臺灣博碩士論文加值系統

本論文旨在探討燃料電池在不同操作環境下，對高分子電解質薄膜所造成之老化現象，並且探討薄膜老化機制，以及老化對薄膜基本性質之影響。


論文的第一部份以全氟系高分子Nafion®115作為電解質材料，探討不同金屬離子、溫度、過氧化氫濃度對老化速率之影響，並且針對老化後薄膜性質進行一系列探討，包括化學結構、熱性質、機械強度和質子傳導率等。 由離子層析得知，薄膜置換不同金屬離子時，發現亞鐵離子與銅離子存在時，能加速薄膜老化速率。而且高溫的環境下，以及高濃度的過氧化氫和亞鐵離子，造成較高的薄膜老化速率。由FTIR分析顯示，在氧化過程中，磺酸根與醚基吸收波峰強度明顯減少，主要因自由基優先攻擊Nafion®115薄膜側鏈段。同時，藉由交流阻抗分析發現，隨著老化時間增加，阻抗值會提高，主因是磺酸根數量減少造成質子導電度的降低。薄膜甲醇滲透率與含水率也隨老化時間而提升，由電子顯微鏡觀察分析結果顯示，隨著老化時間增加，薄膜表層因氧化而形成微小空隙以及孔洞。


藉由熱重分析儀（TGA）和微差掃描熱卡計（DSC）的分析可知，由於老化初期離子團簇受到氧化破壞，使得離子團簇間氫鍵作用力減弱，並且C-S鍵結容易被裂解，其磺酸根裂解溫度與離子團簇轉移溫度降低。老化後期，置換氫型反應溫度80℃剛好接近離子團簇轉移溫度，致使部份離子團簇有足夠能力進行分子鏈的重排，其磺酸根裂解溫度與離子團簇轉移溫度反而增加。由動態機械分析（DMA）得知，老化初期，由於自由基攻擊薄膜分子鏈造成高分子斷鏈，使得薄膜分子量的減少，導致儲存模數(剛性)下降。老化後期，高分子側鏈的分子鏈段解離，非結晶區側鏈段的減少促使Nafion薄膜結晶度提升(XRD證實)，使得儲存模數(剛性)增加。結晶區熔融溫度、主鏈段裂解溫度以及α玻璃轉移溫度則不會隨著老化時間而改變，推測主因是Nafion主鏈段上具有強共價鍵結的C-F結構，致使其不易受化學破壞。


本研究也進行TGA/MS分析，推知Nafion薄膜熱老化過程中，首先溫度低於240℃是去除薄膜內部的水分子。當裂解溫度達到280℃時，開始裂解磺酸根，釋放出SO2；接下來側鏈段連續被裂解形成SOF2、CXFY、CXFYOZ、COF、COF2。最後，當熱裂解溫度達到500℃以上時，碳氟(-CF2-)主鏈段開始被熱裂而解釋放出CXFY氣體。然而，熱裂解溫度在300℃~600℃之間，COF2與水會進行二次反應而形成CO2與HF。


本研究第二部份以碳氫系聚乙烯醇基質子交換薄膜S20P80為探討對象，S20P80係指以20％磺酸化丁二酸(Sulfosuccinic acid, SSA)作為交聯劑，以80％離子性高分子poly(syrene sulfonic acid-co-male acid (PSSA-co-MA)穿網其間，作為提供質子之來源。首先，針對探討老化溫度對S20P80薄膜水解之影響，由FTIR可知，高溫下，薄膜容易遭受水解造成酯基(C-O-C)斷鍵和交聯結構破壞，使得部分PSSA-MA流失，此可由水溶液中之電導度上升以及pH值下降的結果證實。


過氧化氫對S20P80薄膜老化之影響：由FTIR可知，在室溫(30℃)下，自由基攻擊C-O-C、苯環與乙烯基之接點氫原子，導致C-O、SO3H+和苯環特徵波峰強度減弱。溫度增加時，加速自由基對膜材的攻擊，導致相對應之特徵波峰強度也隨之減弱。當薄膜置換成亞鐵離子時，其老化結果亦然。在高溫與高濃度過氧化氫條件下，薄膜重量損失加速，薄膜含水率與甲醇滲透率提高，應是薄膜交聯結構遭受破壞所導致。由XRD與FTIR可知，當老化溫度為35℃時，薄膜結晶度下降，且OH吸收波峰向高波數位移，表示PVA結晶遭受破壞，而PVA上OH的氫鍵作用力降低。當老化溫度增加，薄膜結晶度反有些微提高，而且OH吸收波峰向低波數位移。推測交聯結構破壞和PVA結晶度減少，導致PVA分子鏈更加容易移動，在含水下(塑化效應)，其玻璃轉移溫度大幅下降。當PVA玻璃轉移溫度剛好接近老化溫度時，促使PVA分子鏈部份重新排列可能。由拉力試驗與DMA可知，當老化溫度提高時，楊氏模數、抗張強度、破壞伸長率和儲存模數也隨之下降。

