二次交聯改質聚乙烯醇為直接甲醇燃料電池質子傳導膜之研究

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研究生：	蔡春恩 Chun-En Tsai
論文名稱：	二次交聯改質聚乙烯醇為直接甲醇燃料電池質子傳導膜之研究 Investigation of Poly(Vinyl Alcohol)-based Proton Conducting Membranes Modified by a Two-step Crosslinking Strategy for DMFCs
指導教授：	黃炳照 Bing-Joe Hwang
口試委員:	林智汶 Chi-Wen Ljn 陳志堅 Jyh-Chien Chen 高憲明 Hsien-Ming Kao 劉豫川 Yu-Chung Liu
學位類別：	博士 Doctor
系所名稱：	工程學院 - 化學工程系 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：	182
中文關鍵詞：	直接甲醇燃料電池(DMFC) 、聚乙烯醇、質子傳導、磺酸化、二次交聯、半-互穿網狀
外文關鍵詞：	DMFC, Poly(vinyl alcohol), Proton conducting, Sulfonation, Two-step crosslinking process, semi-interpenetrating network
相關次數：	點閱：242 下載：9
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本研究旨在藉二次交聯步驟改質聚乙烯醇作為低溫操作用的直接甲醇燃料電池(Direct methanol fuel cell, DMFC)之質子傳導電解質薄膜，本研究採用成膜性高、具良好化學穩定性且低價格的聚乙烯醇( Polyvinyl alcohol, PVA)為膜材主體，以二次交聯製程製備改質PVA電解質薄膜，藉以取代價格昂貴又無法有效阻擋甲醇穿透的Nafion膜材。本研究之改質聚乙烯醇薄膜主要分成兩個部份來探討。(一)基本型網狀構造薄膜：係為以丁二酸磺酸（sulfosuccinic acid ，SSA）同時作為磺酸化劑與第一交聯劑，以便在引進磺酸根(SO3H)來提高氫離子傳導性的同時，利用丁二酸磺酸的羧酸基-COOH與聚乙烯醇上的羥基-OH進行酯化交聯反應，此為第一次交聯；並於成膜後，再利用戊二醛(Glutaraldehyde, GA) 作為二次交聯劑，利用GA上的醛基-CHO與PVA上剩餘之羥基-OH進行醇醛縮合之二次交聯反應。(二)半-互穿網狀構造之薄膜：係為在以丁二酸磺酸(SSA)與聚乙烯醇(PVA)進行第一次交聯的同時，於該PVA混合溶液中，摻混以高分子量之聚苯乙烯磺酸(Poly(styrene sulfonic acid)，PSSA)，於成膜時形成半-互穿網狀構造之薄膜，其後再利用戊二醛進行二次交聯反應。
於第一組研究中發現，此二次交聯製程改質聚乙烯醇之質子傳導膜，較以往文獻中只使用一次交聯之改質方式更能提昇薄膜之機械強度及抗水性，即使在高含量的磺酸化劑存在下，例如SO3H/PVA-OH 之莫耳比高於0.45，薄膜亦不會被水溶解，顯示薄膜具有良好之水穩定性。研究顯示此二次交聯改質之聚乙烯醇薄膜，具有良好之質子傳導性，於室溫下測定可達5.3 x 10-2 S cm-1，及良好之甲醇滲透抑制性，同一薄膜之甲醇滲透率為3.53 x 10-7 cm2 S-1，顯示改質聚乙烯醇薄膜之質子傳導性及甲醇滲透抑制性均優於Nafion。惟，在第一組研究中亦發現薄膜之質子傳導率及甲醇滲透率均隨SSA的含量增加而增加，顯示過多的SSA會減少可與GA進行第二次交聯反應之PVA上的OH含量，而使薄膜之外層疏水性保護層變得薄弱，因而降低甲醇滲透抑制性。
在第二組研究中，同樣使用二次交聯程序進行改質PVA，惟，固定適當比例之SSA第一交聯劑含量，其使SSA-SO3H/PVA-OH 之莫耳比=0.22，在第一次交聯的同時摻混以不同含量之高分子量聚苯乙烯磺酸(PSSA)作為磺酸化劑，於成膜時形成半-互穿網狀之構造，此方式不會隨SSA之含量而影響PVA與GA之第二次交聯反應，同時研究顯示，摻混以PSSA之長鏈高分子，當其量夠多時，例如PSSA/poly(vinyl alcohol) (g g−1) 大於0.72時，在此雙交聯的製程下，可因長鏈分子所產生之鏈糾纏效應，而提昇薄膜結構之緻密性，因而同時提昇質子傳導率及甲醇滲透抑制性，獲得較佳選擇率之薄膜，此膜材顯示良好之質子傳導性，於室溫下測定可達5.88 x 10-2 S cm-1，及良好之甲醇滲透抑制性，同一薄膜之甲醇滲透率為1.68 x 10-7 cm2 S-1，亦顯示該等改質聚乙烯醇薄膜之質子傳導性及甲醇滲透抑制性均優於Nafion。

The aim of this study was to investigation of poly(vinyl alcohol)-based proton conducting membranes modified by a two-step crosslinking strategy for low temperature DMFCs. Because of its good chemical stability, film-fabrication ability and low cost, PVA was chosen to be the matrix of developed membranes for substitution the Nafion membrane showing high cost and poor barrier of methanol crossover. There were two systems developed in this study. One is synthesizes poly(vinyl alcohol) (PVA)-based polymer electrolyte membranes by a modified two-step crosslinking process involving esterization and acetal ring formation reactions. The other is Poly(styrene sulfonic acid)/poly(vinyl alcohol) proton-conducting membranes with semi-interpenetrating networks (semi-IPNs) were prepared using a previously modified two-step crosslinking strategy.
