臺灣博碩士論文加值系統

本研究比較不同磺酸化SPPEK DS0.86 和1.10及SPAEEKK不同含量0.7和0.8的磺酸化4,4’-biphenol，並利用乾式成膜法在玻璃板上。
SPPEK-086、SPPEK-110、SPAEEKK-070及SPAEEKK-080膜材的最初熱裂解溫度均高於230 oC。在熱壓製作MEA，可以耐受相當高的熱壓溫度，膜材的結構不會遭到破壞。膜材質子傳導度，隨著磺酸化程度及溫度的上升而提升。因為質子傳導活化能接近14-40 KJ/mol，所以質子傳導方式均屬Grotthus與vehicle mechanism兩種方式同時進行來傳導。當溫度在80 oC，SPAEEKK-080為3.9×10-2 S/cm接近Nafion-117的質子傳導度。
SPPEK-086及SPAEEKK-070的甲醇水溶液吸收量變化與Nafion-117 相近。高磺酸化程度的膜材SPPEK-110在3 M甲醇水溶液溫度為60 oC時，膜材會產生過度膨潤的現象。滲透蒸發實驗觀察，所有膜材其甲醇阻擋效果均優於Nafion-117。Side-by-side滲透係數實驗，所有膜材的滲透係數也低於Nafion-117。四種膜材中，SPAEEKK-070有最佳的阻擋甲醇的能力。SPAEEKK系列的膜材隨著溫度上升，甲醇滲透係數變化小。所以SPAEEKK系列膜材阻擋甲醇滲透是最佳的膜材。
SPPEK-086、SPPEK-110、SPAEEKK-070及SPAEEKK-080膜材質子傳導度均低於Nafion-117；但阻擋甲醇滲透能力均優於Nafion-117，所以在甲醇燃料電池系中可能可以得到一較好的電池效能，且有較長的電池壽命。

In this study, sulfonated poly(phthalazinone ether ketone) with degree of sulfonation (DS) of 0.86 and 1.10 and sulfonated poly(arylene ether ether ketone ketone) with sulfonated 4,4’-biphenol content (B) of 0.7 and 0.8 were fabricated into membranes on glass plates by solvent casting method.
SPPEKs and SPAEEKKs had excellent thermal stability for use in the preparation of MEA for DMFC because the degradation temperature of them was higher than 230 oC. The proton conductivity of SPPEK and SPAEEKK membranes increased as temperature and the degree of sulfonation. The proton conductivity of SPAEEKK-080 was 3.9×10-2 S/cm which was closed to Nafion-117 at 80 oC. According to the activation energy of proton conductivity was closed to 14-40 KJ/mol, proton transport might follow Grotthus and vehicle mechanisms simultaneously.
SPPEK-086 and SPAEEKK-070 had similar solution uptake to Nafion-117. SPPEK-110 might dissolve in 3 M methanol solution at 60 oC. In pervaporation and side-by-side studies, all the SPPEK and SPAEEKK membranes had lower flux and methanol permeability than Nafion-117.Methanol permeabilities were relatively constant for SPAEEKK membranes when temperature is varied. SPAEEKK-070 membrane had the lowest methanol permeability among all the test membranes. Therefore, SPAEEKKs might be a better choice to prevent methanol crossover at high temperature.
Although the proton conductivity of SPPEK and SPAEEKK membranes were lower than Nafion-117, the methanol permeability of them were much lower than Nafion-117.SPPEK and SPAEEKK membranes still could be considered as a candidate for MEA preparation in direct methanol fuel cell.

目 錄
中文摘要 I
英文摘要……………………………………………………………..II
目錄 III
表目錄 VI
圖目錄 VII

第一章 序論 1
1.1 質子交換膜的研究背景 4
1.2 研究目的與範疇 8

第二章 研究方法與原理 11
2.1 甲醇水溶液吸收量實驗 11
2.2 甲醇於薄膜中的滲透行為 12
2.2.1 滲透係數計算方法 12
2.2.2 滲透活化能 14
2.3 滲透蒸發 15
2.3.1 滲透蒸發原理 16
2.3.2 滲透蒸發理論 17
2.3.3 滲透蒸發定義 18
2.3.3.1 通量(Flux) 19
2.3.3.2 滲透蒸發滲透活化能 19
2.4 Membrane-Electrode Assembly (MEA)介紹 19
2.5 燃料電池的過電壓(Overpotential)介紹 21
2.5.1 活性過電壓之活性極化(Activation polarization) 22
2.5.2 歐姆過電壓之歐姆極化(Ohmic polarization) 23
2.5.3 質傳過電壓之濃度極化(Ooncentration polarization) 23

