臺灣博碩士論文加值系統

本研究利用氟化高分子PVdF-co-HFP，分別以鑄膜法以及靜電紡絲技術，製備離子電池之隔離膜。在鑄膜法部分，本研究嘗試以不同比例混合氟化高分子以及離子液體，經由SEM分析表面型態，發現離子液體的添加可增加高分子的孔洞結構；另一方面，在PVdF-co-HFP中添加交聯劑1,3-Diaminopropane(DAP)，並以鑄膜法(CF-1、CF-2、CF-3、CF-4)以及靜電紡絲法(NF-1、NF-2、NF-3、NF-4)分別製備出隔離膜，由SEM、FT-IR、TGA、DSC分析隔離膜的物理性質，以及以交流阻抗法測試纖維隔離膜的導離子度。
由SEM觀察，將PVdF-co-HFP以靜電紡絲法製備成奈米纖維隔離膜，可有效增加孔洞性有助於離子於電池中的移動，在纖維膜浸泡離子液體後，可觀察到離子液體與纖維膜的微相分離。由熱性質分析，可以發現隔離膜再加入交聯劑之後，能夠在熱性質差異不大的情況下隨著交聯劑比例的上升，有效提升隔離膜的機械性質。
在電化學性質上面，將纖維膜浸泡於溶於乙醇的離子液體的電解液中，隨著交聯劑比例的上升，電解液吸收度的下降；在交聯阻抗分析中，也顯示出交聯劑比例的上升，導離子度下降的趨勢，說明了交聯劑對PVdF-co-HFP高分子纖維膜結構的影響，然而總體來說導離子度比一般氟化高分子在鋰離子電池中低。在與鋁離子電池常用之電解液(AlCl3/[EMIm]Cl=1.3)的相容性上，因氟化高分子隔離膜會有與電解液發生化學反應的疑慮，因此推論，若要以鋰離子電池常用的氟化高分子應用於鋁離子電池，需要對高分子進行表面修飾等，以進一步提升氟化高分子在鋁離子電池的相容性。

We utilized the fluoro-based polymer, PVdF-co-HFP to prepare the separators for ion batteries by casting-film and electrospinning membrane. In the part of casting-film, we tried to mix the PVdF-co-HFP and ionic liquid with different ratios. According to the SEM analysis, it would be found that the addition of ionic liquid could increase the porous structure; on the other side, we added the cross-linker 1,3-Diaminopropane(DAP) into the solution of polymer, and then prepare the separators by the casting-film and electrospinning membrane. We tested the physical properties of our separators by SEM、FT-IR、TGA、DSC analysis, and the electrochemical properties by AC impedance analysis.
From the SEM analysis, the electrospinning membrane of PVdF-co-HFP could helpfully increase the mobility since the porous structure. It also could be observed the microphase separation after soaked in the ionic liquid. According to the TGA、DSC analysis, we found that after the addition of cross-linker, the mechanical properties promote with the increasing of the ratio of cross-linker without obvious difference of thermal properties.
In the electrochemical property analysis, the uptake of electrolyte decreased with the increasing of the ratio of cross-linker after the membrane soaked in the ionic liquid; in the AC impedance analysis, it also shows the same tendency of the ionic conductivity. It explained the influence of the cross-linker for the membrane structure, but the ionic conductivities were still lower than the PVdF-co-HFP
separators in lithium-ion batteries. As for the compatibility of aluminum-ion battery, there was a concern about the reactivity for the electrolyte which is wildly used in aluminum-ion battery. It is inferred that if we would like to apply our PVdF-co-HFP electrospinning membrane to aluminum-ion batteries, it is necessary to modify the surface structure of polymer in order to improve the compatibility of aluminum-ion battery.

中文摘要 I
Abstract II
致謝 IX
目錄 XI
圖目錄 XIV
表目錄 XVII
第一章、 緒論 1
1.1前言 1
1.2研究背景與文獻回顧 2
1.2.1二次電池發展史 2
1.2.1.1鉛酸電池 2
1.2.1.2鎳鎘電池 2
1.2.1.3鎳氫電池 2
1.2.1.4鋰離子電池 3
1.2.1.5鋰硫電池 4
1.2.1.6鈉/鎂電池 5
1.2.1.7鋰空氣電池 6
1.2.2鋁離子電池 7
1.2.3鋁離子電池之工作原理 10
1.2.3.1正極材料 11
1.2.3.1.1過渡金屬氧化物(VO2、V2O5)材料 11
1.2.3.1.2碳材(graphite) 13
1.2.3.1.3含硫正極材料(Mo6S8、NiS) 15
1.2.3.1.4鋁離子電池正極材料之比較 16
1.2.3.2負極材料 17
1.2.3.3電解質 18
1.2.3.3.1液態有機電解質 19
1.2.3.3.2高分子電解質 21
1.2.3.3.3膠態高分子電解質 22
1.2.3.3.4固態高分子電解質 23
1.2.3.3.5 PVdF-based 高分子電解質 24
1.2.3.4隔離膜 25
1.2.3.5固態電解質界面膜(Solid electrolyte interphase,SEI) 26
1.2.3.6離子液體與在二次電池的應用 27
1.2.4靜電紡絲技術 29
1.2.4.1 靜電紡絲簡介 29
1.2.4.2靜電紡絲原理與裝置 29
1.2.4.3影響靜電紡絲之參數 30
1.2.5交流阻抗分析 35
1.2.6導離子度 37
1.3研究動機與目的 39
第二章、實驗 40
2.1實驗藥品 40
2.2儀器設備 41
2.3實驗方法 42
2.3.1 高分子/離子液體混摻高分子隔離膜 42
2.3.2交聯之高分子隔離膜製備 43
2.3.3鈕扣電池組裝 45
2.3.4鋁離子電池電解液相容性測試 45
2.3.5導離子度分析(Ionic conductivity, σ) 46
2.4儀器鑑定原理及分析 46
2.4.1掃描式電子顯微鏡(Scanning Electron Microscope, SEM) 46
2.4.2傅立葉轉換紅外線光譜儀(FT-IR) 47
2.4.3熱重量分析(Thermogravimetric analysis, TGA) 47
2.4.4微差式掃描熱卡計(Differential scanning calorimetry, DSC) 48
2.4.5動態熱機械分析儀分析(Dynamic Mechanical Analysis, DMA) 48
2.4.6交流阻抗分析(AC Impedance) 49
第三章、結果與討論 50
3.1高分子隔離膜型態 50
3.1.1高分子/離子液體混摻高分子隔離膜 50
3.1.2交聯之高分子隔離膜 52
3.2 FT-IR (ATR)交聯度分析 56
3.3 TGA熱重分析 58
3.4 DSC熱轉移性質分析 59
3.5 DMA機械拉伸性質分析 61
3.6電解液吸收量(Electrolyte uptake)測試 63
3.7交流阻抗分析導離子度分析 64
3.8鋁離子電池電解液相容性測試 66
第四章、結論 67
第五章、參考文獻 68

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