一般燃料電池的質子傳導薄膜在應用上最常碰到的問題為在低濕度環境下薄膜保存水的能力不足，導致傳遞質子的水分喪失，進而使得質子導電度下降；另一個問題是質子交換膜應用於直接甲醇燃料電池中時，薄膜有嚴重的甲醇滲透現象，導致在陰極產生混合電位降低電池整體的性能表現。
本研究帶有磺酸根的高分歧結構高分子加入薄膜後，可同時提昇薄膜的質子導電度和大幅降低甲醇滲透率。利用雙馬來醯亞胺(1,1’-(Methylenedi-4,1-phenylene) bismaleimide, BMI)與磺酸化N-苯基馬來醯亞胺(sulfonated N-Phenylmaleimide, sPMI)之共聚高分子與Nafion及磺酸化聚二醚酮(sulfonated poly ether ether ketone, sPEEK)製成複合薄膜， sPMI所帶有的磺酸根增進薄膜的導電度以及藉由高歧狀型態的BMI形成半互穿網絡 (semi-Interpenetrating Polymer Network, semi-IPN) 結構降低甲醇滲透，並以不同的BMI與sPMI比例，調控共聚高分子的型態，製備出能降低甲醇滲透但也有好的質子導電度表現的複合薄膜。
由實驗得知，在BMI : sPMI = 1 : 4時所製備的薄膜，無論在sPEEK薄膜或是Nafion薄膜上，都能有效的降低甲醇的滲透。在20%1B4P的sPEEK薄膜其甲醇滲透可達10-7cm2/s；Nafion方面，N-1B4P-24hr薄膜甲醇滲透也能降低至純Nafion的三分之一。而在質子導電度方面，10%1B1P的sPEEK薄膜在100℃時的變濕導電度也高於原本的sPEEK薄膜；在Nafion薄膜中，除了sPMI比例較低的N-4B1P-6hr及N-4B1P-24hr兩薄膜在100℃時的變濕導電度較不及純Nafion外，其他4種組成的薄膜則是優於純Nafion薄膜。而其他如離子交換容量(Ion Exchange Capacity, IEC)、水含量(Water uptake)及熱穩定性等性質，在本篇論文中皆有加以探討、比較。

The most common problems of the fuel cell membranes are the insufficient of the ability to retain water at low humidity that result in the low proton conductivity and on the other hand, the high methanol permeability that deduces the performance of the fuel cell. Because of the morphology of the water channel, the most commonly used commercial Nafion membrane has high rate of soaking and losing water. Therefore, the proton conductivity of Nafion membranes is pretty low under ambient condition. On the other hand, the hydrocarbon proton conducting membranes may have lower proton permeability but the proton conductivity may not be good enough compared to Nafion membrane.
This research introduce the hyperbranch copolymer with sulfonic groups into membranes can promote proton conductivity and reduce methanol permeability simultaneously. We use the copolymer of 1,1’-(Methylenedi-4,1-phenylene) bismaleimide (BMI) and sulfonated N-Phenylmaleimide (sPMI) into Nafion and sulfonated poly ether ether ketone (sPEEK). The proton conductivity will increase by the sulfonic groups of the sPMI and the methanol permeability will decrease by the formation of semi-IPN (semi-Interpenetrating Polymer Network) structure of BMI. The different ration between BMI and sPMI can adjust the structure of semi-IPN in order to prepare an organic/organic composite membrane that has high proton conductivity under low humidity and high methanol resistant ability.
According to the data, we know that while the ratio between BMI and sPMI is 1 : 4, the methanol permeability is effectively decreased in spite of sPEEK and Nafion membranes. The methanol permeability of 20%1B4P sPEEK membrane can reach 10-7cm2/s and N-1B4P-24hr membrane can deduce 1/3 compared to the pure Nafion. The proton conductivity of 10%1B1P sPEEK membrane is higher than pure sPEEK under 100℃ and various humidity. On the other side, except the N-4B1P-6hr and N-4B1P-24hr with fewer sulfonic groups, the proton conductivity of the rest 4 membranes with different composition are better than pure Nafion under 100℃ and various humidity. The Ion Exchange Capacity (IEC), water uptake and the thermal stability are also discussed in the research.

