本研究係以不同分子量之聚乙烯亞胺(PEI，Mw=600、1800、10000) 與聚矽氧烷(GPTMS)在摻合磷酸(H3PO4)的狀態下加熱進行交鏈反應得到高分子質子傳導膜，並進行一系列的探討研究其特性以應用於質子傳導膜燃料電池。首先係利用傅立葉紅外線光譜儀、13C CP/MAS NMR與29Si CP/MAS NMR鑑定質子傳導膜之高分子結構，並利用DSC以及TGA探討其熱穩定性質，藉由交流阻抗分析法(AC-impedance)量測其質子傳導度，利用量測之質子傳導度，搭配1H NMR與31P NMR分析鑑定，藉以探討proton在質子傳導膜中的傳遞機制。本系統針對傳導膜中不同分子量之PEI、摻入磷酸含量(P/N ratio)、不同聚矽氧烷比例(Si/N ratio)進行對溫度與溼度的探討。發現隨著分子量的提升以及Si/N ratio的增加，機械性質有明顯提升的現在，基於機械強度以及導電度，本研究將Si/N ratio定於1/16，而隨著磷酸的摻入能得到較佳之質子傳導度，在80%R.T.、80oC環境下各系列所製備出之質子傳導膜(PEI Mw=600、1800、10000 at P/N=0.5)的質子傳導度(4.5x10-2、4.2x10-2、2.2x10-2 S/cm)具有實際應用於燃料電池之價值。

　　In this study, organic-inorganic hybrid polymer proton conductive membrane have been prepared via sol-gel approach. The significant interactions between the proton and polymer host have been observed for the composite electrolytes in the presence of H3PO4 by means of FT-IR, DSC, TGA, 1H, 13C, 29Si and 31P solid-state NMR. The thermal stability and proton conductivity of these complexes were also investigated by TGA, water uptake and AC-impedance measurements. The results of FT-IR, DSC and TGA measurements indicate the formation of different types of complexes though the interaction of the protons with different coordination sites of polymer electrolyte networks.

　　The DSC data indicate the formation of transient cross-links between GPTMS’s epoxy group and PEI doping with H3PO4, resulting in an increase in the Tg of proton conductive membrane in this system. In addition, the dependence of the proton conductivity was investigated as a function of temperature, humidity, molecular weight and H3PO4 concentration. It is found that the proton transport behavior is affected by the combination of the proton mobility and number of carrier proton. The 1H MAS NMR spectroscopic results of these polymer complexes suggest a significant interaction between proton and polymer host. The temperature, humidity, and H3PO4 concentration are correlated with proton conductivity.

壹、中文摘要……………………………………………………………i
貳、英文摘要……………………………………………………………ii
参、誌謝………………………………………………………………iii
肆、總目錄……………………………………………………………iv
伍、流程目錄………………………………………………………vii
陸、表目錄…………………………………………………………viii
柒、圖目錄……………………………………………………………ix
捌、主文

第一章 緒論………………………………………………………………1

第二章 原理………………………………………………………………14
2.1 EIS 理論……………………………………………14
2.2 固態核磁共振光譜…………………………………19
2.3 魔術旋轉角…………………………………………21
2.4 交叉極化……………………………………………21
2.5 溶膠法………………………………………………22

第三章 製備與性質分析…………………………………………24
3.1 實驗品………………………………………………24
3.2 實驗器材……………………………………………25
3.3 分析儀器……………………………………………25
3.4 質子傳導膜之製備…………………………………26
3.5 高分子之鑑定………………………………………26
3.5.1 傅立葉轉換紅外線光譜儀………………26
3.5.2 交叉極化/ 魔術轉角固態核磁共振光譜儀…27
3.6 熱性質分析…………………………………………27
3.6.1 微差式掃描卡計……………………………27
3.6.2 熱重分析……………………………………27
3.7 交流阻抗分析………………………………………27
3.8 含水量的測試………………………………………28

第四章 結果與討論…………………………………………………………30
4.1 傅立葉轉換紅外線光譜圖…………………………30
4.2 固態核磁共振光譜…………………………………31
4.2.1 13C CP/MAS NMR……………………………31
4.2.2 29Si CP/ MAS NMR…………………………33
4.2.3 1H MAS NMR…………………………………34
4.2.4 31P MAS NMR………………………………35
4.3 熱性質分析…………………………………………37
4.4 交流阻抗分析及質子傳導膜導電度………………………………40
4.4.1 摻入磷酸之濃度對於導電度之影響………41
4.4.1 (a) 溫度探討………………………41
4.4.1 (b) 溼度與持水能力的探討………47
4.4.2 不同分子量對導電度之影響………………49
4.4.3 Si/N 比例對於導電度之影響……………50

第五章 結論……………………………………………………52
玖、 參考文獻………………………………………………………………54
拾、 自述……………………………………………………………………92

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