Proton-Exchange Sulfonated Poly(ether ether ketone)(SPEEK)/SiOx-S Composite Membranes in Direct Methanol Fuel Cells

Abstract

Abstract: A sulfonated poly(ether ether ketone)(SPEEK) membrane with a fairly high degree of sulfonation(DS) can swell excessively and even dissolve at high temperature.To solve these problems,insolvable functionalized silica powder with sulfonic acid groups(SiO_x-S) was added into the SPEEK matrix(DS=55.1%) to prepare SPEEK/SiO_x-S composite membranes.The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiO_x-S powder.Pure SPEEK membrane swelled 52.6% at 80℃,whereas the SPEEK/SiO_x-S(15%,by mass) membrane swelled only 27.3% at the same temperature.From room temperature to 80℃,all SPEEK/SPEEK/SiO_x-S composite membranes had methanol permeability of about o ne order of magnitude lower than that of Nafion 115.Compared with pure SPEEK membranes,the addition of the SiO_x-S powder not only leads to higher proton conductivity,but also increases the dimensional stability at higher temperatures,and greater proton conductivity can be achieved at higher temperature.The SPEEK/SiO_x-S(20%,by mass) membrane could withstand temperature up to 145℃,at which in 100% relative humidity(RH) its proton conductivity exceeded slightly that of Nafion 115 membrane and reached 0.17 S·cm^-1,while pure SPEEK membrane dissolved at 90℃.The SPEEK/SiO_x-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability,high proton conductivity,and low methanol permeability.

Key words: sulfonated poly(ether ether ketone), functionalized silica, composite membrane, direct methanol fuel cell

摘要： A sulfonated poly(ether ether ketone)(SPEEK) membrane with a fairly high degree of sulfonation(DS) can swell excessively and even dissolve at high temperature.To solve these problems,insolvable functionalized silica powder with sulfonic acid groups(SiO_x-S) was added into the SPEEK matrix(DS=55.1%) to prepare SPEEK/SiO_x-S composite membranes.The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiO_x-S powder.Pure SPEEK membrane swelled 52.6% at 80℃,whereas the SPEEK/SiO_x-S(15%,by mass) membrane swelled only 27.3% at the same temperature.From room temperature to 80℃,all SPEEK/SPEEK/SiO_x-S composite membranes had methanol permeability of about o ne order of magnitude lower than that of Nafion 115.Compared with pure SPEEK membranes,the addition of the SiO_x-S powder not only leads to higher proton conductivity,but also increases the dimensional stability at higher temperatures,and greater proton conductivity can be achieved at higher temperature.The SPEEK/SiO_x-S(20%,by mass) membrane could withstand temperature up to 145℃,at which in 100% relative humidity(RH) its proton conductivity exceeded slightly that of Nafion 115 membrane and reached 0.17 S·cm^-1,while pure SPEEK membrane dissolved at 90℃.The SPEEK/SiO_x-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability,high proton conductivity,and low methanol permeability.

关键词: sulfonated poly(ether ether ketone), functionalized silica, composite membrane, direct methanol fuel cell

GAO Qijun, WANG Yuxin, XU Li, WEI Guoqiang, WANG Zhitao. Proton-Exchange Sulfonated Poly(ether ether ketone)(SPEEK)/SiO_x-S Composite Membranes in Direct Methanol Fuel Cells[J]. , 2009, 17(2): 207-213.

高启君, 王宇新, 许莉, 卫国强, 王志涛. Proton-Exchange Sulfonated Poly(ether ether ketone)(SPEEK)/SiO_x-S Composite Membranes in Direct Methanol Fuel Cells[J]. , 2009, 17(2): 207-213.