Part I. The perfluorinated ionomer membrane (Nafion®115) used as the electrolyte material, The effects of metal ions、temperature and hydrogen peroxide concentration were investigated membrane degradation rate and the effect of deteriorated membrane properties such as chemical structure, thermal properties mechanical strength and proton conductivity etc. Ion Chromatography exhibits the presence of Fe2+ and Cu2+ ions enhanced the rate of membrane degradation. And high temperature, high hydrogen peroxide concentration and ferrous ions increased membrane degradation rate. The result of FTIR measurement of deteriorated membrane revealed that side chains absorbed peak strength apparent decreased, most probably because radicals attacked the side chain of Nafion®115. AC Impedance revealed the impedance enhanced with the increasing of degradation time. It is because that sulfonic acid contents reduced leads to proton conductivity decreased. The methanol permeability and water uptake increased with increasing degradation time. SEM revealed the breakdown of the membrane surface started from the formation of small bubbles and the bubbles gradually grew to the pinholes.


TGA and DSC shown ionic clusters oxidation by H2O2 at the primary stage, which ionic clusters hydrogen bonding interaction decrease and C-S bond decomposed easily, which leads to decomposition temperature of sulfonate groups and ionic clusters transition temperature decrease. Displacement of H+ reacting temperature (80℃) exactly to near ionic clusters transition temperature at a later stage, resulting in a part of ionic clusters enough be ability to molecular rearrangement, which decomposition temperature of sulfonate groups and ionic clusters transition temperature increased. DMA data shows that because of free radicals attack the membrane molecular chain to make the macromolecular chain breaking, resulting in the membrane molecular weight and store modulus decreased at the primary stage. The decomposition of molecular chain segment of macromolecular side chain, then the crystallinity of Nafion membrane and store modulus increased with amorphous side chain reduced. The crystalline domains melting、decomposition temperature of main chain and α glass transition temperature had no change with degradation time, which suggested the C-F composition of main chain have strong covalent bonds and have not suffered from chemical break easily.


This paper also TGA/MS was investigated, it is possible to suggest the Nafion membrane thermal degradation process. The first temperature low 240℃ can be attributed to the loss of residual water in the Nafion membrane. The decomposition temperature approached 280℃, the Nafion loses its the sulfonic acid groups and the release of sulfur dioxide, then side chain continuous decomposed the product of SOF2、CXFY、CXFYOZ、COF、COF2. Finally, as the decomposition temperature above 500℃, it began the thermal decomposition of main chain and the released of CXFY gas. At the same time, the thermal decomposition temperature between 300℃ and 600℃, the formation of CO2 and HF, due to a secondary reaction of CF2O and water.


Part II. Hydrocarbon proton exchange membrane base on polyvinyl alcohol (S20P80) was investigated. S20P80 membrane indicates 20% Sulfosuccinic acid as crosslinked agent and 80% poly(syrene sulfonic acid-co-male acid (PSSA-co-MA) as supply with the proton source. First of all, effect of the S20P80 membrane hydrolysis with different degradation temperature. FTIR study, At high temperature, the membrane suffers from hydrolysis easily, which it makes ester group chain scission and crosslink structure is broken, and the part of PSSA-MA flowed away, then water solution test result found electrode conductivity increased and pH value decreased.


The effect of S20P80 membrane degradation with hydrogen peroxide was investigated: FTIR results revealed, radicals attack ester group、aromatic and vinyl on the point of hydrogen atom at room temperature, resulting in C-O、SO3H and aromatic characteristic peak intensity decreased. The temperature increased, accelerating radicals attack on the membrane, leading to opposite of characteristic peak strong decreased. As the replacement of ferrous ions, the result is similar to above. In high temperature and high concentration condition, the membrane weight loss, water uptake and methanol permeability raised, due to the membrane crosslink structure was broken. XRD and FTIR exhibited that degradation temperature 35℃, the membrane crystalline decreased, and OH absorption peak moved to high waveumber. Degradation temperature increased, the membrane little increased and OH absorption peak moved to low waveumber, due to crosslink structure was broken and PVA crystalline decreased, resulting in PVA molecular chain more easy to move. With the water (plasticize effect), the glass transition temperature great decreased. As PVA glass transition temperature is near to degradation temperature, which accelerated PVA molecular chain a part of molecular rearrangement. Mechanical tensile and DMA results, degradation temperature increased, the Young’s modulus、tensile strength、elongation and store modulus decreased.

