臺灣博碩士論文加值系統

本論文研究主旨在探討以異氰酸鹽（isocyanate）官能化石墨烯氧化物（Graphene oxide, GO）修飾聚乙烯醇質子交換膜之研究。以Hummer’s法將天然石墨氧化，製備石墨烯氧化物，再以不同比例之4,4-二異氰酸酯二環已基甲烷（4,4’-Methylenebis(cyclohexyl isocyanate), HDI）官能化石墨烯氧化物。HDI其分子結構在兩端各帶有一個異氰酸酯（-NCO）官能基團，可以與羥基與羧基反應，形成醯胺與胺基甲酸脂，HDI官能化GO大致可以分呈三種情況：（1）兩片GO間接上HDI兩端、（2）HDI兩端接在同片GO表面、（3）在GO表面上接上一端，而另一端-NCO保留未反應。為了討論改質接枝位置的差異，後續以FTIR分析其官能基團，再以XRD分依其層間距變化、SEM觀察表面形態變化，最後以EDS元素分析推測接枝數量的多寡。由結果來看，40 mmol HDI/1g GO(iGO40)表面會帶有做多的-NCO官能基團，當比例上升到60 mmol HDI/1g GO(iGO60)時，表面帶有的-NCO官能基團數量反而會下降，推測是在高改質比例時，會受到分子結構立體阻礙的影響，影響接枝的位置。
以表面異氰酸酯官能基團的多管區分，將iGO10、iGO20與iGO40加入到PVA/SSA/PSSA-co-MA複合膜中，期望藉由酸鹼對的互動強化質子傳導的跳躍機制，克服GO加入會因酯化反應，複合膜進一步交聯的結果使得質子傳導下降的問題。後續以質子傳導率、甲醇滲透率、含水率與選擇率來評估薄膜的性能。由結果來看，酸鹼對的互動有助於質子傳導的增加，又因表面有異氰酸酯官能基團可與PVA上的羥基（-OH）反應，能使薄膜交聯，能使甲醇滲透進一步減少，在PVA/SSA20/PSSA-co-MA60/iGO40 0.5%時會有最高的選擇率，質子傳導率為23.38 mS/cm，甲醇滲透率為3.79×10-7cm2/s。

In this paper, the purpose of this study is to study the modification of polyvinyl
alcohol proton exchange membrane with isocyanate functionalized graphene oxide
(GO). The natural graphite was oxidized by Hummer's method to prepare graphene
oxide and functionalized graphene oxide with different proportions of 4,4'-diisocyanate dicyclohexylmethane (4,4'-Methylenebis (cyclohexyl isocyanate), HDI). HDI its molecular structure at both ends with an isocyanate (-NCO) functional groups, with hydroxyl and carboxyl reaction, the formation of amide and aminocarboxylic acid, HDI functionalized GO can be divided into three cases: (1) two pieces of GO indirectly on both ends of HDI, (2) HDI at both ends connected to the same GO surface, (3) on the GO surface connected to one end, and the other end -NCO remains unreacted. In order to discuss the difference of modified grafting sites, the functional groups were analyzed by FTIR, and the change of the interlayer distance was observed by XRD. The morphological changes were observed by SEM. Finally, the number of grafts was deduced by EDS element analysis. From the results, the surface of 40 mmol HDI / 1 g GO (iGO40) with the largest number of -NCO functional groups, when the proportion rose to 60mmol HDI / 1g GO (iGO60), the surface with the number of -NCO functional groups But will drop, push the test in the high-quality ratio, will be affected by the molecular structure of the impact of three-dimensional, affecting the graft position. In the PVA / SSA / PSSA-co-MA composite membrane, iGO10, iGO20 and iGO40 were added to the surface isocyanate functional groups, and it was expected that the activation of proton conduction by the interaction between acid and alkali pairs Will be due to esterification reaction, composite film further cross-linking results in the problem of proton conduction decline. The performance of the film was evaluated by proton conductivity, methanol permeability, water content and selectivity. From the results, the interaction between acid and alkali pairs contributes to the increase of proton conduction, and because of the presence of isocyanate functional groups on the surface with hydroxyl groups (-OH) on PVA, the film can be crosslinked to further reduce the methanol infiltration , The highest selectivity was observed at PVA / SSA20 / PSSAco-MA60 / iGO40 0.5%, the proton conductivity was 23.38 mS / cm, and the methanol permeability was 3.79 × 10-7 cm2 / s.