References

1 Kuver, A., Kamloth, K.P., “Comparative study of methanol crossover acrosselectropolymerized and commercial proton exchange membrane electrolytes for the acid direct methanol fuel cell”, Electrochim. Acta, 43 (16), 2527-2535 (1998).
2 Ren, X., Zawadzinski, T.A., Uribe, F., Dai, H., “Methanol cross-over in direct methanol fuel cells”, Electrochem. Soc. Proc., 95 (23), 284-289 (1995).
3 Heinzel, A., Barragan, V.M., “A review of the state-of-the-art of the methanol crossover in direct methanol fuel cells”, J. Power Sources, 84, 70-74 (1999).
4 Kreuer, K.D., “On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells”, J. Membr. Sci., 185, 29-39 (2001).
5 Yang, B., Manthiram, A., “Sulfonated poly(ether ether ketone) membranes for direct methanol fuel cells”, Electrochem. Solid-State Lett., 6, A229-A231 (2003).
6 Wycisk, R., Lee, J.K., Pintauro, P.N., “Sulfonated polyphosphazenepolybenzimidazole membranes for DMFCs”, J. Electrochem. Soc., 152, A892-A898 (2005).
7 Dai, H., Guan, R., Li, C.H., Liu, J.H., “Development and characterization of sulfonated poly(ether sulfone) for proton exchange membrane materials”, Solid State Ion., 178, 339-345 (2007).
8 Shahi, V.K., “Highly charged proton-exchange membrane:Sulfonated poly(ether sulfone)-silica polyelectrolyte composite membranes for fuel cells”, Solid State Ion., 177, 3395-3404 (2007).
9 Park, K.T., Jung, U.H., Choi, D.W., Chun, K., Lee, H.M., Kim, S.H., “ZrO₂-SiO₂/Nafion (R) composite membrane for polymer electrolyte membrane fuel cells operation at high temperature and low humidity”, J. Power Sources, 177, 247-253 (2008).
10 Zhao, C., Li, X., Na, H., “Synthesis of sulfonated poly(ether ether ketone) (S-PEEKs) material for proton exchange membrane”, J. Membr. Sci., 280, 643-650 (2006).
11 Mikhailenko, S.U.D., Wang, K.P., Kaliaguine, S., Xing, P.X., Robertson, G.P., Guiver, M.D., “Proton conducting membranes based on cross-linked sulfonated poly(ether ether ketone) (SPEEK)”, J. Membr. Sci., 233, 93-99 (2004).
12 Mikhailenko, S.D., Zaidi, S.M.J., Kaliaguine, S., “Electrical properties of sulfonated polyether ether ketone/polyetherimide blend membranes doped with inorganic acids”, J. Polym. Sci., B:Polym. Phys., 33, 1386-1395 (2000).
13 Manea, C., Mulder, M., “Characterization of polymer blends of polyether sulfone/sulfonated polysulfone and polyether sulfone/sulfonated polyetherether ketone for direct methanol fuel cell applications”, J. Membr. Sci., 206, 443-453 (2002).
14 Zhang, H.Q., Li, X.F., Zhao, C.J., Fu, T.Z., Shi, Y.H., Na, H., “Composite membranes based on highly sulfonated PEEK and PBI:Morphology characteristics and performance”, J. Membr. Sci., 308, 67-74 (2008).
15 Silva, V.S., Ruffmann, B., Silva, H., Gallego, Y.A., Mends, A., Madeira, L.M., Nunes, S.P., “Proton electrolyte membrane properties and direct methanol fuel cell performance/I. Characterization of hybrid sulfonated poly (ether ether ketone)/zirconium oxide membranes”, J. Power Sources, 140, 34-40 (2005).
16 Uchida, H., Ueno,Y., Hagihara, H., Watanabe, M., “Self-humidifying electrolyte membranes for fuel cells-Preparation of highly dispersed TiO 2 particles in Nafion 112”, Electrochem. Soc., 150, A57-A62 (2003).
17 Martinelli, A., Matic, A., Jacobsson, P., borjesson, L., Navarra, M.A., Fernicola, A., Panero, S., Scrosati, B., “Structural analysis of PVA-based proton conducting membranes”, Solid State Ion., 177, 2431-2435 (2006).
18 Kim, D.S., Park, H.B., Rhim, J.W., Lee, Y.M., “Preparation and characterization of crosslinked PVA/SiO₂ hybrid membranes containing sulfonic acid groups for direct methanol fuel cell applications ”, J. Membr. Sci., 240, 37-48 (2004).
19 Croce, F., Persi, L., Scrosati, B., Serraino-Fiory, F., Plichta, E., Hendrickson, M.A., “Role of the ceramic fillers in enhancing the transport properties of composite polymer electrolytes”, Electrochimi. Acta, 46, 2457-2461 (2001).
20 Shao, Z.G.., Joghee, P., Hsing, I.M., “Preparation and characterization of hybrid Nafion-silica membrane doped with phosphotungstic acid for high temperature operation of proton exchange membrane fuel cells”, J. Membr Sci., 229, 43-51 (2004).
21 Xu, W.L., Liu, C.P., Xue, X.Z., Su, Y., Lv, Y.Z., Xing, W., Lu, T.H., “New proton exchange membranes based on poly (vinyl alcohol) for DMFCs”, Solid State Ion., 171, 121-127 (2004).
22 Sambandam, S., Ramani, V., “SPEEK/functionalized silica composite membranes for polymer electrolyte fuel cells”, J. Power Sources, 170, 259-267 (2007).
23 Li, L., Wang, Y.X., “Sulfonated polyethersulfone Cardo membranes for direct methanol fuel cell”, J. Membr. Sci., 246, 167-172 (2005).
24 Li, L., Wang, Y.X., “A hybrid membrane of poly(vinyl alcohol) and phosphotungstic acid for fuel cells”, Chin. J. Chem. Eng., 10 (5), 614-617 (2002).
25 Zaidi, S.M.J., Mikhailenko, S.D., Robertson, G.P., Guiver, M.D., Kaliaguine, S., “Proton conducting composite membranes from polyetherether ketone and heteropolyacids for fuel cell applications”, J. Membr. Sci., 173, 17-34 (2000).
26 Tricoli, V., Carretta, N., Bartolozzi, M., “A comparative investgation of proton and methanol transport in fluorinated ionomeric membranes”, J. Electrochem. Soc., 147, 1286-1290 (2000).
27 Huang, M.Y., Wang, Y.X., Cai, Y.Q., Xu, L., “Sulfonated poly(ether ether ketone)/zirconium tricarboxybutylphosphonate composite proton-exchange membranes for direct methanol fuel cells”, Acta Polymerica Sinica, 4, 337-342 (2007).
28 Gasa, J.V., Boob, S., Weiss, R.A., Shaw, M.T., “Proton-exchange membranes composed of slightly sulfonated poly(ether ketone ketone) and highly sulfonated crosslinked polystyrene particles”, J. Membr. Sci., 269, 177-186 (2006).
29 Kim, Y.S., Wang, F., Hickner, M., Zawodzinski, T.A., McGrath, J.E., “Fabrication and characterization of heteropolyacid (H₃PW₁₂O₄₀)/directly polymerized sulfonated poly(arylene ether sulfone) copolymer composite membranes for higher temperature fuel cell applications”, J. Membr. Sci., 212, 263-282 (2003).
30 Li, Q.F., Huang, R.H., “Approaches and recent development of polymer electrolyte membranes for fuel cells operating above 100℃”, Chem. Mater., 15, 4896-4915 (2003).

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Proton-Exchange Sulfonated Poly(ether ether ketone)(SPEEK)/SiO_x-S Composite Membranes in Direct Methanol Fuel Cells

Proton-Exchange Sulfonated Poly(ether ether ketone)(SPEEK)/SiO_x-S Composite Membranes in Direct Methanol Fuel Cells

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