The first work of this study uses sulfosuccinic acid (SSA) as the first crosslinking agent to form an inter-crosslinked structure and a promoting sulfonating agent. Glutaraldehyde (GA) as the second crosslinking agent, reacts with the spare OH group of PVA and forms, not only a dense structure at the outer membrane surface, but also a hydrophobic protective layer. Compare with membranes prepared by a traditional one-step crosslinking process, membranes prepared by the two-step crosslinking process exhibit excellent dissolution resistance in water. The membranes become water-insoluble even at a molar ratio of SO3H/PVA-OH as high as 0.45. Moreover, the synthesized membranes also exhibit high proton conductivities and high methanol permeability resistance. The current study measures highest proton conductivity of 5.3 x 10-2 S cm-1 at room temperature from one of the synthesized membranes, higher than that of the Nafion® membrane. Methanol permeability of the synthesized membranes measures about 3.53 x 10-7 cm2 S-1, about one order of magnitude lower than that of the Nafion® membrane.
The other work of this study is investigation of poly(styrene sulfonic acid)/poly(vinyl alcohol) proton-conducting membranes with semi-interpenetrating networks (semi-IPNs) were prepared using a modified two-step crosslinking strategy. We previously employed sulfosuccinic acid (SSA) and glutaraldehyde (GA) as crosslinking agents to form a dense hydrophobic layer at the outer membrane surface. Although the proton conductivity of the resulting membrane increased with the content of SSA, the methanol permeability also increased. In this study it was found that the introduction of a sufonating agent, with a high molecular weight, i.e. poly(styrene sulfonic acid) (PSSA), at a PSSA/poly(vinyl alcohol) (g g−1) ratio greater than 0.72, increased the density of the tangled IPN structures that effectively impede the membrane's permeability to MeOH, while enhancing its proton conductivity. The synthesized semi-IPN membranes exhibited high proton conductivities (up to 5.88 × 10−2 S cm−1 at room temperature, i.e. greater than those of Nafion membranes) and high resistances to MeOH permeation (ca. 1.68 × 10−7 cm2 S−1, that is approximately one order of magnitude lower than that of Nafion membranes).

