improved Fuel Cell Chemical Durability of an Heteropoly Acid Functionalized Perfluorinated Terpolymer-Perfluorosulfonic Acid Composite Membrane",

abstract = "Commercial proton exchange membrane heavy-duty fuel cell vehicles will require a five-fold increase in durability compared to current state-of-the art light-duty fuel cell vehicles. We describe a new composite membrane that incorporates silicotungstic heteroply acid (HPA), α-K8SiW11O40▪13H2O, a radical decomposition catalyst and when acid-exchanged can potentially conduct protons. The HPA was covalently bound to a terpolymer of tetrafluoroethylene, vinylidene fluoride, and sulfonyl fluoride containing monomer (1,1,2,2,3,3,4,4-octafluoro-4-((1,2,2-trifluorovinyl)oxy)butane-1-sulfonyl fluoride) by dehydrofluorination followed by addition of diethyl (4-hydroxyphenyl) phosphonate, giving a perfluorosulfonic acid-vinylidene fluoride-heteropoly acid (PFSA-VDF-HPA). A composite membrane was fabricated using a blend of the PFSA-VDF-HPA and the 800EW 3M perfluoro sulfonic acid polymer. The bottom liner-side of the membrane tended to have a higher proportion of HPA moieties compared to the air-side as gravity caused the higher mass density PFSA-VDF-HPA to settle. The composite membrane was shown to have less swelling, more hydrophobic properties, and higher crystallinity than the pure PFSA membrane. The proton conductivity of the membrane was 0.130 ± 0.03 S cm−1 at 80 °C and 95% RH. Impressively, when the membrane with HPA-rich side was facing the anode, the membrane survived more than 800 h under accelerated stress test conditions of open-circuit voltage, 90 °C and 30% RH.",

author = "Kim, {Chul Oong} and Ivy Wu and Kuo, {Mei Chen} and Carmosino, {Dominic J.} and Bloom, {Ethan W.} and Soenke Seifert and Cullen, {David A.} and Phuc Ha and Lindell, {Matthew J.} and Ruichun Jiang and Gittleman, {Craig S.} and Yandrasits, {Michael A.} and Herring, {Andrew M.}",

note = "Publisher Copyright: {\textcopyright} 2023 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited.",

year = "2023",

month = feb,

doi = "10.1149/1945-7111/acb848",

language = "English",

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journal = "Journal of the Electrochemical Society",

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Kim, CO, Wu, I, Kuo, MC, Carmosino, DJ, Bloom, EW, Seifert, S, Cullen, DA, Ha, P, Lindell, MJ, Jiang, R, Gittleman, CS, Yandrasits, MA & Herring, AM 2023, 'Improved Fuel Cell Chemical Durability of an Heteropoly Acid Functionalized Perfluorinated Terpolymer-Perfluorosulfonic Acid Composite Membrane', Journal of the Electrochemical Society, vol. 170, no. 2, 024505. https://doi.org/10.1149/1945-7111/acb848

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T1 - Improved Fuel Cell Chemical Durability of an Heteropoly Acid Functionalized Perfluorinated Terpolymer-Perfluorosulfonic Acid Composite Membrane

AU - Kim, Chul Oong

AU - Wu, Ivy

AU - Kuo, Mei Chen

AU - Carmosino, Dominic J.

AU - Bloom, Ethan W.

AU - Seifert, Soenke

AU - Cullen, David A.

AU - Ha, Phuc

AU - Lindell, Matthew J.

AU - Jiang, Ruichun

AU - Gittleman, Craig S.

AU - Yandrasits, Michael A.

AU - Herring, Andrew M.

PY - 2023/2

Y1 - 2023/2

N2 - Commercial proton exchange membrane heavy-duty fuel cell vehicles will require a five-fold increase in durability compared to current state-of-the art light-duty fuel cell vehicles. We describe a new composite membrane that incorporates silicotungstic heteroply acid (HPA), α-K8SiW11O40▪13H2O, a radical decomposition catalyst and when acid-exchanged can potentially conduct protons. The HPA was covalently bound to a terpolymer of tetrafluoroethylene, vinylidene fluoride, and sulfonyl fluoride containing monomer (1,1,2,2,3,3,4,4-octafluoro-4-((1,2,2-trifluorovinyl)oxy)butane-1-sulfonyl fluoride) by dehydrofluorination followed by addition of diethyl (4-hydroxyphenyl) phosphonate, giving a perfluorosulfonic acid-vinylidene fluoride-heteropoly acid (PFSA-VDF-HPA). A composite membrane was fabricated using a blend of the PFSA-VDF-HPA and the 800EW 3M perfluoro sulfonic acid polymer. The bottom liner-side of the membrane tended to have a higher proportion of HPA moieties compared to the air-side as gravity caused the higher mass density PFSA-VDF-HPA to settle. The composite membrane was shown to have less swelling, more hydrophobic properties, and higher crystallinity than the pure PFSA membrane. The proton conductivity of the membrane was 0.130 ± 0.03 S cm−1 at 80 °C and 95% RH. Impressively, when the membrane with HPA-rich side was facing the anode, the membrane survived more than 800 h under accelerated stress test conditions of open-circuit voltage, 90 °C and 30% RH.

AB - Commercial proton exchange membrane heavy-duty fuel cell vehicles will require a five-fold increase in durability compared to current state-of-the art light-duty fuel cell vehicles. We describe a new composite membrane that incorporates silicotungstic heteroply acid (HPA), α-K8SiW11O40▪13H2O, a radical decomposition catalyst and when acid-exchanged can potentially conduct protons. The HPA was covalently bound to a terpolymer of tetrafluoroethylene, vinylidene fluoride, and sulfonyl fluoride containing monomer (1,1,2,2,3,3,4,4-octafluoro-4-((1,2,2-trifluorovinyl)oxy)butane-1-sulfonyl fluoride) by dehydrofluorination followed by addition of diethyl (4-hydroxyphenyl) phosphonate, giving a perfluorosulfonic acid-vinylidene fluoride-heteropoly acid (PFSA-VDF-HPA). A composite membrane was fabricated using a blend of the PFSA-VDF-HPA and the 800EW 3M perfluoro sulfonic acid polymer. The bottom liner-side of the membrane tended to have a higher proportion of HPA moieties compared to the air-side as gravity caused the higher mass density PFSA-VDF-HPA to settle. The composite membrane was shown to have less swelling, more hydrophobic properties, and higher crystallinity than the pure PFSA membrane. The proton conductivity of the membrane was 0.130 ± 0.03 S cm−1 at 80 °C and 95% RH. Impressively, when the membrane with HPA-rich side was facing the anode, the membrane survived more than 800 h under accelerated stress test conditions of open-circuit voltage, 90 °C and 30% RH.

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Improved Fuel Cell Chemical Durability of an Heteropoly Acid Functionalized Perfluorinated Terpolymer-Perfluorosulfonic Acid Composite Membrane

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