PROCEEDINGS OF THE SHEVCHENKO SCIENTIFIC SOCIETY

Chemical Sciences

Архів / Том LIII 2018

Khrystyna RYMSHA, Mariia ZHYHAILO, Oksana DEMCHYNA, Iryna YEVCHUK

Department of Physico-Chemistry of Fossil Fuels, L.M. Lytvynenko Institute of Physico-Organic Chemistry and Coal Chemistry Naukova Str., 3а, 79053 Lviv, Ukraine

DOI: https://doi.org/10.37827/ntsh.chem.2018.53.068

ORGANO-INORGANIC SULFOGROUP-CONTAINING MEMBRANES FOR FUEL CELLS

The polymeric and organic-inorganic sulfogroup-containing membranes of various composition based on acrylic monomers (acrylonitrile, acrylamide and 3-sulfopropyl acrylate potassium salt) and sol-gel systems of tetraethoxysilane (TEOS – H2O – C2H5OH) were successfully synthesized by in situ photoinitiated copolymerization in the presence of photoinitiator and cross-linker. The determined content of the gel fraction in the synthesized films was > 98 % indicating that the UV-initiated polymerization of acrylates under the chosen conditions was very high. The kinetics of the process of photoinitiated polymerization of a mixture of acrylates in the absence and in the presence of a sol-gel system was studied by means of laser interferometry. Kinetic parameters of the process (time of maximal rate achievement, maximal rate of the process, conversion at maximal rate) were calculated. Free surface energy and its components (dispersive and hydrogen) for prepared polymer and organic-inorganic nanocomposite membranes at varying of acrylic monomers/sol-gel system ratio were estimated by contact angle measurements. The composition of the polymer matrix and the content of the inorganic component have a significant effect on the kinetics of the polymerization process and on the structure of the resulting materials, which is confirmed by the change in their hydrophobic-hydrophilic balance. The presence of sulfogroups in the obtained nanocomposite materials provides their proton conductivity. Specific proton conductivity of the synthesized materials, measured by impedance spectroscopy method, is sufficiently high – 10–3 – 10–2 Sm/cm and comparable with that for Nafion. The conducted researches can be used for the development of efficient proton conductive membranes for application in fuel cells.

Key words: organic-inorganic nanocomposite, sulfocontaining proton-conductive membrane, sol-gel method, photoinitiated polymerization, free surface energy

References:

    1. Draxl C., Nabok D., Hannewald K. Organic/Inorganic Hybrid Materials: Challenges for ab Initio Methodology. Acc. Chem. Res. – 2014. – Vol. 47 (11). – P. 3225–3232. (https://doi.org/10.1021/ar500096q).
    2. Lu Q., Cai Z., Wang S. et al. Controlled Construction of Nanostructured Organic-Inorganic Hybrid Material Induced by Nanocellulose. Sustainable Chemistry & Engineering. – 2017. – Vol. 5 (9). – P. 8456–8463. (https://doi.org/10.1021/acssuschemeng.7b02394).
    3. Tsebriyenko T.V., Yarova N.V., Alekseeva T.T. The effect of poly(titaniumoxide), derived by sol-gel method, on thermophysical properties of organic-inorganic interpenetrating polymer networks. Voprosy khimiyi i khimicheskoy tekhnologiyi. – 2017. – Т. 111(2). – P. 86–91 (in Russian).
    4. Tsebrienko T.V., Alekseeva T.T., Babkina N.V. et al.. Intern. J. Advanced Engineering, Management and Science. – 2017. – Vol. 3(3). – P. 226–232. (https://doi.org/10.24001/ijaems.3.3.13).
    5. Wannek C. High-temperature PEM fuel cells: Electrolytes, cells and stacks. Hydrogen and fcells: Fundamentals, Technologies and Applications, ed. D. Stolten, Weinheim, Germany: Wiley-VCH, 2010, P. 17–40.
    6. Lee S.-Y., Yasuda T., Watanabe M. Fabrication of protic ionic liquid/sulphonated polyimide composite membranes for non-humidified fuel cells. J. Power Sources. – 2010. – Vol. 195 (18). – P. 5909–5914. (https://doi.org/10.1016/j.jpowsour.2009.11.045).
    7. Ye Y.-S., Rick J. and Hwang B.-J. Water Soluble Polymers as Proton Exchange Membranes for Fuel Cells. Polymers. – 2012. – Vol. 4. - P. 913–963. (https://doi.org/10.3390/polym4020913).
    8. Laberty-Robert C., Valle K., Pereira F. et al. Design and properties of functional hybrid organic–inorganic membranes for fuel cells. Chem. Soc. Rev. – 2011. – Vol 40. – P. 961–1005. (doi.org/10.1039/c0cs00144a).
    9. Diao H., Yan F., Qiu L. et al. High performance cross-linked poly(2-acrylamido-2-methylpropansulfonic acid)-based proton exchange membranes for fuel cells. Macromolecules. – 2010. – Vol. 43. - P. 6398–6405. (https://doi.org/10.1021/ma1010099)
    10. Matsuura Yu., Matsukawa K., Kawabata R. et al. Synthesis of polysilane-acrylamide copolymers by photopolymerization and their application to polysilane-silica hybrid thin films. Polymer. – 2002. – Vol. 43. – P. 1549–1553. (https://doi.org/10.1016/S0032-3861(01)00693-0).
    11. Van Krevelen D.W. The properties and chemical structure of polymers. Moscow: Khimiya, 1976 – 413 p. (in Russian).
    12. Janczuk B., Zdziennicka A. A study on the components of surface free energy of quartz from contact angle measurements. Journal of Materials Science. – 1994. – Vol. 29. – P. 3559–3564. (https://doi.org/10.1007/BF00352063).
    13. Dobrovolsky Yu.A., Pisareva А.V., Leonova L.S. et al. Novel proton conductive membranes for fuel cells and gas sensors. Alternativnaya energetika i ekologiya. – 2004. – 12(20). – P. 36–41 (in Russian).
    14. Tamaki R., Naka K., Chujo Y. Synthesis of poly(N,N’-dimethylacrylamide)/silica gel polymer hybrids by in situ polymerization method. Polymer Journal. – 1998. – Vol. 30(1). - P. 60–65. (https://doi.org/10.1295/polymj.30.60).

How to Cite

Rymsha K., Zhyhailo M., Demchyna O., Yevchuk I. ORGANO-INORGANIC SULFOGROUP-CONTAINING MEMBRANES FOR FUEL CELLS Proc. Shevchenko Sci. Soc. Chem. Sci. 2018 Vol. LIII. P. 68-80.

Download the pdf