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Molecular dynamics simulations of Nafion and sulfonated polyether sulfone membranes. I. Effect of hydration on aqueous phase structure

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Abstract

We measured the water uptakes and proton conductivities of a Nafion membrane and three sulfonated polyether sulfone membranes (SPESs) with different values of ion-exchange capacity (IEC = 0.75, 1.0 and 1.4 meq/g) in relation to relative humidity in order to apply the findings to polymer electrolyte membrane fuel cells. The number of water molecules per sulfonic acid group λ at each humidity level was independent of the relative humidity for all membranes, but the proton conductivities of the SPESs were inferior to that of Nafion for the same λ value. Classical molecular dynamics simulations for the same membranes were carried out using a consistent force field at λ = 3, 6, 9, 12 and 15. The structural properties of water molecules and hydronium ions at a molecular level were estimated from radial distribution functions and cluster size distributions of water. We found that the radial distribution function of S(sulfonic acid)–S(sulfonic acid) of Nafion at λ = 3 indicated a significant correlation between the S–S pair, due to water channels, while the S–S pair of the SPESs showed a poor correlation. The cluster size distribution of water was also calculated in order to estimate the connectivity of the water channel. It is clear that some water is present in the SPESs as small, isolated clusters, especially when the water content is low.

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Acknowledgements

We thank F. Sato for helpful discussions on the development of force fields. We are grateful to A. Yashiro of Sumitomo Chemical Co., Ltd. for providing SPES samples. This work was supported by the New Energy Development Organization (NEDO), Japan.

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Author notes

  1. Takahiro Ohkubo

    Present address: Graduate School of Science and Technology, Chiba University, Inage-ku, Chiba, 263-8522, Japan

Authors and Affiliations

  1. FC-Cubic, National Institute of Advanced Industrial Science and Technology (AIST), 2-41-6 Aomi, Koto-ku, Tokyo, 135-0064, Japan

    Takahiro Ohkubo, Koh Kidena, Naohiko Takimoto & Akihiro Ohira

Authors
  1. Takahiro Ohkubo
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  2. Koh Kidena
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Correspondence to Takahiro Ohkubo.

Appendix

Appendix

Force field parameters

Table 2 Developed CFF-type force field parameters for the Nafion fragment with a sulfonic acid group, as shown in Fig. 3a
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Table 3 Developed CFF-type force field parameters for the SPES fragment with a sulfonic acid group, as shown in Fig. 3b
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Table 4 Developed CFF-type force field parameters for hydronium, as shown in Fig. 3c
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Ohkubo, T., Kidena, K., Takimoto, N. et al. Molecular dynamics simulations of Nafion and sulfonated polyether sulfone membranes. I. Effect of hydration on aqueous phase structure. J Mol Model 17, 739–755 (2011). https://doi.org/10.1007/s00894-010-0767-8

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  • DOI: https://doi.org/10.1007/s00894-010-0767-8

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