[1] Grove, W. R., Philos. Mag. Ser. 1839, 3, 14, 127.
[2] Smitha, B.; Sridhar, S.; Khan, A. A., "Solid polymer electrolyte membranes for fuel cell
applications--a review" J. Membr. Sci. 2005, 259, 1-2, 10.
[3] Watanabe M., Uchida H., Seki Y., Emori M., The Electrochemical Society Meeting,
PV94-2, Abstract No.606, Electrochemical Society: Pennington, NJ, 1994, pp946-947.
[4] Mauritz, K. A. Mater. Sci. Eng., C 6 (1998) 121.
[5] Miyake, N. Wainwright, J.S. Savinell, R.F., J. Electrochemical Society. 148 (2001) A898.
[6] Xu, K.; Chanthad, C.; Gadinski, M. R.; Hickner, M. A.; Wang, Q., "Acid-Functionalized
Polysilsesquioxane−Nafion Composite Membranes with High Proton Conductivity and
Enhanced Selectivity" Appl. Mater. Interfaces 2009, 1, 11, 2573.
[7] 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 2008, 177, 2, 247.
[8] Saccà, A.; Gatto, I.; Carbone, A.; Pedicini, R.; Passalacqua, E., "ZrO2-Nafion composite
membranes for polymer electrolyte fuel cells (PEFCs) at intermediate temperature" J.
Power Sources 2006, 163, 1, 47.
[9] Jalani, N. H.; Dunn, K.; Datta, R., "Synthesis and characterization of Nafion® -MO2
(M = Zr, Si, Ti) nanocomposite membranes for higher temperature PEM fuel cells"
Electrochim. Acta 2005, 51, 3, 553.
[10] Zeng, R.; Wang, Y.; Wang, S.; Shen, P. K., "Homogeneous synthesis of PFSI/silica
composite membranes for PEMFC operating at low humidity" Electrochim. Acta 2007, 52,
12, 3895.
[11] Zhai, Y.; Zhang, H.; Hu, J.; Yi, B., "Preparation and characterization of sulfated zirconia
(SO42-/ZrO2)/Nafion composite membranes for PEMFC operation at high
temperature/low humidity" J. Membr. Sci. 2006, 280, 1-2, 148.
[12] Hara, S.; Miyayama, M., "Proton conductivity of superacidic sulfated zirconia" Solid
State Ionics 2004, 168, 1-2, 111.
[13] Thampan, T. M.; Jalani, N. H.; Choi, P.; Datta, R., "Systematic Approach to Design
Higher Temperature Composite PEMs" J. Electrochem. Soc. 2005, 152, 2, A316.
[14] Staiti, P.; Minutoli, M.; Hocevar, S., "Membranes based on phosphotungstic acid and
polybenzimidazole for fuel cell application" J. Power Sources 2000, 90, 2, 231.
[15] Staiti, P.; Minutoli, M., "Influence of composition and acid treatment on proton
conduction of composite polybenzimidazole membranes" J. Power Sources 2001, 94, 1, 9.
[16] Staiti, P., "Proton conductive membranes based on silicotungstic acid/silica and
polybenzimidazole" Mater. Lett. 2001, 47, 4-5, 241.
[17] Honma, I.; Takeda, Y.; Bae, J. M., "Protonic conducting properties of sol-gel derived
organic/inorganic nanocomposite membranes doped with acidic functional molecules"
Solid State Ionics 1999, 120, 1-4, 255.
[18] Honma, I.; Nomura, S.; Nakajima, H., "Protonic conducting organic/inorganic
nanocomposites for polymer electrolyte membrane" J. Membr. Sci. 2001, 185, 1, 83.
