臺灣博碩士論文加值系統

本論文將高分子聚苯並咪唑(PBI)接枝合成丁基磺酸聚苯並咪唑 (PBI-BS)。掺合PBI與PBI-BS製成摻合膜，分析鑑定掺合膜材物理性質，並製作膜電極組進行高溫質子交換膜燃料電池長時間操作安定性測試。利用FTIR及元素分析儀進行PBI及PBI-BS化學結構鑑定，以SEM (Scanning Electron Microscope)觀察膜材表面及截面型態、EDS (Energy Dispersive Spectrometer)分析膜材內元素成分及TGA (Thermogravimetric analysis)檢測膜材熱穩定性。而膜電極組分別於高溫160℃，定電流(電流密度= 200 mAcm−2)作單電池400小時連續安定性測試和298小時開/關(start/stop)循環測試。400小時長時間測試期間每隔12小時測試極化曲線和AC-impedance做膜電極組的阻抗測定。開/關循環測試是以高溫160℃，定電流(電流密度= 200 mAcm−2) 開(start) 10小時，接著中斷(stop) 14小時，作反覆性測試。長時間測試後的結果我們發現：經過400小時的測試，電位值下降約17 %，且膜材與觸媒的阻抗隨著測試時間而增加，另外於陰極所收集到的生成水其pH值小於7，顯示膜電極組中的磷酸不斷被攜出。在298小時的開/關循環測試後發現，電位值幾乎不變，而膜材的阻抗呈穩定狀態，觸媒阻抗則有些微上升，且於陰極所收集到的生成水其pH值小於7，顯示膜電極組中的磷酸會因為溶於陰極的生成水中而被攜帶出來。

In this thesis, we synthesized polybenzimidazole (PBI) and its derivative butyl sulfonated poly(polybenzimidazole) (PBI-BS). PBI/PBI-BS blend membranes were prepared with a PBI/PBI-BS wt ratio of 8/2. The chemical structure and physical properties of the membrane were investigated, using FTIR, SEM, EDS, and TGA. 400 h continuous stability life test and 298 h start/stop cycle test (10 h/start – 14 h/stop) on the MEA prepared from phosphoric acid-doped PBI/PBI-BS were conducted at 160℃with a current density= 200 mAcm−2. i-V polarization curve and AC-impedance test of MEA were performed every 12 h in the long time life test and each cycle in the start/stop cycle test. The data of 400 h life test showed decay of cell voltage V around 17% and the increments of resistance of membrane and electrolyte with increasing test time. The low pH value of the water collected from cathode outlet migration of H3PO4 from MEA. The 298 h start/stop cycle test showed no significant change of cell voltage V and membrane resistance, but increment of charge transfer of catalyst layer. The low pH value of water was also collected from cathode outlet during the start/stop cycle test. This result also indicates migration of H3PO4 during start/stop cycle test.

