本論文的研究目的是將PBI以不同的LiCl比例溶於DMAc，以刮刀方式成膜，並將PBI和PTFE複合，以製備厚度更薄的PBI-PTFE複合膜，使PBI及PBI-PTFE膜材可應用於燃料電池。我們利用FTIR來鑑定合成出的PBI。以SEM (Scanning Electron Microscope)來觀察膜材表面結構，交流阻儀(AC impedance)測定膜材導電度，TGA (thermogravimetric analysis)測定膜材熱穩定性，氣相層析儀(GC)測定甲醇滲透率，並將Nafion117、不同LiCl比例所製備的PBI膜、不同方法製備的PBI-PTFE製作成膜電極組(MEA)，以單電池測試系統測試MEA在70℃、120℃、150℃、180℃質子交換膜燃料電池(PEMFC)的單電池效能，及在操作溫度為90℃時甲醇燃料電池(DMFC)的單電池效能。
PBI-PTFE在操作溫度70℃，氫氧氣進料為200 ml/min(PEMFC)下的效能比Nafion117高出許多，當溫度提升至100℃以上時，效能因為觸媒漿料配方及加入複合膜中的偶合劑使得效能大幅下降。PBI(PP-9.0)在操作溫度90℃，厚度80 μm，甲醇進料2M，氧氣進料為150 ml/min(DMFC)下的最大功率為50.4 mW/cm2較Nafion117在不同進料甲醇濃度(1M、2M、3M)高。

In this thesis PBI membranes (thickness 60~200 μm) were prepared by casting from LiCl / DMAc solutions, and PBI-PTFE composite membranes (20~36 μm thickness) were prepare by impregnating porous PTFE (poly tetrafluoroethylene) in PBI / LiCl / DMAc solutions. Both of these two membranes were than impregnating with phosphoric acid solution and were used to prepare membrane electrolyte assembly (MEA). Though PTFE has a lower conductivity than PBI, however, the high mechanical strength of PTFE allow the PBI-PTFE composite membranes to have a lower thickness when they were used in full cells applications. The lower thickness (20~36 μm) of PBI-PTFE composite membranes caused than to have lower resistance than PBI (60~200 μm) membranes. In this study, we showed that PBI-PTFE composite membranes had better PEMFC performance than Nafion117 and PBI at 70℃, and also PBI-PTFE composite membrane had better PEMFC performance than PBI at 180℃.

第一章 序論...............................................................................................1
1.1 前言……………..................................................................................1
1.2 燃料電池簡介…..................................................................................3
1.3 質子交換膜簡介..................................................................................4
1.4 聚苯咪唑(Polybenzimidazole，PBI)的合成及其在燃料電池之應用…………………………………………………………………….6
1.4.1 PBI的合成.………..………………………......................................7
1.4.2 PBI在燃料電池上的應用………………………………….……....8
1.5 PBI薄膜的製備………………..……………………………………..8
1.5.1 PBI改質薄膜性能……………………………….............................9
1.5.1.1 磺酸化PBI改質膜(PBI-AS)………...……………………….....10
1.5.1.2 PBI與磺酸化高分子摻合膜………………………………...….11
1.6 聚四氟乙烯(PTFE)簡介…………………………………………...12
1.6.1 PTFE於燃料電池上的應用……………………………………....12
1.6.2 PBI-PTFE複合膜…………………………………………………14
1.7 高溫質子交換膜燃料電池(PEMFC)………………………………14
1.7.1 PBI於高溫質子交換膜燃料電池的應用………………………...15
1.8 研究目的……………………………………………………………17

第二章 實驗.............................................................................................18
2.1 實驗藥品……………………………………………………………18
2.2 儀器設備............................................................................................19
2.3 實驗步驟............................................................................................20
2.3.1 PBI合成……………………………………………………….......20
2.3.2 霍式紅外光譜儀(FTIR)結構鑑定..................................................21
2.3.3 固有黏度測定.................................................................................21
2.3.4 PBI薄膜製備……...........................................................................21
2.3.5 PBI-PTFE複合膜製備……………………………………………22
2.3.5.1 方法Ⅰ- PBI-PTFE (Ⅰ)………………………………………...22
2.3.5.2 方法Ⅱ- PBI-PTFE (Ⅱ)…………………………………….......22
2.4 MEA製備………………….. ………………………………………23
2.4.1 低溫漿料配方…………………………………………………….23
2.4.2 高溫漿料配方(PEMFC) …………………………………………24
2.5 PBI薄膜及PBI-PTFE複合膜性質測試…………………………….25
2.5.1 SEM觀察薄膜表面形態………………………………………….25
2.5.2 導電度測量……………………………………………………….25
2.5.3 TGA熱穩定性分析……………………………………………….27
2.5.4 稱重測試………………………………………………………….27
2.5.5 氣體滲透量測…………………………………………………….27
2.5.6 甲醇滲透率的量測……………………………………………….29
2.5.7 質子交換膜燃料電池(PEMFC)低溫性能測試………………….30
2.5.8 直接甲醇燃料電池(DMFC)性能測試…………………………...30
2.5.9 質子交換膜燃料電池(PEMFC)高溫性能測試………………….31
2.5.10 低溫(< 100℃)燃料電池(PEMFC及DMFC)組裝及薄膜活化程序………………………………………………………………………….32
2.5.11 高溫(> 100℃)燃料電池(PEMFC)組裝及薄膜活化程序……...33
2.6 交流阻抗法(AC impedance).............................................................34
2.6.1 AC impedance的技術應用……………………………………….34
2.6.2 交流阻抗操作原理.........................................................................34
2.6.3 等效電路元件.................................................................................37
2.6.4 交流阻抗圖譜分析.........................................................................40

第三章 結果與討論.................................................................................42
3.1 霍式紅外光譜儀(FTIR)結構鑑定分析............................................42
3.1.2 固有黏度(inherent viscosity)測定......................... ........................43
3.2 SEM觀察膜材表面............................................................................45
3.2.1 PBI膜……………...........................................................................45
3.2.2 PTFE膜經偶合劑處理………………............................................45
3.2.3 PBI-PTFE複合膜…………………………………………………45
3.3 導電度測試………………………..………………………………..57
3.4 熱重分析儀(TGA)測試...….....…………………………………….58
3.5 PBI-PTFE秤重測試…..………………………………….…………59
3.6 氣體滲透測試....................................................................................60
3.7 甲醇滲透測試......................... .................... .....................................60
3.8 燃料電池測試……………………………………………................61
3.8.1 低溫質子交換膜燃料電池(PEMFC)...…………………………..62
3.8.2 高溫質子交換膜燃料電池(PEMFC) ....................... ....................65
3.8.3 直接甲醇進料燃料電池(DMFC) ......................... ........................68
3.8.3.1 甲醇濃度1M......................... ..................... ................................68
3.8.3.2 甲醇濃度2M......................... ..................... ................................70
3.8.3.3 甲醇濃度3M....................... ..................... ..................................72

第四章 結論…………………………………………………………….75
4.1 PBI薄膜製備………………………………………………………..75
4.2 PBI-PTFE 薄膜製備……………………………………………….76

第五章 未來工作及建儀……………………………………...……..78
5.1 PBI薄膜製備方式改進…………………………………….……78
5.2 PBI-PTFE複合膜製備方式改進…………………………….….78
5.3 高溫觸媒配方改進……………………………………………...79

第六章 參考文獻………..…………………………………………...80

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