Proton-exchange Sulfonated Poly(ether ether ketone)/Sulfonated Phenolphthalein Poly(ether sulfone) Blend Membranes in DMFCs

›› 2009, Vol. 17 ›› Issue (6): 934-941.

• SEPARATION SCIENCE AND ENGINEERING • Previous Articles Next Articles

Proton-exchange Sulfonated Poly(ether ether ketone)/Sulfonated Phenolphthalein Poly(ether sulfone) Blend Membranes in DMFCs

GAO Qijun^1,2, WANG Yuxin^1,2, XU Li¹, WANG Zhitao^1,2, WEI Guoqiang^1,2

1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
2. State Key Laboratory of Chemical Engineering, Tianjin 300072, China

Received:2008-11-09 Revised:2009-08-18 Online:2009-12-28 Published:2009-12-28
Supported by:
Supported by the State Key Development Program for Basic Research of China (2008CB617502);the National Natural Science Foundation of China (20606025);Program for Changjiang Scholars and Innovative Research Team in University of China (IRT0641)

Proton-exchange Sulfonated Poly(ether ether ketone)/Sulfonated Phenolphthalein Poly(ether sulfone) Blend Membranes in DMFCs

高启君^1,2, 王宇新^1,2, 许莉¹, 王志涛^1,2, 卫国强^1,2

1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
2. State Key Laboratory of Chemical Engineering, Tianjin 300072, China

通讯作者: XU Li,E-mail:xuli620@eyou.com
基金资助:
Supported by the State Key Development Program for Basic Research of China (2008CB617502);the National Natural Science Foundation of China (20606025);Program for Changjiang Scholars and Innovative Research Team in University of China (IRT0641)

Abstract

Abstract: A sulfonated poly(ether ether ketone)(SPEEK) membrane with fairly high degree of sulfonation(DS) swells excessively and even dissolves at high temperature.To solve these problems,sulfonated phenolphthalein poly(ether sulfone)(SPES-C,DS=53.7%) is blended with the SPEEK matrix(DS=55.1%,61.7%) to prepare SPEEK/SPES-C blend membrane.The decrease in swelling degree and methanol permeability of the membrane is dose-dependent.Pure SPEEK(DS=61.7%) membrane dissolves completely in water at 70℃,whereas the swelling degree of the SPEEK(DS=61.7%)/SPES-C(40%,by mass) membrane is 29.7% at 80℃.From room temperature to 80oC,the methanol permeability of all SPEEK(DS=55.1%)/SPES-C blend membranes is about one order of magnitude lower than that of Nafion115.At higher temperature,the addition of SPES-C polymer increases the dimensional stability and greater proton conductivity can be achieved.The SPEEK(DS=55.1%)/SPES-C(40%,by mass) membrane can withstand temperatures up to 150℃.The proton conductivity of SPEEK(DS=55.1%)/SPES-C(30%,by mass) membrane approaches 0.16 S·cm^-1,matching that of Nafion 115 at 140℃ and 100% RH,while pure SPEEK(DS=55.1%) membrane dissolves at 90℃.The SPEEK/SPES-C blend 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), sulfonated phenolphthalein poly(ether sulfone), blend membrane, direct methanol fuel cell

摘要： A sulfonated poly(ether ether ketone)(SPEEK) membrane with fairly high degree of sulfonation(DS) swells excessively and even dissolves at high temperature.To solve these problems,sulfonated phenolphthalein poly(ether sulfone)(SPES-C,DS=53.7%) is blended with the SPEEK matrix(DS=55.1%,61.7%) to prepare SPEEK/SPES-C blend membrane.The decrease in swelling degree and methanol permeability of the membrane is dose-dependent.Pure SPEEK(DS=61.7%) membrane dissolves completely in water at 70℃,whereas the swelling degree of the SPEEK(DS=61.7%)/SPES-C(40%,by mass) membrane is 29.7% at 80℃.From room temperature to 80oC,the methanol permeability of all SPEEK(DS=55.1%)/SPES-C blend membranes is about one order of magnitude lower than that of Nafion115.At higher temperature,the addition of SPES-C polymer increases the dimensional stability and greater proton conductivity can be achieved.The SPEEK(DS=55.1%)/SPES-C(40%,by mass) membrane can withstand temperatures up to 150℃.The proton conductivity of SPEEK(DS=55.1%)/SPES-C(30%,by mass) membrane approaches 0.16 S·cm^-1,matching that of Nafion 115 at 140℃ and 100% RH,while pure SPEEK(DS=55.1%) membrane dissolves at 90℃.The SPEEK/SPES-C blend 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), sulfonated phenolphthalein poly(ether sulfone), blend membrane, direct methanol fuel cell

GAO Qijun, WANG Yuxin, XU Li, WANG Zhitao, WEI Guoqiang. Proton-exchange Sulfonated Poly(ether ether ketone)/Sulfonated Phenolphthalein Poly(ether sulfone) Blend Membranes in DMFCs[J]. , 2009, 17(6): 934-941.

高启君, 王宇新, 许莉, 王志涛, 卫国强. Proton-exchange Sulfonated Poly(ether ether ketone)/Sulfonated Phenolphthalein Poly(ether sulfone) Blend Membranes in DMFCs[J]. , 2009, 17(6): 934-941.