目錄

摘要 I
致謝 III
目錄 IV
圖目錄 VII
表目錄 X
第一章 緒論 1
1-1 前言 1
1-2 燃料電池簡介 2
1-2.1 燃料電池分類與優缺點 2
1-2.2 發電原理及構造 4
1-3 質子交換膜簡介 6
1-4 聚苯並咪唑(POLYBENZIMIDAZOLE，PBI)簡介 8
1-4.1 PBI的合成 9
1-4.2 PBI薄膜的製備 12
1-4.3 PBI在燃料電池上的應用 13
1-4.4 PBI的磺酸化方法 15
1-4.5 烷基磺酸PBI在燃料電池上的應用 17
1-4.6 PBI與磺酸化高分子摻合膜在燃料電池上的應用 18
1-5 PBI膜材的老化測試 19
1-6 研究目的 21
第二章 實驗 22
2-1 實驗流程 22
2-2 藥品 23
2-3 儀器設備 25
2-4 實驗步驟 26
2-4.1 PBI合成化學反應方程式及步驟 26
2-4.2 PBI-BS合成步驟 27
2-4.3 PBI和PBI-BS的結構鑑定和性質分析 28
2-4.3.1霍式紅外光譜儀(FTIR)結構鑑定 28
2-4.3.2元素分析儀(EA)性質分析 28
2-4.3.3 PBI固有黏度測定 28
2-4.4 PBI, PBI-BS與PBI/PBI-BS膜材的製備 29
2-4.4.1 PBI膜材的製備 29
2-4.4.2 PBI-BS膜材的製備 29
2-4.4.3 PBI/PBI-BS膜材的製備 29
2-4.5 PBI, PBI-BS, PBI/PBI-BS膜材性質分析 30
2-4.5.1 SEM觀察薄膜表面型態 30
2-4.5.2 EDS元素分析 30
2-4.5.3 TGA熱穩定性分析 30
2-4.5.4 含酸率測量 30
2-4.6 高溫質子交換膜燃料電池膜電極組(MEA)製備 31
2-4.6.1 PBI/PBI-BS膜材前處理 31
2-4.6.2 電極製備 31
2-4.6.3 膜電極組(MEA)製備 32
2-5 PBI/PBI-BS質子交換膜燃料電池高溫長時間使用壽命測試 33
2-5.1 PBI/PBI-BS膜電極組長時間操作電池失誤診斷分析 33
2-5.2實驗系統與量測儀器 34
2-5.3長時間操作測試步驟 38
2-6 PBI/PBI-BS膜電極組START/STOP循環測試實驗 39
2-6.1 PBI/PBI-BS膜電極組start/stop循環測試電池失誤診斷分析 39
2-6.2 Start/Stop循環測試步驟 40
第三章 結果與討論 41
3-1 PBI 性質結構鑑定 41
3-1.1 PBI的霍式紅外光譜儀(FTIR)分析 41
3-1.2 PBI的固有黏度測定 42
3-2 PBI-BS的結構鑑定 43
3-2.1 PBI-BS的FTIR光譜 43
3-2.2 PBI-BS元素分析(EA)鑑定 44
3-3 PBI，PBI-BS及PBI/PBI-BS膜材性質分析 45
3-3.1 SEM結構分析 45
3-3.2 EDS元素分析 49
3-3.3 TGA熱穩定性分析 53
3-3.4 膜材含酸率測定 55
3-4 PBI/PBI-BS質子交換膜燃料電池高溫長時間操作測試 56
3-4.1 PBI/PBI-BS摻合膜48小時連續操作測試—自製電極 56
3-4.2 PBI/PBI-BS摻合膜400小時連續長時間操作測試—商購電極 61
3-4.3 PBI/PBI-BS摻合膜start/stop循環測試—商購電極 72
第四章 結論 84
第五章 未來工作與建議 85
第六章 參考文獻 86
附 錄 ㄧ 96
附 錄 二 103
