[19] Amarilla, J. M.; Rojas, R. M.; Rojo, J. M.; Cubillo, M. J.; Linares, A.; Acosta, J. L.,
"Antimonic acid and sulfonated polystyrene proton-conducting polymeric composites"
Solid State Ionics 2000, 127, 1-2, 133.
[20] Bonnet, B., Jones, D. J., Roziere, J., Tchicaya, L., Alberti, G., Casciola, M. Massinelli, L.,
Baner, B., Peraio, A., Ramunni, E. “Electrochemical characterisation of sulfonated
polyetherketone membranes”; J. New Mater. Electrochem. Syst. 2000, 3, 87.
[21] Zaidi, S. M. J.; Mikhailenko, S. D.; Robertson, G. P.; Guiver, M. D.; Kaliaguine, S.,
"Proton conducting composite membranes from polyether ether ketone and
heteropolyacids for fuel cell applications" J. Membr. Sci. 2000, 173, 1, 17.
[22] Nunes, S. P.; Ruffmann, B.; Rikowski, E.; Vetter, S.; Richau, K., "Inorganic modification
of proton conductive polymer membranes for direct methanol fuel cells" J. Membr. Sci.
2002, 203, 1-2, 215.
[23] Kaliaguine, S.; Mikhailenko, S. D.; Wang, K. P.; Xing, P.; Robertson, G.; Guiver, M.,
"Properties of SPEEK based PEMs for fuel cell application" Catal. Today 2003, 82, 1-4,
213.
[24] Rozie´re, J., Jones, D. J., Tchicaya-Bouckary, L., Bauer, B. WO 02/05370, 2000.
[25] Marani, D.; D’Epifanio, A.; Traversa, E.; Miyayama, M.; Licoccia, S., "Titania
Nanosheets (TNS)/Sulfonated Poly Ether Ether Ketone (SPEEK) Nanocomposite Proton
Exchange Membranes for Fuel Cells†" Chem. Mater. 2009, 22, 3, 1126.
[26] Jones, D. J.; Roziere, “Advances in the Development of Inorganic–Organic Membranes
for Fuel Cell Applications” J. Adv. Polym. Sci. 2008, 215, 219–264.
[27] Einsla, M. L.; Kim, Y. S.; Hawley, M.; Lee, H.-S.; McGrath, J. E.; Liu, B.; Guiver, M.
D.; Pivovar, B. S. “Toward Improved Conductivity of Sulfonated Aromatic Proton
Exchange Membranes at Low Relative Humidity”Chem. Mater. 2008, 20, 5636.
[28] Kim, T. W.; Sahimi, M.; Tsotsis, T. T., "Preparation and Characterization of Hybrid
Hydrotalcite-Sulfonated Polyetheretherketone (SPEEK) Cation-Exchange Membranes"
Ind. Eng. Chem. Res. 2009, 48, 21, 9504.
[29] Lee, K.; Nam, J. H.; Lee, J. H.; Lee, Y.; Cho, S. M.; Jung, C. H.; Choi, H. G.; Chang, Y.
Y.; Kwon, Y. U.; Nam, J. D., "Methanol and proton transport control by using layered
double hydroxide nanoplatelets for direct methanol fuel cell" Electrochem. Commun.
2005, 7, 1, 113.
[30] Lee, K.; Nam, J. D., "Optimum ionic conductivity and diffusion coefficient of
ion-exchange membranes at high methanol feed concentrations in a direct methanol fuel
cell" J. Power Sources 2006, 157, 1, 201.
[31] Decker, B.; Hartmann-Thompson, C.; Carver, P. I.; Keinath, S. E.; Santurri, P. R.,
"Multilayer Sulfonated Polyhedral Oligosilsesquioxane (S-POSS)-Sulfonated
Polyphenylsulfone (S-PPSU) Composite Proton Exchange Membranes†" Chem. Mater.