目錄
摘要….................................................................................................I
Abstract…........................................................................................... IⅤ
誌謝........................................................................................ⅤII
目錄………………………………………...…………..…………IX
圖目錄…………………………………….………………………… XⅤ
表目錄………………………………………………...……………XXII
符號表.............................................................................................. XXIⅤ
第一章	緒論……………………………………………………………..1
   1.1前言………………………………………………………1
   1.2燃料電池的發展簡介……………………………………………2
   1.3 燃料電池種類………………………………………………….3
     1.3.1鹼液型燃料電池 (Alkaline Fuel Cell, AFC) ……...…6
     1.3.2磷酸型燃料電池 (Phosphoric Acid Fuel Cells, PAFC) ..…8
1.3.3熔融碳酸鹽型燃料電池 (Molten Carbonate Fuel Cells,
 MCFC)…………………………………….………….……..9
1.3.4固態氧化物型燃料電池 (Solid Electrolyte Fuel Cells, SOFC)………………………………..…10
1.3.5質子交換薄膜型燃料電池 (Proton Exchange Membrane Fuel Cells , PEMFC) ………………………………………11
1.3.6直接甲醇燃料電池 (Direct Methanol Fuel Cells, DMFC) ………………13
1.4直接甲醇燃料電池之電化學原理………………….…………13
1.5直接甲醇燃料電池所面臨之瓶頸與發展方向………….……16
1.5.1 DMFC之陽極材料及其反應機制……………..…….……17
1.5.2 DMFC之陰極材料及其反應機制……………...…………21
1.5.3 DMFC之電解質薄膜材料………………………...………23
1.6 研究動機與目的………………….……………………………25
1.7 研究架構………………………………….……………………26
第二章	文獻回顧………………………………………………………29
2.1質子交換膜的工作原理………………………………………29
2.2高分子電解質薄膜材料的分類及發展現況………………..30
2.2.1 Nafion 薄膜材料系列………….………………………32
2.2.2 Nafion改質薄膜材料系列…………………………………36
2.2.3其它有機高分子薄膜材料系列…………………………38
2.2.4無機高分子薄膜材料系類…………………………………47
2.2.5有機-無機混成高分子薄膜材料系列…………………48
2.3高分子電解質薄膜之氫離子傳導機制………..………..50
第三章	實驗藥品、設備、步驟與原理…………………………………56
3.1實驗藥品與設備………………………………………………56
3.1.1實驗藥品……………………………………………………56
3.1.2實驗設備與器材……………………………………………57
3.2改質聚乙烯醇薄膜的製備……………………………………58
3.2.1 PVA-SSA-GA系列網狀構造薄膜製備………………58
     3.2.2  PVA-PSSA-SSA-GA系列半-互穿網狀構造薄膜製備…60
3.3聚乙烯醇的磺酸化、交聯反應與薄膜製備原理……………62
3.3.1聚乙烯醇之簡介……………………………………………61
3.3.2磺酸化的原理………………………………………………63
3.3.3聚乙烯醇磺酸化的原理………………………………63
3.3.4聚乙烯醇與戊二醛之縮合交聯原理……………………64
3.3.5聚乙烯醇的磺酸化、二次交聯改質薄膜的原理……65
3.3.5.1 PVA-SSA-GA系列網狀構造薄膜…...………..…...…65
3.3.5.2 PVA-PSSA-SSA-GA系列之半-互穿網狀構造薄膜66
3.4薄膜的成型原理………………………………………………...69
3.4.1相轉換法（phase transfer）…………………………………69
3.5實驗方法與原理………………………………………………70
3.5.1薄膜之結構鑑定…………………………………………70
3.5.1.1傅立葉轉換紅外光譜儀(FTIR)鑑定分析……….……70
3.5.1.2 X光射線繞射（X-ray diffraction）分析………….……71
3.5.2薄膜之熱性質分析…………………………………………72
3.5.2.1 DSC示差掃瞄熱分析…………………..……………72
3.5.2.2 TGA熱重分析……………………………………73
3.5.2.3熱程序升溫脫附反應(TPD)分析…………......………74
3.5.3薄膜之電化學性質分析………..…………..………………76
3.5.3.1 AC-Impedance交流阻抗電化學特性分析…...………76
3.5.4薄膜之物理性質分析………………………………………84
3.5.4.1薄膜含水率測試………………………………………84
3.5.4.2離子交換(Ion exchange capacity, IEC)容量測試……85
3.5.4.3甲醇滲透率量測……………………………………86
第四章	實驗結果……………………………………………………88
4.1改質PVA薄膜結構的鑑定……………………………………88
4.1.1 Pure PVA薄膜的官能基鑑定（FTIR/ATR分析）…………88
