| 摘要: | 本論文研究為兩個題目，分別是水電解之兩性離子交換膜和鋰離子電池之固態電解質。開發新型含有親水端和疏水端之聚合單體，並利用開環移位聚合反應 (Ring-Opening Metathesis Polymerization, ROMP) 製備以 polynorbornene 作為骨架，具親水端之兩性離子交換膜和固態電解質。
第一系列為 PNB-NImS-3 之兩性離子交換膜，此膜材由 PNB-CImS 改良，期望將 Imidazole 之 C2 位置裸露能與工研院交聯試劑反應，因此設計 PNB-NImS-3 之兩性離子高分子。成功合成親水端比例 50%、60% 和 70% 之 PNB-NImS-3 高分子。PNB-NImS-3 系列中，當親水端比例為 60% 時，膜材的尺寸變化率和吸水膨潤比僅有 6.8% 和 9.5%。當親水端比例為 50% 時，質子導電度高達 0.0625 Scm-1。但是此系列高分子溶解度不好，因此設計系列二。
第二系列為 PNB-NImS-6 之兩性離子交換膜，改良 PNB-NImS-3 之親水端單體結構，增加單體之碳鏈長度，設計新型親水端單體 NB-NImBr-6，以提升其溶解度。成功合成親水端比例 50% 和 60% 之 PNB-NImS-3 高分子。其中 PNB-NImS-6-50 擁有比 PNB-NImS-3-50更好的機械穩定性、化學穩定性和溶解度。當親水端比例為 50% 時，膜材的尺寸變化率和吸水膨潤比僅有 7.6% 和 8.3%，以及質子導電度高達 0.0413 Scm-1。
第三系列為固態電解質 PNB-DiLi。此為自身帶有鋰離子之高分子，成功合成不同親水端比例 30%、40% 和 50% 之 PNB-DiLi。其中 PNB-DiLi-30 粗估離子導電率為 8.49 x 10-5 Scm-1。由於 PNB-DiLi 系列膜材機械性質和溶解度差，成膜再現性低，因此設計系列四。
第四系列為 PNB-ODiLi 和 aPNB-ODiLi 之固態電解質。開發新型疏水端單體 NBO-b8，增加疏水端碳鏈長度，以提升溶解度。成功合成不同親水端比例30%、40% 和 50% 之 PNBO-DiLi，正在嘗試成膜，待測後續性質。然而，在PNBO-DiLi 的反應過程中，藉由 1H-NMR 圖譜追蹤發現，此高分子之聚合非化學性的共聚。因此將 PNBO-DiLi 與 AIBN 二次聚合，得固態電解質 aPNBO-DiLi。已經成功合成 30%、40% 和 50% 之 aPNB-DiLi 高分子，正在嘗試成膜中，待測後續性質。
;In this study, two new series of amphoteric ion-exchange membranes were developed for electrolytic water splitting. In addition, another two new series of solid polymeric electrolytes were developed for lithium-ion batteries. Ring-opening metathesis polymerization (ROMP) is used to prepare a series of hydrophilic amphoteric ion exchange membranes and solid polymer is electrolytes with polynorbornene backbone.
The first series is the development of the PNB-NImS-3-based amphoteric ion-exchange membrane. This membrane is aimed to improved the previous PNB-CImS series. The C2 position of imidazole is expected to react with the cross-linking reagent of the Industrial Technology Research Institute. We have successfully synthesized PNB- NImS-3 with different hydrophilic ratios of 50%, 60%, and 70%. Membrane prepared with 60% hydrophilic ratio ionic polymer, PNB-NImS-3, exhibited 6.8% membrane swelling ratio and 9.5% water uptake. Membrane prepared with 50% hydrophilic ratio ionic polymer, PNB-NImS-3, exhibited 0.0625 Scm-1 proton ion conductivity.
The second series is the development of the PNB-NImS-6-based amphoteric ion-exchange membrane, which increases the length of the carbon chain of the hydrophilic monomer NB-NImBr-6 to improve polymer solubility. We have successfully synthesized PNB- NImS-6 with different hydrophilic ratios of 50% and 60%. Among them, PNB-NImS-6-50 exhibited better mechanical stability, chemical stability, and solubility than PNB-NImS-3-50. Membrane prepared by PNB-NImS-6-50 exhibited 7.6% membrane swelling ratio and 8.3% water uptake, and high proton ion conductivity of 0.0413 Scm-1.
The third series is the development of the solid polymeric electrolyte PNB-DiLi. We have successfully synthesized PNB-DiLi with different hydrophilic ratios of 30%, 40%, and 50%. Among them, PNB-DiLi-30 exhibited a rough estimated ionic conductivity of 8.49*10-5 Scm-1. Since PNB-DiLi series membranes have poor mechanical properties and solubility, low reproducibility of the deposition, we move forward to develop the fourth series.
The fourth series is the development of the solid polymeric electrolytes PNBO-DiLi and aPNBO-DiLi, which increase the length of the carbon chain of the hydrophobic monomer NBO-b8 to improve membrane solubility. We have successfully synthesized PNBO-DiLi with different hydrophilic ratios of 30%, 40%, and 50%. PNBO-DiLi series were tried to form a film, for the membrane properties examination. However, during the polymerization of PNBO-DiLi, monitored by 1H-NMR spectrum it was found that polymerization of this series is a non-chemical copolymer. Therefore, the solid polymeric electrolyte of aPNBO-DiLi is obtained by the secondary polymerization of PNBO-DiLi and AIBN. We have successfully synthesized aPNBO-DiLi with different hydrophilic ratios of 30%, 40%, and 50%. Film preparation of these new series of polymer is undergoing. |
