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Proton-conducting phosphotungstic acid/sulfonated fluorinated block copolymer composite membrane for polymer electrolyte fuel cells with reduced hydrogen permeability

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Abstract

A sulfonated fluorinated block copolymer (SFBC) consisting of sulfone and ether bridges was synthesized via nucleophilic substitution polymerization, and then incorporated with 10, 20 or 30 wt% of phosphotungstic acid (PWA) using facile solution casting approach to fabricate composite membranes. The monomer sulfonation was carried out for SFBC to avoid the random sulfonation that can degrade the mechanical strength of polymer chains. A higher local concentration of acidic moieties within molecular frameworks of PWA and good mechanical properties allow for an unprecedented approach to tailor the proton conductivity as well as mechanical strength of composite membrane, as evidenced by alternating current (AC) impedance and dynamic mechanical (DMA) analyses. The surface morphological properties and roughness of membranes were investigated by field emission scanning electron microscope (FE-SEM) and atomic force microscope (AFM); the composite membranes exhibited even and denser dispersion of PWA in polymer matrix. Compared to pristine SFBC-50, the water uptake, hydrophilicity and ion exchange capacity of SFBC-50/PWA-X membranes were significantly improved. The peak proton conductivity of SFBC-50/PWA-30 membrane at 90 °C under 100% relative humidity (RH) is 105.22 mS/cm, which is 2.55 folds higher than that of pristine SFBC-50 (41.11 mS/cm) and 1.2 folds lower than that of Nafion-117 membrane (127.12 mS/cm). The peak power density delivered by the PEFC containing SFBC-50/PWA-30 membrane is 377.83 mW/cm2 at a load current of 864.29 mA/cm2 while operating the cell at 60 °C under 100% RH. In contrast, under identical condition, the pristine SFBC-50 membrane delivered the peak power density of 147.37 mW/cm2 at a load current of 353.52 mA/cm2, a 2.56-fold lower performance compared to composite membrane. Furthermore, composite membrane exhibited much lower H2 permeability compared to that of SFBC-50 and Nafion-117 membrane.

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Acknowledgements

This work (Grants No. S2136752) was supported by Business for Cooperative R&D between Industry, Academy, and Research Institute funded Korea Small and Medium Business Administration in 2013.

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Authors and Affiliations

  1. Department of Bioenvironmental Chemistry, Chonbuk National University and R&D Center for Canutech, Business Incubation Center of Chonbuk National University, Jeonju, Jeollabuk-do, 54896, Republic of Korea

    Ae Rhan Kim

  2. Graduate School, Department of Energy Storage/Conversion Engineering, Hydrogen and Fuel Cell Research Center, Chonbuk National University, Jeonju, Jeollabuk-do, 54896, Republic of Korea

    Mohanraj Vinothkannan & Dong Jin Yoo

  3. School of Semiconductor and Chemical Engineering, Chonbuk National University, Jeonju, Jeollabuk-do, 54896, Republic of Korea

    Jong Seok Kim

  4. Department of Life Science, Chonbuk National University, Jeonju, Jeollabuk-do, 54896, Republic of Korea

    Dong Jin Yoo

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  1. Ae Rhan Kim
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Kim, A.R., Vinothkannan, M., Kim, J.S. et al. Proton-conducting phosphotungstic acid/sulfonated fluorinated block copolymer composite membrane for polymer electrolyte fuel cells with reduced hydrogen permeability. Polym. Bull. 75, 2779–2804 (2018). https://doi.org/10.1007/s00289-017-2180-2

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