4.1.2 PVA-SSA-GA改質薄膜的官能基鑑定（FTIR/ATR分析） ………………………………………………………90
4.1.3 PVA-PSSA-SSA-GA改質薄膜的官能基鑑定（FTIR/ATR分析）...............102
4.1.4 X光射線繞射（X-ray diffraction）分析…………………108
4.2改質PVA薄膜之熱性質分析…………...…………………….112
4.2.1改質PVA薄膜之DSC示差掃瞄熱分析………………….112
4.2.2改質PVA薄膜之TGA熱重分析………………...……….115
4.2.3改質PVA薄膜之熱程控脫附反應 (TPD)與質譜儀(MS)分析.........................119
4.3改質PVA薄膜之電化學性質分析………………....…………132
4.3.1 AC-Impedance 交流阻抗分析……..…………...………132
4.4改質PVA薄膜之物理性質分析……………………..………134
4.4.1改質PVA薄膜之離子交換容量（IEC）分析……………134
4.4.2改質PVA薄膜之含水率分析……………………………135
4.4.3改質PVA薄膜之甲醇滲透率分析…………………...…142
4.4.4改質PVA薄膜之選擇率評估………………………...…144
第五章	 綜合討論………………………………………………….150
5.1影響薄膜性質之主要因素……………………….………..150
5.1.1薄膜之磺酸化…………………………………………….150
5.1.2薄膜之交聯反應…………………………………………151
5.2影響薄膜導電度的主要因素………………………………154
5.2.1分子結構…………………………………..……………154
5.2.2電荷載子的數目…………………………………………155
5.2.3電荷載子的遷移速率……………………………………156
5.2.4溫度…………………………………..……..……………158
5.3影響甲醇滲透率的主要因素…..…………….……………160
第六章	 結論………………………………………162
第七章	參考文獻……………………………………………………..165
作者簡介…………………………………………………178









圖目錄
Fig. 1.1 Schematic principle of a direct methanol fuel cell……………15
Fig. 1.2 The polarization curves for a direct methanol fuel cell……...…16
Fig. 1.3 The possible dehydration reactions for methanol on the anode catalysts……………………………….…...19
Fig. 1.4 The dehydration of water on anode catalysts…………...……...20
Fig. 1.5 The re-dehydration and desorption of carbon dioxide on anode catalysts……………………….….20
Fig.1.6 Oxygen reduction mechanisms on the cathode catalysts………………………..22
Fig. 1.7 The experimental flow chart………………………….………..28
Fig. 2.1 Transport mechanism in membrane………………..…………..29
Fig. 2.2 Chemical structure of the perfluorosulfonic acid electrolyte……………………….…………...33
Fig. 2.3 Dimensions of water-filled micropores……………….………..34
Fig. 2.4 Different forms of proton in water medium………………….52
Fig. 2.5 Proton conduction in water: mobility of proton………………..53
Fig. 2.6 Proton hops between two water molecules……………………53
Fig. 2.7 Proton mobility via a Zundel ion complex………………….. 54
Fig. 2.8 Mechanism of proton conduction in water…..………………55
Fig. 3.1 The experimental flow chart for the synthesis of PVA-SSA-GA membranes…………………………………………..58
Fig. 3.2 The experimental flow chart for the synthesis of PVA-PSSA-SSA-GA membranes………………………………….60
Fig. 3.3 The structure of PVA………………………………….62
Fig. 3.4 The structure of poly vinyl acetate ( PVAc ) monomer….….…62
Fig. 3.5 Crosslinking reaction between PVA and GA…………………..64
Fig. 3.6 Scheme：Crosslinking PVA formed by reaction between PVA and GA (a)Acetal ring group or ether linkage and (b) Aldehyde formation by monofunctional reaction…………...………………..65
Fig. 3.7 Possible crosslinking structure of PVA, SSA and GA…………67
Fig. 3.8 Semi-IPN structure of PVA-PSSA-SSA-GA membrane……….68
Fig. 3.9 AgO TPR reaction of TCD signal curve……..……...75
