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Partially Fluorinated Polyphenylene Ionomers as Proton Exchange Membranes for Fuel Cells: Effect of Pendant Multi-Sulfophenylene Groups

  • Zhi Long
    Zhi Long
    Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, 4 Takeda, Kofu, Yamanashi 400-8510, Japan
    More by Zhi Long
  • Junpei Miyake
    Junpei Miyake
    Clean Energy Research Center, University of Yamanashi, 4 Takeda, Kofu, Yamanashi 400-8510, Japan
  • , and 
  • Kenji Miyatake*
    Kenji Miyatake
    Clean Energy Research Center, University of Yamanashi, 4 Takeda, Kofu, Yamanashi 400-8510, Japan
    Fuel Cell Nanomaterials Center, University of Yamanashi, 4-3 Takeda, Kofu 400-8511, Japan
    *E-mail: [email protected]
Cite this: ACS Appl. Energy Mater. 2019, 2, 10, 7527–7534
Publication Date (Web):October 7, 2019
https://doi.org/10.1021/acsaem.9b01513
Copyright © 2019 American Chemical Society

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    Abstract

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    The six kinds of sulfonated poly(arylene perfluoroalkylene) (SPAF) ionomers with pendant multi-sulfophenylene groups were designed and synthesized to apply to fuel cells as proton exchange membranes. The SPAF polymers possessed high ion exchange capacity (IEC) values (2.07–2.15 mequiv g–1), good solubility in organic solvents, and high molecular weight, providing the flexible membranes by solution casting. Compared with our previous SPAF-MM membrane (with no pendant sulfophenylene groups), the introduction of the pendant sulfophenylene groups resulted in the significant improvement of proton conductivity, whereas it did not deteriorate the other favorable membrane properties, such as gas impermeability and mechanical properties. The SPAF-BM, as the chosen membrane, exhibited higher fuel cell performance than that of our previous SPAF-MM membrane under low humidified conditions. During the open circuit voltage (OCV) hold test, the SPAF-BM cell showed the low average decay of 40 μV h–1 and kept high OCV even after 1000 h. Post-test analyses proved that the SPAF-BM membrane after the OCV hold test retained the original fuel cell performance without practical changes in the molecular structure and molecular weight due to the high chemical stability of SPAF-BM.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsaem.9b01513.

    • Materials, measurement methods, synthesis, and NMR spectra of monomers, molecular weight and yield of PAF polymers, NMR spectra and GPC profiles of PAF polymers and SPAF polymers, number of absorbed water molecules per sulfonic acid group (λ) values of SPAF membranes as a function of RH, proton conductivity of SPAF membranes as a function of λ, linear sweep voltammograms (LSVs) of fuel cells using SPAF-BM, IR-free polarization curves for SPAF-BM and SPAF-MM cells, mass activity (MA) of Pt catalysts with hydrogen/oxygen or air, NMR and GPC profiles SPAF-BM before and after OCV hold test for 1000 h (PDF)

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