第三章 實驗方法 26
3.1實驗藥品 26
3.2 實驗設備與器材 26
3.3 元素分析(EA)測試 29
3.3.1 簡介 29
3.3.2 實驗步驟 29
3.4 FTIR-ATR測試 29
3.4.1 簡介 29
3.4.2 實驗步驟 29
3.5 酸鹼滴定實驗 30
3.5.1 簡介 30
3.5.2 實驗步驟 30
3.6 熱重分析(TGA)測試 30
3.6.1 簡介 31
3.6.2 實驗步驟 31
3.7 膜材交流阻抗(AC Impedance)測定 31
3.7.1 簡介 31
3.7.2 實驗步驟 31
3.8 膜材溶液吸收量實驗 34
3.8.1 簡介 34
3.8.2 實驗步驟 34
3.9 GC分析 34
3.10 液相吸附選擇性實驗 34
3.10.1簡介 34
3.10.2 頂空間(Head space)分析 35
3.11 滲透蒸發實驗 35
3.11.1 簡介 35
3.11.2 實驗步驟 35
3.12 Side-by-side滲透實驗 38
3.11.1 簡介 38
3.11.2 實驗步驟 38
3.13 單電池測試 40
3.13.1 簡介 40
3.13.2 實驗步驟 40

第四章 結果與討論 45
4.1 膜材的定性分析 45
4.1.1 薄膜的製備 45
4.1.2 FTIR-ATR分析 45
4.1.3 元素分析與酸鹼滴定實驗 46
4.2 膜材熱穩定分析 46
4.3 膜材質子傳導度分析 47
4.4 膜材溶液吸收量實驗 48
4.5 滲透蒸發與液相吸附選擇性實驗 51
4.6 Side-by-side滲透實驗 53
第五章 結論 84

文獻回顧 85
表 目 錄

表 1.1 各種燃料電池性能比較 3
表 4.1 不同磺酸化程度SPPEK及SPAEEKK之元素分析與離子交換容積(IEC) 55
表 4.2 膜材熱降解溫度 55
表 4.3 膜材質子傳導活化能 55
表 4.4 膜材Nafion-117( 187 ?慆)於不同溫度及不同進料甲醇濃度水溶液，滲透端水和甲醇通量比較表 56
表 4.5 膜材SPPEK-086( 78 ?慆)於不同溫度及不同進料甲醇濃度水溶液，滲透端水和甲醇通量比較表 56
表 4.6 膜材SPPEK-110( 76 ?慆)於不同溫度及不同進料甲醇濃度水溶液，滲透端水和甲醇通量比較表 57
表 4. 7 膜材SPAEEKK-070 (58?慆)於不同溫度及不同進料甲醇濃度水溶液，滲透端水和甲醇通量比較表 57
表 4. 8 膜材SPAEEKK-080 (48?慆)於不同溫度及不同進料甲醇濃度水溶液，滲透端水和甲醇通量比較表 58
表 4.9 膜材甲醇與水之滲透活化能(滲透蒸發) 58
表 4.10 膜材甲醇滲透活化能(side-by-side) 59