Fig. 3.10 Phase diagram showing the relationship between alternating current and voltage signals at frequency ω……………………….77
Fig. 3.11 Calculation of total impedance from component impedances..78
Fig. 3.12 Equivalent circuit of an electrochemical cell………..………..80
Fig. 3.13 (a) Nyquist plot  (b)Bode plot………………………….……82
Fig. 3.14 The top view and cross-section view of AC impedance cell
(a) real equipment ,  (b) Schematic diagram…………...….……..84
Fig. 3.15 Schematic diagram of methanol diffusion cell………………..87
Fig. 4.1 ATR IR curve of Pure PVA membrane…………………………89
Fig. 4.2 Compare the ATR IR curve of Pure PVA and PVA-SSA membrane………………………………………….90
Fig. 4.3 Crosslinking PVA formed by reaction between PVA and GA…91
Fig. 4.4 Compare the ATR IR cure (500〜4000 cm-1) of Pure PVA, PVA-SSA and PVA-SSA-GA membrane……………………….…92
Fig. 4.5 (a)〜(c) ATR IR spectra of the membrane with various molar ratios of SSA/OH (a) 0.152(1-PVA-SSA), (b) 0.222(2-PVA-SSA); and the second crosslinking step with GA for 1 hr (C1)and 2 hr (C2) ; and followed by heat treatment for 2 hr (H2), (c) the membranes with various molar ratios of SSA/OH = 0.152（1-PVA-SSA）, 0.222（2-PVA-SSA）, 0.293（3-PVA-SSA）, 0.364（4-PVA-SSA）for the second crosslinking step with GA for 1 hr (C1)…………...……101
Fig. 4.6 (a)〜(c) ATR IR spectra of membranes made with 22 mol% SSA/PVA-OH, and PSSA/PVA (g g–1) ratios of 0.00 (PVA-SSA), 0.36(1-PVA-PSSA-SSA), 0.54(2-PVA-PSSA-SSA), 0.72(3-PVA-PSSA-SSA), 0.9(4-PVA-PSSA-SSA) and 1.33(5-PVA-PSSA-SSA) after crosslinking with GA for 1 hr (C1) or 2 hr (C2) , and subsequent heat treatment for 2 hr (H2)…………107
Fig. 4.7 (a)〜(d) XRD curves of the membranes with various molar ratios of SSA/OH (a) 0.152(1-PVA-SSA), (b) 0.222(2-PVA-SSA), (c) 0.293（3-PVA-SSA）, (d) 0.364（4-PVA-SSA）; C1 and C2 means the second crosslinking step with GA for one and two hours; H2 means by heat treatment for two hours……………………..……110
Fig. 4.8 XRD curves of the membrane with various molar ratios of SSA/OH = 0.152（1-PVA-SSA）, 0.222（2-PVA-SSA）, 0.293（3-PVA-SSA）, 0.364（4-PVA-SSA） for the second crosslinking step with GA: (a) for 1 hr (C1) , and (b) for 2 hr (C2), with the second crosslinking step followed by heat treatment for 2 hr (H2)111
Fig. 4.9 (a)〜(d) XRD curves of membranes made with 22 mol% SSA/PVA-OH and PSSA/PVA (g g-1) ratios of (a) 0.36(1-PVA-PSSA-SSA), (b) 0.54(2-PVA-PSSA-SSA), (c) 0.72(3-PVA-PSSA-SSA), and (d) 0.9(4-PVA-PSSA-SSA) after crosslinking with GA for 1 hr (C1) or 2 hr (C2) and subsequent heat treatment for 2 hr (H2)…………………………111
Fig. 4.10  XRD curves of membranes made with 22 mol% SSA/PVA-OH and PSSA/PVA (g g-1) ratios of 0.36(1-PVA-PSSA-SSA), 0.54(2-PVA-PSSA-SSA), 0.72(3-PVA-PSSA-SSA), and 0.9(4-PVA-PSSA-SSA) after crosslinking with GA for 1 hr (C1) and subsequent heat treatment for 2 hr (H2)………………………..……..112
