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研究生：	許晃銘 Hus, Haung-Ming
論文名稱：	磺酸化磷酸鋯或芘基磺酸/磺酸化嵌段(苯乙烯-異戊二烯-苯乙烯)共聚物之質子傳導層之合成與鑑定 Synthesis and Characterization of Sulfonated Zirconium-Phosphate or Pyrenesulfonic acid / Poly(styrene-b-isoprene-b-styrene) Composite Membrane for Fuel Cell Applications
指導教授：	郭炳林 Kuo, Ping-Ling
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2011
畢業學年度：	99
語文別：	中文
論文頁數：	71
中文關鍵詞：	磺酸化嵌段(苯乙烯-異戊二烯-苯乙烯)共聚高分子、奈米複合膜、磷酸鋯、芘基磺酸、質子交換膜、直接甲醇燃料電池
外文關鍵詞：	Nanocomposite membrane, Pyrenesulfonic acid, Sulfonated Zirconium- phosphate nanoplates, Sulfonated Poly (styrene-b-isoprene-b-styrene), Proton exchange membrane, Direct methanol fuel cell
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本研究利用陰離子聚合反應得嵌段(苯乙烯-異戊二烯-苯乙烯)共聚高分子(PSPIPS)，再以磺酸化劑反應成磺酸化嵌段(苯乙烯-異戊二烯-苯乙烯)共聚高分子(sPSPIPS)，再將合成之磺酸化磷酸鋯(ZrP)或芘基磺酸(PSA)與sPSPIPS混摻成奈米複合膜，並藉由不同程度之混摻而得一系列質子交換膜。藉由FT-IR圖譜、1H-NMR及GPC圖譜鑑定薄膜結構與分子量。由TEM分析微觀型態，由分析顯示加入PSA確實使親水區域之密度增加，能較有效型成離子渠道，有利質子傳導。由TGA顯示，Td5約在200℃，顯示本系列薄膜具有良好的熱穩定性。複合膜隨混摻比例上升質子交換當量也隨之上升，且含水率、自由水及結合水也隨之上升。其中混摻 PSA之奈米複合膜，於95 %RH、30℃時，質子傳導度可達6.6x10-2 S/cｍ，為未混摻薄膜36.6倍。由直接甲醇燃料電池單電池組測試結果，可知混摻PSA之複合膜為未混摻薄膜效能之2.28倍，可知混摻PSA唯一提升質子傳導度之有效方法。

A new class of nanocomposite membranes have been developed by
incorporating pyrenesulfonic acid(PSA) or sulfonated zirconium-phosphate nanoplates (ZrP) into Poly (styrene-b-isoprene-b-styrene)(sPSPIPS) matrix via anionic polymerization and sulfonated agent arecasting by solution. The structural characterizations of sPSPIPS systemand PSA or ZrP at various weight ratio is studied by FT-IR, 1H-NMR andGPC spectra. From TEM analysis, the hydrophilic domain for PSAsystem has higher density than pure membrane. From TGA analysis,these membranes possess good thermal stability(Td5=200℃). The IEC ofcomposite membranes increase with PSA and ZrP wt% increasing and thewater uptake, freeze water and bound water of composite membranesincrease with IEC. The highest proton conductivity of compositemembrane of PSA system is 6.6×10-2 Scm-1 under 95%RH at 30℃ being 36.6 times of pure membrane. The maximum power density of compositemembrane of PSA system for Direct Methanol Fuel Cell is 2.28 times ofpure membraneat 30℃.