中文摘要…………………………………………………Ⅰ
英文摘要…………………………………………………Ⅲ
誌謝………………………………………………………Ⅵ
總目錄……………………………………………………Ⅶ
表目錄……………………………………………………Ⅹ
圖目錄……………………………………………………ⅩI

第一章 緒論....................................1
1.1 簡介....................................1
1.2 薄膜種類................................1
1.3 燃料電池運作............................3
1.4 研究動機與目的..........................4
第二章 文獻回顧................................6
2.1 薄膜機械老化............................6
2.1.1 低溼度..................................6
2.1.2 高電池電壓..............................7
2.1.3 高溫度..................................7
2.1.4 其他....................................8
2.2 薄膜熱老化.............................10
2.3 薄膜化學老化與電化學老化...............13
2.3.1 電池運作中自由基之產生.................13
2.3.2 自由基對薄膜老化之影響.................16
2.3.3 金屬污染物對薄膜老化之影響.............17
2.3.4 不飽和芳香族薄膜之老化.................20
2.3.5 接枝薄膜之老化.........................22
2.3.6 Nafion®薄膜之老化......................24
第三章 原理...................................29
3.1 傅立葉紅外線吸收光譜儀.................29
3.2 熱重損失分析儀 (Thermo-gravimetric Analysis，TGA)................................30
3.3 交流阻抗分析儀 (AC-Impendence).........31
3.4 動態機械分析儀 (Dynamic Mechanical Analysis，DMA)................................36
3.5 X光繞射分析儀 (X-ray diffraction，XRD)..........................................40
3.6 掃描式電子顯微鏡 (Scanning Electron Microscopy，SEM)..............................41
3.7 示差掃描式熱卡計 (Differential Scanning Calorimeter，DSC).............................42
3.8 離子層析儀 (Ion Chromatography，IC)....43
3.9 熱分析-質譜出氣分析儀..................43
3.10 拉伸測試 (Tension Test)................45
第四章 實驗設備與步驟.........................46
4.1 實驗藥品...............................46
4.2 實驗儀器...............................48
4.3 材料製備...............................49
4.3.1 Nafion®115薄膜前處理...................49
4.3.2 將Nafion®115薄膜置換為不同型金屬.......50
4.3.3 Nafion®115薄膜老化測試.................50
4.3.4 前處理 PSSA-MA......................51
4.3.5 PVA系薄膜製備..........................51
4.3.6 PVA系薄膜老化測試......................53
4.4 薄膜老化之分析與鑑定...................54
4.4.1 傅立葉紅外線光譜分析...................54
4.4.2 熱重分析儀.............................54
4.4.3 示差掃描式熱卡計.......................54
4.4.4 交流阻抗實驗流程.......................54
4.4.5 飽和含水率分析.........................55
4.4.6 離子交換容量實驗流程...................56
4.4.7 甲醇滲透率實驗.........................56
4.4.8 X光繞射分析............................57
4.4.9 動態機械熱分析儀.......................57
4.4.10 拉伸測試...............................58
4.4.11 離子層析儀.............................58
4.4.12 熱分析-質譜出氣分析儀..................58
第五章 結果與討論.............................59
5.1 薄膜老化的變因.........................59
5.1.1 金屬離子對薄膜老化速率的影響...........59
5.1.2 溫度對薄膜老化速率的影響...............61
5.1.3 亞鐵離子濃度對薄膜老化速率的影響.......62
5.1.4 過氧化氫濃度對薄膜老化速率的影響.......64
5.2 薄膜的重量損失.........................65
5.3 傅立葉轉換紅外線光譜儀(FTIR)...........66
5.4 老化對質子傳導率和離子交換容量的影響...70
5.5 掃描電子顯微鏡觀察老化後薄膜的型態.....71
5.6 老化對甲醇滲透率與飽和含水率的影響.....73
5.7 熱重損失分析儀(TGA)與微差式掃描熱卡計(DSC)..................................74
5.8 老化對薄膜機械性質之影響-動態機械熱分析 (DMA).........................79
5.9 老化對薄膜結晶度之影響.................81
5.10 熱分析-質譜出氣分析儀(TG/MS)...........83
5.11 S20P80薄膜之水解.......................90
5.11.1 溫度對S20P80薄膜水解之影響.............91
5.11.2 溫度對PVA/SSA20薄膜水解之影響..........95
5.12 H2O2對S20P80薄膜老化之影響.............97
5.12.1 溫度對S20P80薄膜老化之影響.............97
5.12.2 H2O2對Fe2+-S20P80薄膜老化之影響.......100
5.13 H2O2對S20P80薄膜重量損失之影響........101
5.14 H2O2對S20P80薄膜含水率和甲醇滲透率之影響...........................................103
5.15 H2O2對S20P80薄膜結晶度之影響..........104
5.16 H2O2對S20P80薄膜質子傳導率和IEC值之影響...........................................106
5.17 H2O2對S20P80薄膜對機械強度之影響-動態機械熱分析、拉力試驗....107
5.18 添加不同含量硫酸氫銫S20P80薄膜對重量損失的影響.................109
第六章 結論..................................111
第七章 參考文獻..............................113

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