圖目錄

圖1.1 質子交換膜燃料電池構造示意圖[Rikukawa，2000] 4
圖1.2 直接甲醇燃料電池構造示意圖[Lu，2004] 5
圖1.3 全氟磺酸化聚電解質薄膜(Nafion)化學結構 6
[Grot，1978；Rikukawa，2000] 6
圖1.4 PBI化學結構 8
圖2.1 實驗架構 22
圖2.2 PBI合成反應式 26
圖2.3 PBI-BS合成反應式 27
圖2.4 觸媒層塗佈示意圖 32
圖2.5 MEA壓合示意圖 32
圖2.6 MEA長時間測試流程圖 33
圖2.7 雙極板陽極兩蛇蛇型流道(左圖)，陰極三蛇蛇型流道(右圖) (PEMEAS) 34
圖2.8 高溫電池結構圖：電池外觀(包含保溫包)；電池實體外觀(PEMEAS) 34
圖2.9 單電池組合結構示意圖 35
圖2.10 高溫單電池性能測試實驗裝置圖 36
圖2.11 模擬電路圖 37
圖2.12 MEA start/stop循環測試流程圖 39
圖3.1 PBI的FTIR光譜 41
圖3.2 PBI-BS的FTIR光譜 43
圖3.3 PBI膜材表面(左圖)與截面(右圖)SEM圖 (未浸漬磷酸) 46
圖3.4 PBI-BS膜材表面(左圖)與截面(右圖)SEM圖 (未浸漬磷酸) 47
圖3.5 PBI/PBI-BS膜材表面(左圖)與截面(右圖)SEM圖 (未浸漬磷酸) 48
圖3.6 PBI/PBI-BS膜(正面)的EDX圖(左圖)和mapping圖(右圖) (未浸漬磷酸) 49
圖3.7 PBI/PBI-BS膜(截面)的EDX圖(左圖)和mapping圖(右圖) (未浸漬磷酸) 50
圖3.8 PBI/PBI-BS膜(正面)的EDX圖(左圖)和mapping圖(右圖) (未浸漬磷酸) 51
圖3.9 PBI/PBI-BS膜(截面)的EDX圖(左圖)和mapping圖(右圖) (未浸漬磷酸) 52
圖3.10 PBI, PBI-BS, PBI/PBI-BS之TGA圖：(—) PBI；(---) PBI-BS；(— —) PBI/PBI-BS (未浸漬磷酸) 54
圖3.11 PBI, PBI-BS, PBI/PBI-BS之TGA圖：(—) PBI；(---) PBI-BS；(— —) PBI/PBI-BS (浸漬磷酸) 54
圖3.12 PBI/PBI-BS膜(90 μm)PEMFC膜電極組於160℃下定電流 57
(i= 200 mA/cm2)之電池電位對操作時間曲線圖(自製電極) 57
圖3.13 PBI/PBI-BS膜(90 μm)電極組分別於不同時間下的單電池 58
i-V曲線圖：(+) 0 h；(◇) 12 h；(□) 24 h；(○) 36 h；(△) 48 h 58
圖3.14 PBI/PBI-BS膜(90 μm)電極組分別於不同時間下的單電池 58
i-P曲線圖：(+) 0 h；(◇) 12 h；(□) 24 h；(○) 36 h；(△) 48 h 58
圖3.15 不同操作時間所量測的能奎斯特圖曲線圖：(+) 0 h；(◇) 12 h；(□) 24 h；(○) 36 h；(△) 48 h (active area 50 cm2) 59
圖3.16 膜電極組等效電路圖 59
圖3.17 PBI/PBI-BS膜(90 μm)PEMFC膜電極組於160 ℃下定電流 63
(i = 200 mA/cm2)之電池電位對操作時間曲線圖 (E-TEK電極) 63
圖3.18 定電流(i = 200 mA/cm2)連續長時間操作下，各操作時間的開路電位曲線圖(O2/H2流量為600 ml/min，常壓，160 ℃) 63
圖3.19 PBI /PBI-BS膜(90 μm)電極組在不同時間下的單電池i-V曲線圖(O2/H2流量為600 ml/min，常壓，160 ℃)：(+) 0 h；(◇) 24 h；(□) 60 h；(△) 108 h；(○) 180 h；(▽) 288 h；(×) 324 h；(☆) 400 h 64
圖3.20 PBI /PBI-BS膜(90 μm)電極組在不同時間下的單電池i-P曲線圖(O2/H2流量為600 ml/min，常壓，160 ℃)，(+) 0 h；(◇) 24 h；(□) 60 h；(△) 108 h；(○) 180 h；(▽) 288 h；(×) 324 h；(☆) 400 h 64
圖3.21 不同操作時間下所量測的能奎斯特圖曲線圖：(+) 0 h；(◇) 24； 65
(□) 60 h；(△) 108 h；(○) 180 h；(▽) 288 h；(×) 324 h；(☆) 400 h 65
(active area 50 cm2) 65
圖3.22 膜材阻抗(Rs)與時間關係圖 66
圖3.23 觸媒阻抗(Rc)與時間關係圖 66
圖3.24陰極反應生成水的pH值與時間關係圖 67
圖3.25 PBI/PBI-BS膜電極組(MEA)不同倍率下的截面SEM圖：長時間測試前(before)(左圖)與400小時測試後(after)(右圖) 68
圖3.26 膜電極組400小時測試前(before)的截面SEM&EDS 69
((a)截面SEM：(---)C；(---)P; (b) C元素的EDS; (c) P元素的EDS) 69
圖3.27 膜電極組長時間400小時測試後(after)的截面SEM&EDS 70
((a)截面SEM：(---)C；(---)P; (b) C元素的EDS; (c) P元素的EDS) 70
圖3.28 MEA截面SEM及磷元素EDS (after 400 h test) 71
圖3.29 MEA截面磷元素含量比(after 400 h test) 71
圖3.30 PBI/PBI-BS膜電極組(MEA) 的截面SEM圖：長時間測試前(before)(左圖)與400小時測試後(after)(右圖) 71
圖3.31 PBI/PBI-BS(膜厚85 μm)PEMFC膜電極組於160℃下定電流 74
(i= 200 mA/cm2)電池電位對時間曲線圖(start/stop) (E-TEK電極) 74
圖3.32 PBI/PBI-BS(膜厚85 μm)PEMFC膜電極組於160 ℃下定電流 74
(i = 200 mA/cm2)電池電位對時間曲線圖(僅start時) (E-TEK電極) 74
圖3.33 定電流(i = 200 mA/cm2)長時間操作，開路電位對時間曲線圖(O2/H2流量為600 ml/min，常壓，160 ℃) 75
圖3.34 PBI /PBI-BS膜(85 μm)電極組在不同時間下的單電池i-V曲線圖(O2/H2流量為600 ml/min，常壓，160 ℃)下：(◇) 0 h; (◆) 10 h; 75
(□) 34 h; (○) 82 h; (▽) 178 h; (▼) 226 h; (★) 298 h 75
圖3.35 PBI /PBI-BS膜(85 μm)電極組在不同時間下的單電池i-P曲線圖(O2/H2流量為600 ml/min，常壓，160 ℃)下：(◇) 0 h; (◆) 10 h; 76
(□) 34 h; (○) 82 h; (▽) 178 h; (▼) 226 h; (★) 298 h 76
圖3.36 不同操作時間下的能奎斯特圖曲線圖：(◇) 0 h; (◆) 10 h; 76
(□) 34 h; (○) 82 h; (▽) 178 h; (▼) 226 h; (★) 298 h 76
圖3.37 膜材阻抗(Rs)與時間關係圖 77
圖3.38 觸媒阻抗(Rc)與時間關係圖 78
圖3.39陰極反應生成水的pH值與時間關係圖 79
圖3.40 PBI/PBI-BS膜電極組(MEA)不同倍率下的截面SEM圖：長時間測試前(before)(左圖)與298小時循環測試後(after)(右圖) 80
圖3.41 膜電極組長時間298小時循環測試前(before)的截面SEM&EDS((a)截面SEM：(---)C；(---)P; (b) C元素的EDS; (c) P元素的EDS) 81
圖3.42 膜電極組長時間298小時循環測試後(after)的截面SEM&EDS 82
((a)截面SEM：(---)C；(---)P; (b) C元素的EDS; (c) P元素的EDS) 82
圖3.43 MEA截面SEM及磷元素EDS (after 298 h test) 83
圖3.44 MEA截面磷元素含量比(after 298 h test) 83
圖3.45 PBI/PBI-BS膜電極組(MEA) 的截面SEM圖：長時間測試前(before)(左圖)與298小時start/stop循環測試後(after)(右圖) 83