圖 目 錄

圖 1.1 甲醇燃料電池工作原理 2
圖 1.2 SPPEK磺酸化步驟 10
圖 1.3 SPAEEKK磺酸化步驟 10
圖 2.1 滲透原理簡示圖 13
圖 2.2 孔洞傳送機制示意圖 16
圖 2.3 溶解-擴散傳送機制示意圖 17
圖 2.4 典型質子交換膜燃料電池電位VS電流密度 25
圖 3.1 (a)夾膜電極cell俯視與側視圖、
(b)離子導電度實驗裝置系統簡圖 33
圖 3.2 滲透蒸發裝置圖 37
圖 3.3 Side-by-side雙槽式擴散槽裝置 39
圖 3.4 DMFC單電池示意圖 43
圖 3.5 甲醇燃料電池測試機台裝置圖 44
圖 4.1 膜材(a) PPEK, (b) SPPEK-086, (c) SPPEK-110, (d) SPAEEKK-070, (e) SPAEEKK-080之ATR-FTIR圖 59
圖4.2 Nafion、PPEK、SPPEK-086、SPPEK-110、SPAEEKK-070與 SPAEEKK-080之TGA圖譜 60
圖4.3 Nafion、PPEK、SPPEK-086、SPPEK-110、SPAEEKK-070與 SPAEEKK-080於不同溫度下之質子傳導度圖(相對溼度為95%) 61
圖4.4 SPPEK-086與Nafion-117在水與不同甲醇濃度水溶液下膜材的吸收量 62
圖4.5 SPPEK-110和Nafion-117在水與不同甲醇濃度水溶液下膜材吸收量 63
圖4.6 SPAEEKK-070與Nafion-117在水與不同甲醇濃度水溶液下膜材吸收量 64
圖4.7 SPAEEKK-080與Nafion-117在水與不同甲醇濃度水溶液下膜材吸收量 65
圖4.8 各膜材在不同溫度下，每個SO3-官能基可吸收水分子個數之關係圖 66
圖4.9 膜材Nafion-117、SPPEK-086、SPPEK-110、SPEEKK-070與SPEEKK-080於30 oC膜材吸收甲醇濃度與進料組成之關係圖 67
圖4.10 膜材Nafion-117、SPPEK-086、SPPEK-110、SPEEKK-070與SPEEKK-080於40 oC膜材吸收甲醇濃度與進料組成之關係圖 68
圖4.11 膜材Nafion-117、SPPEK-086、SPPEK-110、SPEEKK-070與SPEEKK-080於50 oC膜材吸收甲醇濃度與進料組成之關係圖 69
圖4.12 膜材Nafion-117(187 ?慆)、SPPEK-086(78 ?慆)與SPAEEKK-070 (58 ?慆)於30 oC下滲透通量對進料組成之關係圖 70
圖4.13 膜材Nafion-117、SPPEK-086與SPAEEKK-070於30 oC下滲透物組成對進料組成之關係圖膜材 71
圖4.14 Nafion-117(187 ?慆)、SPPEK-086 (78 ?慆)、SPPEK-110 (76?n?慆)、SPAEEKK-070(58 ?慆)與SPAEEKK-080(48 ?慆)於40 oC下滲透通量對進料組成之關係圖 72
圖4.15 Nafion-117、SPPEK-086、SPPEK-110、SPAEEKK-070與SPAEEKK-080於40 oC下滲透物組成對進料組成之關係圖 73
圖4.16 膜材Nafion-117(187 ?慆)、SPPEK-086(78 ?慆)、SPPEK-110 (76 ?慆)、SPAEEKK-070(58 ?慆)與SPAEEKK-080(48 ?慆)於50 oC下滲透通量對進料組成之關係圖 74
圖4.17 膜材Nafion-117、SPPEK-086、SPPEK-110、SPAEEKK-070與SPAEEKK-080於50 oC下滲透物組成對進料組成之關係圖膜材 75
圖4.18 膜材Nafion-117(187 ?慆)、SPPEK-086(78 ?慆)、SPPEK-110(76 ?慆)、SPAEEKK-070(58 ?慆)與SPAEEKK-080(48 ?慆)之溫度對水滲透量關係圖 76
圖4.19 膜材Nafion-117(187 ?慆)、SPPEK-086(78 ?慆)、SPPEK-110(76 ?慆)、SPAEEKK-070(58 ?慆)與SPAEEKK-080(48?n?慆)於1 M進料甲醇水溶液之溫度對滲透量關係圖 77
圖4.20 膜材Nafion-117、SPPEK-086、SPPEK-110、SPAEEKK-070與SPAEEKK-080於1M進料甲醇水溶液之溫度對滲透物組成關係圖 78
圖4.21 膜材Nafion-117(187 ?慆)、SPPEK-086(78 ?慆)、SPPEK-110(76 ?慆)、SPAEEKK-070(58 ?慆)與SPAEEKK-080(48 ?慆)於3M進料甲醇水溶液之溫度對滲透量關係圖 79
圖4.22 膜材Nafion-117、SPPEK-086、SPPEK-110、SPAEEKK-070與SPAEEKK-080於3M進料甲醇水溶液之溫度對滲透物組成關係圖 80
圖4.23 膜材Nafion-117(187 ?慆)、SPPEK-086(78 ?慆)、SPPEK-110(76 ?慆)、SPAEEKK-070(58 ?慆)與SPAEEKK-080(48 ?慆)於5M進料甲醇水溶液之溫度對滲透量關係圖 81
圖4.24 膜材Nafion-117、SPPEK-086、SPPEK-110、SPAEEKK-070與SPAEEKK-080於5M進料甲醇水溶液之溫度對滲透物組成關係 82
圖4.25 膜材Nafion-117、SPPEK-086、SPPEK-110、SPAEEKK-070與SPAEEKK-080在進料3 M甲醇水溶液下，滲透係數對溫度之關係圖 83

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