2009, 22, 3, 942.
[32] Hartmann-Thompson, C.; Merrington, A.; Carver, P. I.; Keeley, D. L.; Rousseau, J. L.;
Hucul, D.; Bruza, K. J.; Thomas, L. S.; Keinath, S. E.; Nowak, R. M.; Katona, D. M.;
Santurri, P. R., "Proton-conducting polyhedral oligosilsesquioxane nanoadditives for
sulfonated polyphenylsulfone hydrogen fuel cell proton exchange membranes" J. Appl.
Polym. Sci. 2008, 110, 2, 958.
[33] Sun, J.; Jordan, L. R.; Forsyth, M.; MacFarlane, D. R., "Acid-Organic base swollen
polymer membranes" Electrochim. Acta 2001, 46, 10-11, 1703.
[34] Fu, Y.-Z.; Manthiram, A., "Nafion--Imidazole--H3PO4Composite Membranes for Proton
Exchange Membrane Fuel Cells" J. Electrochem. Soc. 2007, 154, 1, B8.
[35] Deimede, V.; Voyiatzis, G. A.; Kallitsis, J. K.; Qingfeng, L.; Bjerrum, N. J., "Miscibility
Behavior of Polybenzimidazole/Sulfonated Polysulfone Blends for Use in Fuel Cell
Applications" Macromolecules 2000, 33, 20, 7609.
[36] Qingfeng, L.; Hjuler, H. A.; Bjerrum, N. J., "Phosphoric acid doped polybenzimidazole
membranes: Physiochemical characterization and fuel cell applications" J. Appl.
Electrochem. 2001, 31, 7, 773.
[37] Felice, C.; Ye, S.; Qu, D., "Nafion−Montmorillonite Nanocomposite Membrane for the
Effective Reduction of Fuel Crossover" Ind. Eng. Chem. Res. 2010, 49, 4, 1514.
[38]Ladewig, B. P.; Knott, R. B.; Hill, A. J.; Riches, J. D.; White, J. W.; Martin, D. J.; Diniz
da Costa, J. C.; Lu, G. Q., "Physical and Electrochemical Characterization of Nanocomposite Membranes of Nafion and Functionalized Silicon Oxide" Chem. Mater. 2007, 19, 9, 2372.
[39] Lee, K.-S.; Jeong, M.-H.; Lee, J.-P.; Lee, J.-S., "End-Group Cross-Linked Poly(arylene
ether) for Proton Exchange Membranes" Macromolecules 2009, 42, 3, 584.
[40] 侯勝澍，「含交聯矽氧烷高分子摻合物之製備與其物性之研究」，國立成功大學，
博士論文，民國九十年。
[41] Mishra, S.; Bajpai, R.; Katare, R.; Bajpai, A., "On the mechanical strength of
biocompatible semi-IPNs of polyvinyl alcohol and polyacrylamide" Microsyst. Technol.
2008, 14, 2, 193.
[42] 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.
[43] Qiao, J.; Ikesaka, S.; Saito, M.; Kuwano, J.; Okada, T., "Life test of DMFC using
poly(ethylene glycol)bis(carboxymethyl)ether plasticized PVA/PAMPS
proton-conducting semi-IPNs" Electrochem. Commun. 2007, 9, 8, 1945.
[44] Wu, H.-L.; Ma, C.-C. M.; Kuan, H.-C.; Wang, C.-H.; Chen, C.-Y.; Chiang, C.-L.,
"Sulfonated poly(ether ether ketone)/poly(vinylpyrrolidone) acid-base polymer blends for
direct methanol fuel cell application" J. Polym. Sci., Part B: Polym. Phys. 2006, 44, 3,
565.
[45] Malmstroem, E.; Johansson, M.; Hult, A., "Hyperbranched Aliphatic Polyesters"
Macromolecules 1995, 28, 5, 1698.