目錄
中文摘要………………………………………………………………..I
英文摘要………………………………………………………...……….II
致謝…………………………………………………………………….III
目錄…………………………………………………………………….IV
表目錄………………………………………………………………VIII
圖目錄………………………………………………………………..…IX
第一章  緒論………………………………………………………...….1
第二章  文獻回顧…………………………………………………...….3
2-1  燃料電池之歷史與優點……………………………………3
2-2  燃料電池種類……………………………..……………….…3
2-3  質子交換膜燃料電池….……………………………..………7
2-4  直接甲醇燃料電池….…………….…………………………9
2-5  質子交換膜….………………………………………………10
2-5.1 改質型氟系質子交換膜…………………………….12
2-5.2 磺酸化碳氫質子交換膜………………………….….13
2-5.3 有機-無機膜…………………..…………………….14
2-5.4 親水性無機及其複合膜膜……………………….….16
2-6  磷酸鋯之結構及其衍生物….………………………………16
2-7  陰離子聚合反應原理….……………………………………18
2-7.1 起始聚合與起始反應……………………………….19
2-7.2 成長反應…………………..……………………….22
2-7.3 無終止反應與其特色………..……………….…..….23
2-8  嵌段共聚物……………..….……………………………..…23
2-8.1 嵌段共聚物之合成原理…………………..………....24
2-9  MEA製備……..…..….……………………………………..25
2-10 極化曲線……………..….…………………………………..26
2-11 交流阻抗分析……..….……………………………………..27
2-11.1 基礎電路簡介…………………..…………………..27
2-11.2 交流阻抗分析…………………..………………….30
第三章  實驗內容………………………………………….………….34
3-1  實驗藥品.……..…..….………………………….…………..34
3-2  實驗儀器.……..…..….……………….……………………..35
3-3  磺酸化共具高分子之製備.……..…………………………..36
3-3.1 嵌段(苯乙烯-異戊二烯-苯乙烯)共聚高分子之製備流
     程……………………………………………………..36
3-3.2 磺酸化嵌段(苯乙烯-異戊二烯-苯乙烯)共聚高分子之
     製備流程……………………………………………..37
3-3.3 磺酸化磷酸鋯之製備…..…..……………….……….38
3-4  質子交換膜之鑑定.……..……………………….………..39
3-4.1 傅立葉轉換紅外線光譜儀..………..……….……….39
3-4.2 核磁共振光譜儀…………………………….……….39
3-4.3 離子交換當量…………….……………….……….39
3-4.4 熱重分析…………………….…………….……….40
3-4.5 凝膠滲透層析儀…………………...……………….40
3-4.6 含水率測試….…………….………...……………….40
3-4.7 結合水………….…………….………...…………….41
3-4.8 交流阻抗分析…………….………...……………….42
3-4.9 甲醇穿透…….…………….………...…….……….43
3-4.10 X光繞射儀…….…………….……….…………….44
3-4.11 微相結構…….…………….………...…………….44
3-4.12 膜電極製備與單電池測試……………………….45
第四章  實驗內容…………………………………………….……….46
4-1  質子交換膜之製備與鑑定.……..…………………………..46
4-1.1 傅立葉轉換紅外線光譜…...……………….……….46
4-1.2 氫式核磁共振光譜……………...………….……….48
4-1.3 凝膠滲透層析法……….………...………………….50
4-1.4 X光繞射圖譜.…………….………...……………….50
4-2 熱重分析………….…………………...…………………….51
4-3 質子交換當量與質子傳導度...………..…………….….….53
4-4 含水率與質子交換膜中水狀態.…………………….……….57
4-5微相結構…………….………...……………………………..61
4-6 甲醇穿透…….…………….………...……………..……….63
4-7 單電池測試…….…………….……….……………..……….64
第五章  結論…………………………………………………….…….66
第六章  參考文獻…….……………………………………….…….68


表目錄
Table 2-1: Summary of Fuel-Cell types………………………...……...	6

Table 2-2: Summary of inorganic-organic composite membranes under      developmemt	15

Table 2-3: Impedance equations for equivalent circuit elements…….…29

Table 4-1: The IEC values and conductivity of sPSPIPS, sPSPIPS-PSA-x %, sPSPIPS-ZrP-x% and sPSPIPS-PSA-1%- ZrP-1%.............55

Table 4-2: The IEC values and state of water of sPSPIPS, sPSPIPS-PSA- x%, sPSPIPS-ZrP-x% and sPSPIPS-PSA-1%- ZrP-1%...........58

Table 4-3: The IEC values and state of water of sPSPIPS, sPSPIPS-PSA- x %, sPSPIPS-ZrP-x% and sPSPIPS-PSA-1%- ZrP-1%..........63


