無鋰金屬電池 (Lithium-Free Battery) 負極因擁有高能量密度 (3860 mAh/g) 與相對鋰金屬電池來說更低的安全疑慮使之成為下世代電池中最具競爭力的候選者，但銅箔與電解液之間的低親和力使得鋰枝晶於循環過程更易生成，因枝晶鋰所增加的比表面積會加速電解液的消耗、形成更多的固態電解質介面膜 (SEI) 、並增加鈍化層的厚度，再者，不可逆的容量損耗與循環過程所產生的體積變化降低了其被實際應用的可能性。因此，本研究透過靜電紡絲技術製造了一層高親鋰性的聚丙烯腈/二氧化鈦複合保護層於銅箔上使電鍍鋰金屬更為均勻，從結果來說，我們使用相對更高的 0.5C 充電 1C 放電速率，達到了於 100 圈下 51.8%的高容量維持率 (無保護層的為40.3%) ，另外，相對於研究保護層對於正負極所產生的影響而使用的半電池二極式系統來說 (e.g. Li||Cu, LFP||Li) ，我們使用三極式系統，直接的量測於無鋰金屬電池 (LFP||Cu) 充放電過程當中，兩極分別的電位變化情形，並透過所蒐集的結果提出對於 LFP||Cu 充放電機制的解釋，總體而言，我們除了提供一個高電流密度保護層的新思路外，還展現了一個研究無鋰金屬電池的新角度。

Lithium-free batteries are considered to be a promising candidate for the next generation lithium batteries due to their higher energy density (3860 mAh/g) and reduced safety concerns. However, because of the low affinity of copper substrates to the electrolyte, lithium dendrites are easily generated during the charge-discharge cycling process. The enhanced surface area, due to the lithium dendrite formation, accelerates the electrolyte consumption to generate solid electrolyte interface (SEI) on the newly born Li surface, and further thickens the passivation layer. In addition, both the irreversible capacity loss and infinite volume change during the charge-discharge cycling may hinder its commercial application. Herein, we construct a lithiophilic nanofibrous membrane consisting of polyacrylonitrile (PAN) and titanium dioxide (TiO2) via an electrospinning process on the copper foil to deposit lithium uniformly. As a result, we achieved higher retention rate (51.8%) and greater discharge capacity (77.32 mAh/g) compared with the unprotected copper foil (40.3% retention rate, 52.73mAh/g discharge capacity) in the 0.5C-charge-1C-discharge program for 100 cycles in the lithium-free battery. Besides, rather than the approaches using the two-electrode cell configurations (e.g., Li||Cu, LFP||Li), we directly decouple the potential variations of each electrode in LFP||Cu to gain the understanding on both electrodes within the charge-discharge mechanisms in a three-electrode system. Lastly, this work not only constructs an effective modified electrode, allowing the high current density operation, but also demonstrates a broad scope for studying the lithium-free battery mechanism.

摘要 I
ABSTRACT II
誌謝 IV
目錄 VI
圖目錄 X
表目錄 XV
第一章 緒論 1
1-1 電化學原理 1
1-1-1電化學反應系統 1
1-1-2 影響電化學反應系統之變數 4
1-2 無鋰金屬電池 (Lithium-free Battery) 5
1-2-1 鋰電池的發展 5
1-2-2 鋰離子電池的簡介 6
1-2-3 鋰金屬電池 13
1-2-4 無鋰金屬電池基本工作原理與挑戰 16
1-3 靜電紡絲 17
1-3-1 靜電紡絲基本原理 17
1-3-2 靜電紡絲參數 19
1-3-3 聚丙烯腈 (PAN) 靜電紡絲 25
第二章 文獻回顧 26
2-1 鋰電池電解質 26
2-1-1 碳酸鹽類電解質 (Carbonate based electrolyte) 26
2-1-2 醚類電解質 (Ether based electrolyte) 29
2-2 人造負極保護層 (Artificial SEI) 31
2-2-1 電解質添加劑 31
2-2-2 高分子塗層 33
2-2-3 陶瓷材料 39
2-2-4 混合材料 41
2-3 靜電紡絲於鋰金屬電池之應用 42
第三章 實驗方法、步驟與儀器 43
3-1 研究動機 43
3-2 實驗架構圖 44
3-3 實驗藥品 45
3-4 實驗步驟 47
3-5 鈕扣式電池組裝 48
3-6 實驗儀器與設備原理 49
3-6-1 實驗儀器與設備列表 49
3-6-2 實驗儀器與設備原理 (細分成材料和電化學) 52
第四章 聚丙烯腈二氧化鈦複合電紡負極保護層 58
4-1 材料分析 58
4-1-1 材料性質鑑定 (XRD、SEM、FT-IR) 58
4-1-2 接觸角結果分析 (Contact angle test) 62
4-1-3 離子電導度分析(Ionic conductivity) 63
4-1-4 電化學穩定窗口分析 (LSV) 64
4-1-5小結 65
4-2 鋰銅半電池測試 (Li || Cu) 66
4-2-1 電化學結果分析 66
4-3 無負極鋰金屬電池 (LFP || Cu) 72
4-3-1 電化學結果分析 72
第五章 鋰電鍍原理與機制之探討 85
5-1 二氧化鈦 (TiO2) 影響電鍍行為的機制 86
5-2 無鋰金屬電池充放電機制 (三極式) 91
5-2-1 恆電流充放電測試 (Voltage Profile Analyzation) 91
5-2-2 恆電流充放電測試 (EIS Analyzation) 99
5-2-3 恆電流充放電測試 (總結論述) 106
第六章 未來工作 111
參考文獻 113

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