表目錄

表1.1 燃料電池的分類[黃朝榮，2003] 2
表1.2 PBI合成相關文獻 10
表1.3 PBI製膜參考文獻摘要 12
表1.4 PBI膜材應用於燃料電池相關文獻摘要 14
表1.5 PBI各種磺酸化方法的比較 15
表1.6 烷基磺酸PBI合成相關文獻摘要 17
表1.7 PBI膜電極組老化測試相關文獻 20
表2.1 PBI之固有黏度之數值Choe [1996] 28
表3.1 PBI之IR peaks分析[Asensio，2002] 42
表3.2 固有黏度溶液流動時間數據表 42
表3.3 不同支鏈的磺酸根吸收位置[Gieselman，1992] 43
表3.4 PBI-BS元素分析結果及磺酸化比例計算 44
表3.5 PBI/PBI-BS正面EDX的元素分析(未浸漬磷酸) 49
表3.6 PBI/PBI-BS截面EDX的元素分析 (未浸漬磷酸) 50
表3.7 PBI/PBI-BS正面EDX的元素分析(浸漬磷酸) 51
表3.8 PBI/PBI-BS截面EDX的元素分析(浸漬磷酸) 52
表3.9 膜材內各成分重量 53
表3.10 膜材含酸率 55
表3.11 自製電極觸媒層配方表 57
表3.12連續(48 h)操作下，各操作時間的開路電位 59
表3.13 連續(48 h)操作下，各操作時間MEA阻抗Rs，Rc，Cd值 60
(active area 50 cm2) 60
表3.14 連續(48 h)操作下，反應生成水的pH值 60
表3.15 長時間連續(400 h)操作下，各操作時間MEA阻抗Rs，Rc，Cd值(active area 50 cm2) 65
表3.16 400小時長時間連續操作下，反應生成水的pH值 67
表3.17 start/stop循環操作下，各操作時間MEA的阻抗Rs, Rc, Cd值 77
(active area= 50 cm2) 77
表3.18 298小時start/stop循環操作下，反應生成水的pH值 78

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