References

1 Hogarth, M.P., Hards, G.A., “Direct methanol fuel cells, Technological advances and further requirements”, Platinum Met. Rev., 40, 150-159(1996).
2 Surampudi, S., Narayanan, S.R., Vamous, E., Frank, H., Halpert, G., Lconti, A., Kosek, J., Prakash, G.K., Olah, G.A., “Advances in direct oxidation methanol fuel cells”, J. Power Sources, 47, 377-385(1994).
3 Kuver, A., Kamloth, K.P., “Comparative study of methanol crossover across electropolymerized and commercial proton exchange membrane electrolytes for the acid direct methanol fuel cell”, Electrochim. Acta, 43, 2527-2535(1998).
4 Ren, X., Zawadzinski, T.A., Uribe, F., Dai, H., “Methanol cross-over in direct methanol fuel cells”, Electrochem. Soc. Proc., 95, 284-289(1995).
5 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).
6 Kreuer, K.D., “On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells”, J. Membr. Sci., 185, 29-39(2001).
7 Yang, B., Manthiram, A., “Sulfonated poly(ether ether ketone) membranes for direct methanol fuel cells”, Electrochem. Solid-State Lett., 6, A229-A231(2003).
8 Wycisk, R., Lee, J.K., Pintauro, P.N., “Sulfonated polyphosphazene-polybenzimidazole membranes for DMFCs”, J. Electrochem. Soc., 152, A892-A898(2005).
9 Gu, S., He, G.H., Wu, X.M., Guo, Y.J., Liu, H.J., Peng, L., Xiao, G.k., “Preparation and characteristics of crosslinked sulfonated poly(phthalazinone ether sulfone ketone) with poly(vinyl alcohol) for proton exchange membrane”, J. Membr. Sci., 312, 48-58(2008).
10 Yamada, O., Yin, Y., Tanaka, K., Kita, H., Okamoto, K., “Polymer electrolyte fuel cells based on main-chain-type sulfonated polyimides”, Electrochim. Acta, 50, 2655-2659(2005).
11 Song, J.M., Miyatake, K., Uchida, H., Watanabe, M., “Investigation of direct methanol fuel cell performance of sulfonated polyimide membrane”, Electrochim. Acta, 51, 4497-4504(2005).
12 Othman, M.H.D., Ismail, A.F., Mustafa, A., “Proton conducting composite membrane from sulfonated poly(ether ether ketone) and boron orthophosphate for direct methanol fuel cell application”, J. Membr. Sci., 299, 156-165(2007).
13 Lin, Y.F., Hsiao, Y.H., Yen, C.Y., Chiang, C.L., Lee, C.H., Huang, C.C., Ma, C.C.M., “Sulfonated poly(propylene oxide) oligomers/Nafion acid-base blend membranes for DMFC”, J. Power Sources, 172, 570-577(2007).
14 Ramya, K., Dhathathreyan, K.S., “Methanol crossover studies on heat-treated Nafion membranes”, J. Membr. Sci., 311, 121-127(2008).
15 Park, K.T., Jung, U.H., Choi, D.W., Chun, K., Lee, H.M., Kim, S.H., “ZrO₂-SiO₂/Nafion composite membrane for polymer electrolyte membrane fuel cells operation at high temperature and low humidity”, J. Power Sources, 177, 247-253(2008).
16 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).
17 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).
18 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).
19 Mikhailenko, S.U.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).
20 Kerres, J., Ullrich, A., Meier, F., Haring, T., “Synthesis and characterization of novel acid-base polymer blends for application in membrane fuel cells”, Solid State Ion., 125, 243-249(1999).
21 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).
22 Nagarale, R.K., Gohil, G.S., Shahi, V.K., “Sulfonated poly(ether ether ketone)/polyaniline composite proton-exchange membrane”, J. Membr. Sci., 280, 389-396(2006).
23 Zaidi, S.M.J., “Preparation and characterization of composite membranes using blends of SPEEK/PBI with boron phosphate”, Electrochim. Acta, 50, 4771-4777(2005).
24 Jung, H.Y., Park, J.K., “Blend membranes based on sulfonated poly(ether ether ketone) and poly(vinylidene fluoride) for high performance direct methanol fuel cell”, Electrochim. Acta, 52, 7464-7468(2007).
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 Jung, B., Kim, B., Yang, J.M., “Transport of methanol and protons through partially sulfonated polymer blend membranes for direct methanol fuel cell”, J. Membr. Sci., 245, 61-69(2004).
27 Swier, S., Ramani, V., Fenton, J.M., Kunz, H.R., Shaw, M.T., Weiss, R.A., “Polymer blends based on sulfonated poly(ether ketone ketone) and poly(ether sulfone) as proton exchange membranes for fuel cells”, J. Membr. Sci., 256, 122-133(2005).
28 Jia, L.D., Xu, X.F., Zhang, H.J., Xu, J.P., “Permeation of nitrogen and water vapor through sulfonated polyetherethersulfone membrane”, J. Polym. Sci., B:Polym. Phys., 35, 2133-2140(1997).
29 Li, L., Wang, Y.X., “Sulfonated polyethersulfone Cardo membranes for direct methanol fuel cell”, J. Membr. Sci., 246, 167-172(2005).
30 Wu, P.X., Zhang, L.C., Polymer Blending Modification, China Light Industry Press, Beijing, 29-31(1996).
31 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).
32 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).
33 Li, Q.F., Huang, R.H., “Approaches and recent development of polymer electrolyte membranes for fuel cells operating above 100oC”, Chem. Mater., 15, 4896-4915(2003).

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Proton-exchange Sulfonated Poly(ether ether ketone)/Sulfonated Phenolphthalein Poly(ether sulfone) Blend Membranes in DMFCs

Proton-exchange Sulfonated Poly(ether ether ketone)/Sulfonated Phenolphthalein Poly(ether sulfone) Blend Membranes in DMFCs

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