圖目錄
Figure 2-1: Membrane electrode assembly, MEA………………….…....8
Figure 2-2: Operating scheme of DMFC……………………………….10
Figure 2-3: Structure of Nafion…………………………………....…...11
Figure 2-4: Cluster-network model of hydrated Nafion………..….…....11
Figure 2-5: Schematic representation of redistribution of ion exchange sites which occurs on dehydration of polymer………….....12
Figure 2-6: Schematic representation of the microstructures of Nafion and a sulfonated poly(ether ketone)…….……...………............13
Figure 2-7: Chemical structure of unit cell of α-zirconium phosphate.....17
Figure 2-8: Chemical structure of Sulfonated Zirconium-Phosphate…..17
Figure 2-9: Polarization curve…………….………………………….....27
Figure2-10: Phase diagram showing the relationship between alternating current and voltage signals at frequency ω…………….......28
Figure2-11: Equivalent circuit of an electrochemical cell……………..30
Figure2-12: Nyquist plot of equivalent circuit……………….………31
Figure2-13: Impedance representation of a resistor and a Constant Phase Element (a) in series; (b) in parallel…………………..….32
Figure 3-1: Preparation of polystyrene-polyisoprene-polystyrene)…….36
Figure 3-2: 1-Pyrene sulfonic acid………………………...……………37
Figure 3-3: (a) Sulfonated agent and (b) Sulfonated Poly(styrene-b-isoprene-b-styrene)………………………..38
Figure 3-4 : Schematic of the measurement cell for proton conductivity.43
Figure 3-5 : Scheme diagram of the cell for the methanol crossover measurement…………..………………………………..….44
Figure 4-1: FTIR spectra of PSPIPS and sPSPIPS…..………………….47
Figure 4-2: H-NMR spectra of PSPIPS……………………….………...49
Figure 4-3: H-NMR spectra of PSPIPS and sPSPIPS…………………..49
Figure 4-4: GPC of PSPIPS……………...……………….……………..50
Figure 4-5: X-ray powder pattern of ZrP………………………….…….51
Figure 4-6: TGA spectra of PSPIPS and sPSPIPS………………...…….52
Figure 4-7: Differentiate TGA spectra of PSPIPS and sPSPIPS………..52
Figure 4-8: The residual of PSPIPS and sPSPIPS…………………...….53
Figure 4-9: Conductivity of the sPSPIPS, sPSPIPS-PSA-x%, sPSPIPS-Zr P -x%, sPSPIPS-PSA-1%-ZrP-1%and Nafion at 330.15K and 95% RH……………………………………………............56
Figure4-10: Temperature dependence of the proton Conductivity for (a) sPSPIPSsPSPIPS-PSA-x% (b) sPSPIPS, sPSPIPS-ZrP-x% at 95RH……………………………………………………....56
Figure4-11: DSC thermograms of the sPSPIPS and sPSPIPS-PSA-x%..59
Figure4-12: DSC thermograms of the sPSPIPS, sPSPIPS-ZrP-x% and sPSPIPS-PSA-1%-ZrP-1%...................................................59
Figure4-13: The degree of bound water of sPSPIPS-PSA-x%................60
Figure4-14: The dependences of conductivity on water uptake at 303.15K ,333.15K and 353.15K………...…………...….....60
Figure4-15: TEM micrographs of (a)Nafion(b)sPSPIPS(c) sPSPIPS-PSA-1.5% (d) sPSPIPS-PSA-2%(e) sPSPIPS-PSA-2.5%(f) sPSPIPS-ZrP-2% at 100nm scale bar…………………………………………………..……...62
Figure4-16: Selectivity of sPSPIPS, sPSPIPS-PSA-x% and sPSPIPS-ZrP-2%..................................................................64
Figure4-17: Schematic diagram of the single cell test system for DMFC…………..….………………………………………65
Figure4-18: Polarization curves for the sPSPIPS-PSA-2% and sPSPIPS operating at 30℃………………...……………...…………65


                                    

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