臺灣博碩士論文加值系統

本研究以溶膠－凝膠法塗佈於多孔PVDF有機膜上，合成具有介孔結構的二氧化矽有機－無機複合膜，並應用在全釩液流電池的隔離膜。而為了增加溶膠－凝膠溶液和多孔PVDF的親和性，使用脈衝雷射沉積法對多孔PVDF進行表面修飾及改質。修飾過的PVDF膜做為溶膠－凝膠法的基板，可以生成約4微米厚的介孔二氧化矽緻密層，藉由同步形成的磺酸官能基增加質子通透速率。在離子選擇率測試當中，使選擇率超過Nafion膜。

The purpose of this study is to synthesize mesoporous silica organic-inorganic complex membranes for vanadium redox flow batteries via sol-gel method dip-coating on porous PVDF membranes. Pulsed laser deposition (PLD) was utilized for modifying the porous PVDF membranes in order to enhance the bonding between the sol-gel solution and the porous PVDF membranes. A 4 μm thick mesoporous silica coating over the membrane, achieved from dip-coating, resulted in the formation of an organic-inorganic composite membrane which by far improved the proton transport through sulfonic functional groups. The modified mesoporous silica organic-inorganic complex membrane was found to have better selectivity compared to the regular Nafion membranes.

目次
摘要 I
Abstract II
目次 III
圖目次 V
表目次 VI
第一章　緒論 1
第一節 儲能系統 1
第二節 全釩液流電池（VRB） 6
第三節 VRB半透膜必須具備的特性 8
第四節 VRB半透膜的設計 11
第五節 PVDF的親水性加強 19
第六節 研究動機 23
第七節 研究目的 24
第二章　藥品與儀器 25
第一節 使用藥品 25
第二節 使用儀器 26
第三章　實驗步驟 29
第一節 oPDA-HNbWO6•xH2O混合PVDF 29
第二節 PVDF混紡 HEMA有機聚合膜製備（PVDF Blending poly-HEMA，PBH） 30
第三節 無機粉末混合PBH 32
第四節 溶膠－凝膠法（sol-gel）合成介孔二氧化矽（Mesoporous Silica，MS） 33
第五節 脈衝雷射沉積法（Pulsed Laser Deposition，PLD）對PBH80進行表面修飾及改質 38
第六節 離子選擇率測試（ion selectivity test） 40
第七節 簡寫對照表 43
第四章　結果與討論 44
第一節 HNbWO6•xH2O做為功能性材料 44
第二節 oPDA-HNbWO6•xH2O混合PVDF 47
第三節 PVDF混紡 HEMA改善膜的親水性 50
第四節 無機粉末混合PBH離子選擇率測試 57
第五節 溶膠－凝膠法合成介孔二氧化矽無機層(MS) 59
第六節 MS塗佈於PBH80半透膜 62
第七節 脈衝雷射沉積法修飾及改質PBH80半透膜 67
第八節 MS塗佈於PLD-PBH80半透膜 67
第九節 PLD-PBH80、PLD-MS1半透膜的離子選擇率測試 71
第十節 結論 73
參考文獻 74

圖目次
圖 1 1：再生能源的年發電量，佔年總再生能源的百分比。 4
圖 1 2：三種能夠行媒介傳導質子的官能基 9
圖 1 3：三種常見的陽離子交換膜結構圖 13
圖 1 4：三種含有四級銨的陰離子交換膜結構圖 14
圖 1 5：兩種兩性聚合物的合成及結構 15
圖 3 1：合成PBH所使用的藥品結構 31
圖 3 2：EISA反應的相圖 36
圖 3 3：合成MS所使用的藥品結構 37
圖 3 4：PLD簡易裝置示意圖 39
圖 3 5：離子選擇率測試容器架設示意圖 41
圖 3 6：PBH80離子選擇率測試莫耳數對時間的線性關係圖 42
圖 4 1：oPDA-HNbWO6•1.5H2O合成示意圖 45
圖 4 2：oPDA-HNbWO6•xH2O粉末的XRD圖譜 46
圖 4 3：HNbWO6•xH2O插層反應的XRD圖譜 49
圖 4 4：合成PBH有機膜的示意圖 52
圖 4 5：PBH的FTIR吸收光譜 53
圖 4 6：PBH50俯視SEM影像 54
圖 4 7：PBH50橫截面SEM影像 55
圖 4 8：MS的合成示意圖 60
圖 4 9：溶膠－凝膠薄膜在載玻片上的XRD繞射圖 61
圖 4 10：sol-gel MS塗佈於PBH80的SEM影像 65
圖 4 11：半透膜高分子纖維的FESEM影像 66
圖 4 12：PLD-PBH80的SEM影像 68
圖 4 13：PLD-MS1的SEM影像 69
圖 4 14：PLD-PBH80以及PLD-MS1的FESEM影像 70

表目次
表 1 1：各儲能系統目前的最佳性能 5
表 1 2：Daramic及其修飾過的半透膜，在VRB性能比較。 16
表 3 1：簡寫對照 43
表 4 1：各比例oPDA-HNbWO6•xH2O PVDF複合膜的配方 48
表 4 2：無機材料混合PVDF的離子選擇率測試 48
表 4 3：PBH50和PBH80半透膜結構 56
表 4 4：PBH混合無機粉末的離子選擇率測試 58
表 4 5：MS塗佈於PBH80半透膜的離子選擇率測試 64
表 4 6：PLD-PBH80以及PLD-MS1的離子選擇率測試 72

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