Chemistry, Physics and Technology of Surface

ISSN 2518-1238 (Online), ISSN 2079-1704 (Print)

The aim of the work is to synthesize polymer and hybrid polymer-inorganic proton conductive membranes on the base of water soluble acrylic monomers and sol-gel precursor, and characterize their properties.

Materials, used for membrane preparation - acrylonitrile (AN), acrylic acid (AA), 3-sulfopropyl acrylate potassium salt (SPAK), tetraethoxysilane (TEOS), 3-methacryloxypropyltrimethoxysilane (MAPTMS), ethyleneglycol dimethacrylate (EGDMA), 2,2-dimethoxy-2-phenylacetophenone (DMPA) and phosphoric acid (85 wt. %).

Methods of investigation – impedance spectroscopy, water and methanol uptake measurement, laser interferometry, SEM.

Proton conductive polymer and organic-inorganic membranes were synthesized based on acrylic monomers and silica inorganic component, derived as a result of sol-gel transformation of precursors – tetraethoxysilane (TEOS) and 3-methacryloxypropyl trimethoxysilane (MAPTMS). AA, AN and SPAK were cross-linked by irradiation with UV light at the presence of photoinitiator DMPA and cross-linker EGDMA and simultaneous hydrolytic polycondensation of sol-gel precursors. Kinetics of polymerization in situ was investigated by laser interferometry. Membranes characterization includes morphology, methanol uptake and proton conductivity at different temperatures. Morphology of the membranes investigated using SEM evidences that the material structure is homogeneous without cracks and phase separation. The membranes obtained exhibit low methanol uptake and high values of proton conductivities (3.6·10^–3–9.6·10^–3 Sm/cm) making them attractive for fuel cell application. Contact angle measurements allow to evaluate free surface energy of the membranes.

The proposed method of UV-іnitiated polymerization in situ allows one to obtain cross-linked sulfo groupcontaining polymer and hybrid polymer-inorganic materials, which possesses a complex of necessary properties for their use in methanol fuel cells. 

1. Winter M., Brodd R.J. What are batteries, fuel cells, and supercapacitors? Chem. Rev. 2004. 104(10): 4245. https://doi.org/10.1021/cr020730k

2. Yun-Sheng Ye, John Rick, Bing-Joe Hwang. Water soluble polymers as proton exchange membranes for fuel cells. Polymers. 2012. 4(2): 913. https://doi.org/10.3390/polym4020913

3. Dillon R., Srinivasan S., Arico A.S., Antonucci V. International activities in DMFC R&D: status of technologies and potential applications. J. Power Sources. 2004. 127(1–2): 112. https://doi.org/10.1016/j.jpowsour.2003.09.032

4. Bolto B., Gregory J. Organic polyelectrolytes in water treatment. Water Res. 2007. 41(11): 2301. https://doi.org/10.1016/j.watres.2007.03.012

5. Bai H., Ho W.S.W. New poly(ethylene oxide) soft segment-containing sulfonated polyimide copolymers for high temperature proton-exchange membrane fuel cells. J. Membr. Sci. 2008. 313(1–2): 5. https://doi.org/10.1016/j.memsci.2007.12.062

6. Lee S., Jang W., Choi S., Tharanikkarasu K., Shul Y., Han H. Sulfonated polyimide and poly (ethylene glycol) diacrylate based semi-interpenetrating polymer network membranes for fuel cells. J. Appl. Polym. Sci. 2007. 104(5): 2965. https://doi.org/10.1002/app.25966

7. Kerres J.A. Development of ionomer membranes for fuel cells. J. Membr. Sci. 2001. 185(1): 3. https://doi.org/10.1016/S0376-7388(00)00631-1

8. Huang Y.F., Chuang L.C., Kannan A.M., Lin C.W. Proton-conducting membranes with high selectivity from cross-linked poly(vinyl alcohol) and poly(vinyl pyrrolidone) for direct methanol fuel cell applications. J. Power Sources. 2009. 186(1): 22. https://doi.org/10.1016/j.jpowsour.2008.09.072

9. Shylova O.A., Shylov V.V. Nanocomposite oxide and hybrid organo-inorganic materials, obtained by sol-gel method. Synthesis. Properties. Application. Nanosystems, nanomaterials, nanotechnologies. 2003. 1(1): 9.

10. Gurtekin M., Kayaman-Apohan N., Kahraman M.V., Menceloglu Y., Gungor A. UV curable sulfonated hybrid materials and their performance as proton exchange membranes. React. Funct. Polym. 2009. 69(9): 698. https://doi.org/10.1016/j.reactfunctpolym.2009.05.004

11. Qiu Y., Park K. Superporous IPN hydrogels having enhanced mechanical properties. AAPS Pharm. Sci. Tech. 2003. 4(4): 406. https://doi.org/10.1208/pt040451

12. Diao H., Yan F., Qiu L., Lu J., Lu X., Lin B., Li Q., Shang S., Liu W., Liu J. High performance cross-linked poly(2-acrylamido-2-methylpropanesulfonic acid)-based proton exchange membranes for fuel cells. Macromolecules. 2010. 43(15): 6398. https://doi.org/10.1021/ma1010099

13. Aparicio M., Mosa J., Etienne M., Duran A. Proton-conducting methacrylate-silica sol-gel membranes containing tungstophosphoric acid. J. Power Sources. 2005. 145(2): 231. https://doi.org/10.1016/j.jpowsour.2005.01.071