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研究生:鄭武輝
研究生(外文):Wu-Huei Jheng
論文名稱:側接磺酸基之交聯型醯亞胺/矽氧烷混成複合膜之製備與質子傳導特性研究
論文名稱(外文):Preparation and Proton-conducting Properties of Crosslinked Imide/Siloxane Hybrid Membranes Grafted with Sulfonic Acid
指導教授:郭炳林郭炳林引用關係
指導教授(外文):Ping-Ling Kuo
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2008
畢業學年度:96
語文別:英文
論文頁數:71
中文關鍵詞:質子傳導膜複合膜溶膠法聚(苯乙烯-馬來酸酐)聚矽氧烷
外文關鍵詞:proton-conducting membranehybridpolysiloxanepoly(styrene-co-maleic anhydride)sol-gel
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本研究利用具有磺酸基之monoamine(AESA-Na)與aminopropyltriethoxysilane(APTES)依等化學計量與帶有酸酐基之聚(苯乙烯-馬來酸酐)進行反應,而後經由溶膠法(sol-gel process)進行交聯,製備成一系列含有不同磺酸基之新型的醯亞胺/矽氧烷混成型質子傳導膜。研究結果顯示,此系列高分子質子傳導膜呈現均相結構並具有不錯的機械強度及氧化穩定性;由FT-IR及solid-state 13C 與 29Si NMR可確定本實驗成功製備出混成型質子傳導膜。在TGA結果方面其Td0.1約在420oC,顯示本系列薄膜具有良好的熱穩定性。此外,導入的無機聚矽氧烷增加與水之間的氫鍵作用力而促進結合水率(Bound water degree)的提升,使得複合膜的擁有低於商用品Nafion-117的甲醇穿透係數7.76×10-7 cm2s-1;且質子傳導度在完全水合狀態及30 oC可達0.0570 Scm-1,並可在60 oC下得到24.9 mW cm-2的最大功率均優於商用品Nafion-117 (質子傳導度 = 0.0541 Scm-1, 甲醇穿透係數= 2.51×10-6 cm2s-1 and 最大功率 = 21.1 mW cm-2)。
A new type of hybrid proton-conducting membranes with crosslinked polysiloxane framework was designed and prepared via sol-gel approach based on poly(styrene-co-maleic anhydride) modified with 2-aminoethanesulfonic acid sodium salt (AESA-Na) and Aminopropyltriethoxysilane (APTES). The number density of the pendant of sulfonate group was controlled by the ratio of AESA-Na to APTES. The resulted membranes own good mechanical strength. The structural characterizations of these membranes were confirmed by FT-IR and solid-state 13C and 29Si NMR spectra. All of these membranes exhibit a wholly amorphous morphology, perform adequate oxidative stability in Fenton’s reagent at 80 �aC for 1 h, and show two step of weight loss from 350 �aC, indicating their good thermal stability. The polysiloxane network is contributive to the increase in bound water degree and decrease in methanol permeability. The HPM sample with 1.3 theoretical mequiv SO3H/g reaches the proton conductivity of 0.0570 Scm-1 at 30 �aC and 0.125 Scm-1 at 70 �aC, respectively. Moreover, it also has low methanol permeability of 7.76×10-7 cm2s-1 at 30 �aC, and yield maximum power density of 24.9 mW cm-2 at 60 �aC. The HPM performed slightly better than Nafion 117 (proton conductivity = 0.0541 Scm-1, methanol permeability = 2.51×10-6 cm2s-1 and power density = 21.1 mW cm-2) under the same conditions.
CONTENTS
ABSTRACT……………………………………………………………………………i
摘要……………………………………………………………………………………ii
誌謝……………………………………………………………………………………iii
LIST OF TABLES……………………………………………………………………iv
LIST OF SCHEMES…………………………………………………………………v
LIST OF FIGURES……………………………………………………………………vi

CHAPTER 1. INTRODUCTION……………………………………………………1
1-1 Background………………………………………………………1
1-2 Types of Fuel Cell……………………………………………………2
1-2.1 Proton exchange membrane fuel cell……………………………6
1-2.2 Direct methanol fuel cell…………………………………………6
1-3 Overview of PEM-based fuel cell………………………………………………………………………8
1-3.1 Membrane electrode assembly (MEA)……………………………8
1-3.2 Electrocatalyst and carbon support………………………………10
1-3.3 Proton exchange membrane……………………………………11
1-3.3.1 Functionalized sulfonic acid of hydrocarbon type proton exchange membranes……………………………………13
1-3.3.2 Organic-inorganic hybrid membranes……………………14
1-3.4 Polarization curve………………………………………………16
1-4 Prospects of direct methanol fuel cells………………………………17
1-4.1 Slow kinetics of methanol eletro-oxidation……………………17
1-4.2 Methanol crossover………………………………………………19
1-5 Research Motivation…………………………………………………20
CHAPTER 2. THEOREMS………………………………………………………21
2-1 Solid-State Nuclear Magnetic Resonance…………………………21
2-2 Alternating current impedance spectroscopy………………………23
2-2.1 Introduction of fundamental electrical circuits…………………23
2-2.2 Analysis of AC impedance………………………………………26
2-3 Imidization……………………………………………………………29
2-3.1 Thermal (Bulk) Imidization……………………………………30
2-3.2 Solution Imidization……………………………………………32
2-3.3 Chemical Imidization……………………………………………32
2-4 Sol-gel process………………………………………………………33
CHAPTER 3. EXPERIMENTAL SECTION……………………………………36
3-1 Materials………………………………………………………………………………………………36
3-2 Experimental Steps…………………………………………………36
3-2.1 Synthesis of Sodium 2-Aminoethanesulfonate (AESA-Na)……36
3-2.2 Synthesis of hybrid proton-conducting membranes (HPM)……37
3-3 Characterizations……………………………………………………39
CHAPTER 4. RESULTS AND DISCUSSION……………………………………46
4-1 Characterization of Organic-inorganic Hybrid Proton-conducting Membranes…………………………………………………………46
4-1.1 FT-IR Studies…………………………………………………47
4-1.2 13C CP/MAS NMR ………………………………………………49
4-1.3 29Si CP/MAS NMR……………………………………………50
4-2 Thermal behavior……………………………………………………51
4-3 IEC…………………………………………………………………53
4-4 Water uptake and State of water……………………………………55
4-5 Methanol Permeability……………………………………………57
4-6 Proton conductivity measurements………………………………57
4-7 Microscopic characterization………………………………………58
4-8 Oxidative Stability…………………………………………………59
4-9 Tensile strength……………………………………………………60
4-10 Single Cell Performance……………………………………………60
CHAPTER 5. GENERAL CONCLUSIONS………………………………………62
REFERENCE…………………………………………………………………………63
VITA……………………………………………………………………………………71
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