摘要i
ABSTRACTii
目錄iv
表目錄vii
圖目錄viii
第1章緒論1
1.1 前言1
1.2 燃料電池的種類2
1.3 質子交換膜燃料電池3
1.3.1 膜材的種類5
1.3.2 商業化質子交換膜（Nafion7
1.4 直接甲醇型燃料電池8
1.5 影響質子交換膜中質子性能的因素9
1.5.1 可調參數9
1.5.2 結構的特性10
1.6 關於石墨烯與石墨烯氧化物12
1.6.1 石墨烯的發現12
1.6.2 石墨烯的導電性與熱傳導性15
1.6.3 石墨烯的機械性質15
1.6.4 製備石墨烯之方法16
1.7 研究動機18
第2章文獻回顧20
2.1 質子交換膜中的傳導機制20
2.1.1 質子交換膜中質子與甲醇的傳導機制20
2.1.2 質子傳導的水合形態21
2.2 以聚乙烯醇為基材之質子交換膜24
2.2.1 PVA化學交聯24
2.2.2 PVA與PSSA-co-MA相關研究25
2.3 石墨烯氧化物（Graphene oxide, GO）27
2.3.1 應用於質子交換膜27
2.3.2 磺酸官能化28
2.3.3 異氰酸酯官能化30
第3章儀器與實驗原理36
3.1 傅立葉紅外線吸收光譜儀（Fourier Transform Infrared, FTIR）36
3.2 X光繞射分析儀（X-ray diffraction, XRD）36
3.3 掃描式電子顯微鏡（Scanning Electron Microscopy, SEM）37
3.4 能量散佈光譜儀（Energy Dispersive Spectrometer, EDS）37
3.5 交流阻抗分析（AC-Impendence）38
3.6 電化學阻抗圖譜（Electrochemical impedence spectroscopy, EIS）43
3.7 甲醇滲透率（Methanol Permeability）44
第4章實驗設備與步驟47
4.1 實驗藥品47
4.2 實驗儀器48
4.3 無機物製備49
4.3.1 石墨烯氧化物（Graphene oxide, GO）製備49
4.3.2 4,4-二異氰酸酯二環己基甲烷（HDI）改質GO（iGO）50
4.4 薄膜製備51
4.4.1 PSSA-co-MA前處理51
4.4.2 PVA/SSA/PSSA-co-MA複合膜51
4.4.3 iGO複合膜52
4.5 官能化石墨烯氧化物之分析與鑑定53
4.5.1 傅立葉轉換紅外線分光分析(FTIR-ATR)53
4.5.2 X光繞射分析53
4.6 薄膜分析與鑑定53
4.6.1 飽和含水率53
4.6.2 交流阻抗實驗54
4.6.3 甲醇滲透率實驗55
第5章結果與討論56
5.1 石墨烯氧化物（GO）之分析56
5.1.1 FTIR分析56
5.1.2 XRD分析57
5.1.3 SEM分析58
5.2 異氰酸酯官能化石墨烯氧化物（iGO）之分析60
5.2.1 FTIR分析61
5.2.2 XRD分析64
5.2.3 SEM分析66
5.2.4 EDS分析67
5.3 複合膜之分析69
5.3.1 基本性質分析總表69
5.3.2 質子傳導率71
5.3.3 甲醇滲透率73
5.3.4 含水率75
5.3.5 選擇率76
5.3.6 接近領域的比較78
第6章結論79
參考文獻82

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