本論文主要研究奈米不織布單離子導電電解質 (SICE) 膜在室溫環境下具有傑出的效能。與商業PP隔離膜相比，藉由lithium poly[4-styrenesulfonyl(phenylsulfonyl)imide]和聚丙烯腈的混合溶液製備的SICE膜具有優異的溶劑化特性，並且具有多孔結構可以促進鋰離子傳遞。在室溫環境下，奈米電解質膜在碳酸酯溶劑的系統中具有優良的離子導電率(3.9 × 10−3 S/cm)、電化學穩定視窗高達5.2 V (vs. Li/Li+)，而離子遷移率也達0.93。此外，將奈米電解質膜與磷酸鋰鐵正極製備成半電池進行測試，發現不僅在0.2 C和0.5 C下獲得了163 mAh/g的放電容量(這是SICE迄今為止報導的最高值，並且為LiFePO4 理論電容量的95.9％)，而且在2 C的充放電速率下電容量也比與商業隔膜/雙離子電解質系統高。這種令人鼓舞的創新方法，可能是未來商業電解質膜的設計和製造技術的選擇之一。

In this study, a nonwoven nanofabric single-ion conducting electrolyte (SICE) membrane exhibiting excellent electrochemical performance in ambient environment has been fabricated. Compared to commercial polypropylene separators, the SICE membrane, fabricated via electrospinning of the hybrid solution containing lithium poly[4-styrenesulfonyl(phenylsulfonyl)imide] and polyacrylonitrile, possesses excellent solvation characteristics due to porous morphology that facilitates transportation of lithium ions. It shows superior ionic conductivity of 3.9 × 10−3 S cm−1 and a broader electrochemical window of up to 5.2 V (vs. Li/Li+) with a lithium transference number (t_(〖Li〗^+ )) of 0.93 at 30 °C under ethylene carbonate/propylene carbonate/diethyl carbonate (=3/2/5, v/v/v) solvent system. Furthermore, fabricated with this SICE membrane, the lithium ion batteries made from LiFePO4 cathode demonstrate not only a discharge capacity of 163 mAh/g at 0.2 and 0.5 C, which is the highest value reported so far for SICEs (95.9% of the theoretical capacity of LiFePO4) but also higher discharge capacities up to 2 C in comparison with the commercial separator/dual-ion salt electrolyte system. Those encouraging results with this innovative approach indicate this might be a potential candidate for the design and fabrication techniques of commercial electrolyte membranes in future.

目錄
論文審定書 i
論文公開授權書 ii
謝誌 iii
摘要 v
Abstract vi
目錄 vii
圖目錄 x
表目錄 xii
第一章 緒論 1
1-1 前言 2
1-2 研究動機 3
第二章 文獻回顧 4
2-1 鋰離子電池 5
2-1.1 一次電池和二次電池簡介 5
2-1.2 工作原理 6
2-1.3 陰極材料 7
2-1.4 陽極材料 7
2-2 電解質的介紹 8
2-2.1 液態電解質 (Liquid electrolytes) 8
2-2.2 固態高分子電解質 (Solid polymer electrolytes, SPEs) 10
2-2.3 膠態高分子電解質 (Gel Polymer Electrolytes, GPEs) 11
2-2.4 單離子導體高分子電解質
(Single-Ion Conducting Electrolytes, SICEs) 12
2-3 靜電紡絲 13
2-3.1 研究歷史 13
2-3.2 工作原理 13
2-3.3 實驗參數 14
第三章 實驗方法 15
3-1 實驗藥品材料以及器材 16
3-2 實驗步驟 19
3-2.1 單離子導體高分子合成 19
3-2.2 靜電紡絲不織布薄膜製備 23
3-2.3 磷酸鋰鐵正極材料製備 24
3-2.4 鋰離子電池組裝 25
3-3 高分子分析鑑定儀器介紹 26
3-3.1 高磁場液態核磁共振儀 (500 MHz NMR) 26
3-3.2 電噴灑質譜儀 (ESI/MS) 26
3-3.3 元素分析儀 (Element Analysis, EA) 26
3-3.4 感應耦合電漿質譜分析儀 (ICP-MS) 26
3-3.5 熱重量分析 (TGA) 26
3-3.6 凝膠滲透層析儀 (Gel Permeation Chromatograph, GPC) 27
3-3.7 解析掃描式電子顯微鏡 (SEM) 27
3-4 電化學測試儀器介紹 28
3-4.1 線性掃瞄伏安法 (LSV) 28
3-4.2 交流阻抗測試 (AC-impedance) 29
3-4.3 鋰離子遷移數分析 29
3-4.4 循環伏安法測試 (CV) 31
3-4.5 半電池充放電測試 (Charge-discharge & C-rate performance) 32
第四章 結果討論 33
4-1 單離子導體高分子之結構鑑定 34
4-1.1 高磁場液態核磁共振儀 34
4-1.2 電噴灑質譜儀 & 凝膠滲透層析儀 37
4-1.3 元素分析儀、感應耦合電漿質譜分析儀 40
4-2 熱穩定性分析 41
4-3 電化學穩定度 42
4-4 離子傳導度 43
4-5 鋰離子遷移數 45
4-6 電解液吸收度 47
4-7 半電池測試 49
4-7.1 循環伏安法 49
4-7.2 充放電曲線比較 51
4-7.3 循環壽命比較 55
4-8 充放電前後電池結構檢測 56
第五章 總結 57
第六章 參考文獻 59
第七章 附錄 63

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