Fig. 4. 11 DSC curve of pure PVA…………………….113
Fig. 4.12 (a)〜(b) DSC curve of the membrane with various molar ratios of SSA/OH = 0.152（1-PVA-SSA）, 0.222（2-PVA-SSA）, 0.293（3-PVA-SSA）, 0.364（4-PVA-SSA） for the second crosslinking step with GA: (a) for 1 hr (C1), and (b) for 2 hr (C2), with the second crosslinking step followed by heat treatment for 2 hr (H2)…………………………………….……114
Fig. 4.13 DSC curve of the membranes made with 22 mol% SSA/PVA-OH and PSSA/PVA (g g-1) ratios of 0.36(1-PVA-PSSA-SSA), 0.54(2-PVA-PSSA-SSA), 0.72(3-PVA-PSSA-SSA), 0.9(4-PVA-PSSA-SSA), and 1.33(5-PVA-PSSA-SSA) after crosslinking with GA for 1 h (C1) and subsequent heat treatment for 2 hr(H2) …………………….……115
Fig . 4.14 TGA curve of pure PVA……………………….……116
Fig. 4.15 (a)〜(b) TGA curves of the membrane with various molar ratios of SSA/OH = 0.152（1-PVA-SSA）, 0.222（2-PVA-SSA）, 0.293（3-PVA-SSA）, 0.364（4-PVA-SSA） for the second crosslinking step with GA: (a) 1 hr (C1) , and (b) for 2 hr (C2), with the second crosslinking step followed by heat treatment for 2 hr (H2) ……117
Fig. 4.16  TGA curve of the membranes made with 22 mol% SSA/PVA-OH and PSSA/PVA (g g-1) ratios of 0.36(1-PVA-PSSA-SSA), 0.54(2-PVA-PSSA-SSA), 0.72(3-PVA-PSSA-SSA), 0.9(4-PVA-PSSA-SSA), and 1.33(5-PVA-PSSA-SSA) after crosslinking with GA for 1 hr (C1) and subsequent heat treatment for 2 hr (H2) ……………….……119
Fig. 4.17 Temperature programmed desorption (TPD) curve of pure PVA………………………………………….120
Fig 4.18 Decompsion mass of pure PVA at defferennt temperature：（a）90℃ (b) 140℃ (c) 258℃ (d) 329℃ (e) 400℃…………….…121
Fig. 4.19 Temperature programmed desorption (TPD) curve of 2-PVA-SSA membrane……………………….124
Fig. 4.20 Temperature programmed desorption (TPD) curve of 1-PVA-SSA-GA-C2H2 membrane…………………..……..…….125
Fig. 4.21 Temperature programmed desorption (TPD) curve of 4-PVA-PSSA-SSA-GA-C1H2 membrane…………..……..…….125
Fig. 4.22 Decompsion mass of 2-PVA-SSA membrane at defferennt temperature：（a）50℃ (b) 100℃ (c) 150℃ (d) 200℃ (e) 250℃(f)350℃(g)400℃(h)450℃………………..…………….…….127
Fig. 4.23 Decompsion mass of 1-PVA-SSA-C2H2 membrane at defferennt temperature：（a）60℃ (b) 100℃ (c) 150℃ (d) 200℃ (e) 250℃(f)300℃……………………..………….128
Fig. 4.24 Decompsion mass of 4-PVA-PSSA-SSA-C1H2 membrane at defferennt temperature：（a）50℃ (b) 100℃ (c) 150℃ (d) 200℃ (e) 250℃(f)300℃(g)350℃(h)550℃……………...…..………….130
Fig. 4.25 Decompsion mass of 4-PVA-PSSA-SSA-C1H2 membrane at defferennt temperature：（a）M=14 (b) M=18 (c) M=17 (d) M=32〜64………………………………………………….132
Fig. 4.26 (a), (b) DSC curves of PVA-SSA-GA membranes……….….141
Fig. 4.27 DSC curves of PVA-PSSA-SSA-GA membranes……..…….142
Fig. 4.28 Calibration curve of Methanol concentration vs. dn/dc….….144
