4.7 Article

Dual-sulfonated MOF/polysulfone composite membranes boosting performance for proton exchange membrane fuel cells

Journal

EUROPEAN POLYMER JOURNAL
Volume 180, Issue -, Pages -

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.eurpolymj.2022.111601

Keywords

Metal-organic frameworks (MOFs); Composite membranes; Sulfonation; Proton exchange membranes; Fuel cells

Funding

  1. National Research Foundation of Korea (NRF) - Korean government (MSIP) [NRF-2020R1F1A1075098]
  2. Ministry of Trade, Industry and Energy (MOTIE, Korea) [20229A10100170]
  3. National R&D Program through the National Research Foundation of Korea (NRF) - Ministry of Science and ICT [NRF-2020M3H4A3105824]
  4. Korea Evaluation Institute of Industrial Technology (KEIT) [20229A10100170] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)

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In this study, dual-sulfonated polysulfone/metal-organic framework composite membranes were designed as proton exchange membranes. The membranes showed improved proton conductivity and dimensional stability due to the incorporation of sulfonated MOFs and the controllable sulfonation degree of the polysulfone matrix. The composite membranes exhibited high proton conductivity and moderate swelling ratio, even at high temperatures and humidity levels.
Nafion is the most widely used polymer electrolyte membrane (PEM) owing to its excellent physical stability and superior proton conductivity in the presence of long-side-chain perfluorinated sulfonic acid. However, commercially available Nafion is very expensive, limiting its practical application. Thus, a new proton exchange membrane must be developed to replace conventional Nafion for practical electrochemical system operations. In this study, we rationally designed dual-sulfonated polysulfone (PSF)/metal-organic framework (MOF) composite membranes for use as PEMs. Sulfonated PSF (sPSF) was systematically prepared with a controllable sulfonation degree. Additionally, sulfonated MOFs (sMOF; MIL-101(Cr)-SO3H and UiO-66(Zr)-SO3H) were incorporated into the sPSF matrix to form dual-sulfonated PSF/MOF composite membranes. The sMOF offers a high Brunauer-Emmett-Teller (BET) surface area with sulfonated sites that can effectively control water molecules and ion transport, increasing proton conductivity and dimensional stability. With an optimal MOF loading (-3 wt%), the sPSF/sMOF composite membranes exhibited a high proton conductivity (-0.18 S/cm) at room temperature under fully humid conditions. Additionally, the sPSF/sMOF composite membranes showed a moderate swelling ratio owing to the high dimensional stability due to the adsorbed molecules in the MOF framework. Particularly, the sPSF/sMOF composite membranes also exhibited a high proton conductivity at high temperatures (-75 degrees C) and moderate relative humidity (-60-80 % RH), demonstrating their high potential for practical operation. Thus, the sPSF/sMOF composite membranes show good potential as a novel PEM for electrochemical applications.

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