電場誘導高離子導向之混摻高分子固態電解質

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姓名

張倚涵(Yi-Han Chang) 查詢紙本館藏

畢業系所

化學學系

論文名稱

電場誘導高離子導向之混摻高分子固態電解質

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摘要(中)

鋰離子二次電池廣泛使用在各個電子產品與行動裝置，為重要儲能裝置之一；由於一般鋰電池之電解液在使用上，有安全性上之隱憂，因此發展不具揮發性之固態電解質為解決此問題之方法之一。
本研究利用兩種不同比例之PMMA及PVDF-HFP高分子混摻及非揮發性離子液體之結合，於電場誘導極化下製成高離子導電度之固態電解質。在電場中，非結晶區之高分子鏈形成有序之排列；結晶區結晶度下降，提供鋰離子有更多之運動空間，增加導離子導電度，此系統之樣品之導電度皆可達10-3 S/cm以上。尤其是主體高分子比例為PVDF-HFP:PMMA=50:50電場處理後之e5EL樣品，在溫度70oC，導電度可高達10-2 S/cm。由於電場誘導之結構上的改變，非結晶區形成長程有序的排列，進而使薄膜緻密化，不但增加薄膜之機械強度提高PVDF-HFP/PMMA之相容性，伴隨著提升薄膜之熱穩定性及電化學穩定性，電化學視窗最高可達5.58 V。此外電解質與電極之介面電阻也由於PMMA及電場極化之效應得以改善。
電性測試上，在0.1C時，皆都可達120mAh/g以上，e5EL電容量可達150mAh/g，而在0.5C充放電速率下，e3EL電容量可以達70mAh/g，在庫倫效率，皆可達100%左右。

摘要(英)

Lithium-ion battery holds great promises for automobile applications and for energy storage purpose. In this work, we present a highly ion conducting solid polymer electrolytes (SPEs) membrane, prepared under external electric field (EF) poling where nonvolatile conducting medium, ionic liquids (ILs) in solid polymer electrolytes. The poling created aligned morphology in PVDF-HFP and PMMA blending system yielding long-range ordered morphology, but remains nearly total amorphous where nonflammable ionic liquids is fully dispersed to deliver unusually high Li+ transport. Room temperature conductivity reached above 10-3S/cm and the highest conductivity of 10-2 S/cm is observed at 70oC for polymer electrolyte containing PMMA/PVDF-HFP (50/50 wt%, e5EL). The alignment by the external electric field not only altered the interaction between polymer components which has suppressed PVDF-HPF crystallinity in the SPEs, but it also improves mechanical strength of the membrane, and reduced the electrode-electrolyte interface resistance. The coin cell (R2032) using e5EL, e4EL and e3EL as the SPEs and LiFePO4 cathode shows fair half-cell performance and durable cycle stability. Under 0.1C-rate the half-cell displayed discharge capacity which could above a1most 120 mAh/g, and at 0.5C-rate the capacity reached above 60mAh/g , especially e3EL reached 70mAh/g.

關鍵字(中)

★ 固態電解質
★ 混摻高分子
★ 離子液體
★ 電場誘導
★ 鋰離子二次電池

關鍵字(英)

論文目次

摘要 i
Abstract ii
目錄 iii
圖目錄 vii
表目錄 x
第1.章緒論 1
1.1. 研究背景 1
1.2. 鋰離子二次電池之發展與簡介 2
1.3. 研究動機與目的 6
第2.章文獻回顧 8
2.1. 聚合物電解質 9
2.1.1. 聚合物電解質之發展 9
2.1.2. 聚合物電解質之簡介與分類 11
2.1.3. 聚合物電解質之內部形貌 12
2.1.4. 聚合物電解質之目標性質 14
2.1.5. 聚合物電解質之製程技術 16
2.1.6. 聚合物混摻電解質之發展與簡介 17
2.2. PVDF-HFP及PMMA之介紹與應用 19
2.2.1. 聚偏二氟乙烯六氟丙烯(PVDF-HFP) 19
2.2.2. 聚甲丙烯酸甲酯(PMMA) 22
2.3. 離子液體 27
2.3.1. 離子液體之簡介與特性 27
2.3.2. 離子液體在高分子電解質上之應用 28
2.4. 外加電場之影響 30
第3.章實驗方法 32
3.1. 實驗藥品與儀器 32
3.1.1. 實驗藥品 32
3.1.2. 實驗儀器 34
3.2. 實驗流程與操作 35
3.2.1. 薄膜製備 35
3.2.2. 鈕扣型半電池之製備 36
3.3. 儀器簡介與用途 37
3.3.1. 示差掃秒式熱差儀 37
3.3.2. 線性掃描式伏安法之分析 39
第4.章實驗結果與討論 42
4.1. 薄膜之結晶性與物化性 43
4.1.1. 結晶性 43
4.1.2. 以DSC鑑定樣品之熱性質探討與結晶變化 44
4.1.3. 機械性質之探討 46
4.1.4. SEM之固態電解質表面之鑑定 47
4.1.5. 變溫導電度之探討 49
4.2. 薄膜之穩定性質 52
4.2.1. 熱穩定性 52
4.2.2. 電化學穩定性 54
4.2.3. 鋰離子於電解質之中傳導機制 57
4.3. 電解質與電極之介面探討 58
4.3.1. 電化學介面光譜之鑑定 58
4.3.2. 以SEM鑑定充放電後之薄膜表面 60
4.4. 半電池之電性測試 62
第5.章結論與未來展望 66
5.1. 結論 66
5.2. 未來展望 66
參考文獻 68

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指導教授

諸柏仁(Po-Jen Chu)

審核日期

2016-7-26

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