Fig. 4.29 (a), (b) Methanol permeability and proton conductivity of PVA-SSA-GA membranes at different molar ratio percentages of SO3H/OH………………………….147
Fig. 4.30 Methanol permeabilities and proton conductivities of PVA-PSSA-SSA-GA membranes were featuring 22 mol% SSA/PVA-OH and PSSA/PVA (g g–1) ratios of 0.00, 0.36, 0.54, 0.72, 0.9, and 1.33. These membranes were crosslinked with GA for 1 h and then subjected to heat treatment for 2 h…………..……….148
Fig. 4.31 (a)〜(c) The relation with proton conductivities and ion exchange capacity (IEC) of (a) PVA-SSA-GA-C1H2，(b) PVA-SSA-GA-C2H2，and (c) PVA-PSSA-SSA-GA-C1H2 membranes…………………….149
Fig.5.1  Profile structure of SPVA membrane....................……….….152
Fig.5.2 Over swellen in the inert of film case curly and stratify…...….153




















表目錄
Table 1.1 The developing history of fuel cells……………………..…....4
Table 1.2 Comparision of different fuel cells……………………..……..5
Table 2.1 The permeabilities of Nafion membranes…………….………36
Table 2.2 The methanol crossover rate of PBI membrane on open circuit potential (OPC)………………………………..46
Table 2.3 The effect fuel cell operation factors on methanol crossover and performance. The PBI membrane was employed in this test…………………………………………………46
Table 3.1 Typical circuit elements………………………79
Table4.1  Assignments of the ATR IR (500〜4000 cm-1) peaks of pure PVA membrane……………………………….…89
Table 4.2 Assignments of the ATR IR (500〜4000 cm-1) peaks of PVA-SSA-GA membranes………………………..………….95
Table 4.3 Assignments of the signals in the ATR IR spectra (500〜4000 cm–1) of the PVA-PSSA-SSA-GA membranes………………………..………104
Table 4.4 Compare with Definition IEC and Real IEC of PVA-SSA-GA membranes……………….……….136
Table 4.5 Compare with Definition IEC and Real IEC of PVA-PSSA-SSA-GA membranes…………………...136
Table 4.6  Compare with the free water and bonding water contant of the PVA, Nafion, and PVA-SSA-GA membranes…………………………………140
Table 4.7  Compare with the free water and bonding water contant of the PVA, Nafion, and PVA-PSSA-SSA-GA membranes……...140
Table 4.8 The Methanol Permeability、Proton Conductivity and Selectivity of  PVA-SSA-GA membranes………………..146
Table 4.9 The Methanol Permeability、Proton Conductivity and Selectivity of  PVA-PSSA-SSA-GA membranes………...146






























符號表
Ea：氧化電位，V
Ec：還原電位，V
Ecell：全電池的電位，V
q：散射向量
λ：銅靶的Kα值之波長，A
Wdry：乾膜重，g
Wwet：濕膜重，g
P：滲透係數，cm2/s
IEC：離子交換容量，m mole/g
f：頻率，Hz
E(t)：瞬時電位
I(t)：瞬時電流
ω：角頻率
Θ：相角差
Z：阻抗，Ω
Rs：溶液阻抗，Ω
Rp：鈍化膜阻抗，Ω
Rct：電荷轉移阻抗，Ω
σ：導電度，S/cm
σ0：頻率因子
k：波茲曼常數，8.625x10-5 eV/K
V：strength vibration，拉伸振動
δ：bending vibration ，彎曲振動
ω：wagging vibration，搖擺振動
γ：rocking vibration，搖擺振動
Vs：對稱性的拉伸振動
Vas：非對稱性的拉伸振動
δas：非對稱性的彎曲振動
ni：電荷載子的數目
qi：載子所帶電荷
μi：載子的遷移率

                                

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