Acta Phys. -Chim. Sin. ›› 2022, Vol. 38 ›› Issue (3): 1912052.doi: 10.3866/PKU.WHXB201912052

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Effects of Dispersion Solvents on Proton Conduction Behavior of Ultrathin Nafion Films in the Catalyst Layers of Proton Exchange Membrane Fuel Cells

Aidi Han, Xiaohui Yan, Junren Chen, Xiaojing Cheng, Junliang Zhang()   

  • Received:2019-12-23 Accepted:2020-01-20 Published:2020-03-05
  • Contact: Junliang Zhang
  • About author:Junliang Zhang, Email:; Tel.: +86-21-34207439
  • Supported by:
    the National Natural Science Foundation of China(21706158);the National Natural Science Foundation of China(21533005)


Although there has been great progress, the commercialization of proton exchange membrane fuel cells (PEMFCs) is still hindered by high cost due to the use of Pt catalysts. Furthermore, structural improvement of the catalyst layers is limited by inadequate studies of the ultrathin perfluorosulfonic acid ionomer (e.g., Nafion ionomer) film in the catalyst layers. During the preparation of the catalyst ink, the dispersion solvent affects the morphology of Nafion ionomers, which affects the microstructure and proton conduction behavior of the Nafion thin film wrapped on the surface of the catalyst particles after the catalyst layer is formed. To simulate the aggregation of ionomers in the catalyst layer, a self-assembly technology was used to obtain nanoscale Nafion thin films with precise and controllable thickness on a SiO2 model substrate. The proton conductivity and microstructure of the Nafion thin films were obtained through electrochemical impedance spectroscopy and a series of micro-characterization methods. Furthermore, the relationship between proton conduction behavior within ultrathin Nafion films and colloidal morphology in Nafion solution was studied using different organic solvents. The goal was to explore and establish the microstructure model of nanoscale Nafion thin films through micro-characterization technologies, such as nuclear magnetic resonance and dynamic light scattering. It was found that at the nanoscale, Nafion thin films (~40 nm) result in low proton conductivity; an order of magnitude lower than that of bulk membranes (~10–100 μm). However, replacing iso-propanol with n-butanol (which has a lower dielectric constant) as the dispersion media of the Nafion ionomer improved the proton conductivity of the Nafion thin films. This is because Nafion in solvents with a lower dielectric constant possesses higher main chain solubility and mobility. Thus, Nafion molecules more easily aggregate into large rod-shaped micelles, which is beneficial to the construction of proton conduction channels after the self-assembly process. Furthermore, the electrostatic force between Nafion aggregates and the substrate in solvents with lower dielectric constant is smaller. This means more sulfonic groups are involved in the formation of proton conduction channels that in turn improve the proton conductivity of the Nafion thin film. In general, Nafion in solvents with lower dielectric constant leads to a structure that can facilitate proton conduction. This study provides guidance for optimizing the structure of ultrathin Nafion films and improving the proton conduction in the catalyst layers of PEMFCs.

Key words: Proton exchange membrane fuel cell, Catalyst layer, Ultrathin Nafion film, Proton conduction, Solvent effect


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