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研究生： 鄭兆軒
Zhao-Xuan Zheng
論文名稱： 電場誘導高導電度TiO2奈米材料高分子複合薄膜於鋰離子電池的應用
指導教授： 諸柏仁
Po-Jen Chu
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學學系
Department of Chemistry
論文出版年： 2018
畢業學年度： 106
語文別： 中文
論文頁數： 104
中文關鍵詞： 固態電解質
相關次數： 點閱：18  下載：0 
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    • 鋰離子電池是廣泛使用在電子產品當中的電池，是重要的儲能裝置之一，在發展過程中為了改善安全性及耐用性，固態高分子電解質薄膜成為重要的議題之一。固態高分子電解質雖然有許多的優點，但在離子導電性以及與電極之間的界面相容性還是比傳統的液體電解質差，因此致力於提升離子導電度以及界面相容性就成為固態高分子電解質主要發展的目標。
    在本實驗中，我們研究一款新穎的固態電解質，利用離子液體[EMIM]+[FSI]-和TiO2奈米顆粒添加到PVDF-HFP及PMMA混摻高分子薄膜中，並且在浸泡離子液體，在電場極化下，橢圓的TiO2奈米顆粒在高分子非結晶區有序地被誘導成順向，有利於離子更直接的在薄膜中傳導。此外高極性的TiO2奈米顆粒可以有效的減弱離子液體的鍵結，釋放出鋰離子提供更高的運輸程度。因此導電度在室溫下到達1.16×10-3 S/cm，在TiO2奈米顆粒添加至3%並且在80oC下導電度可到達4.52×10-3 S/cm。
    儘管此在室溫下的導電度還是不高，但是在電場極化產生的有序排列以及來自TiO2奈米顆粒高介電常數下建立了有利於離子液體傳導離子的機制，結合了電極的PvDF/PMMA黏合性能，介面電阻有顯著的下降，發現使用包含離子液體和TiO2顆粒的固態高分子電解質的鋰電池半電池以及磷酸鋰鐵作為陰極，優異且穩定的循環容量在100圈充電和放電循環後在0.2C下仍然保持在140mAh/g。

    Lithium-ion battery is an important energy storage device, widely used in electronic products. In order to improve the durability and safety, solvent free polymer electrolyte becomes one of the critical components to meet the growing challenge. Although with many promising material advantages, solid polymer electrolyte is far inferior to the liquid electrolyte in ion conductivity. A second drawback is the huge interface resistance between the electrolyte and the electrodes, due to the voids created by incomplete adhesion of the two solids.
    In this paper, we report a novel solid polymer electrolytes where ionic liquid [EMIM] + [FSI] - and TiO2 nanoparticles were impregnate with polymer blend of PVDF-HFP and PMMA. Under electric field poling, the oval shape TiO2 nano-particles is re-oriented with preferentially ordered arrangement in non-crystalline regions of the polymer blends which served to facilitate fluent ion migration induced in more straight forward manner. Furthermore, high dielectric constant of TiO2 nanoparticles weakens the ionic force within ionic liquid which liberates lithium ion for better transport. Both factors contribute to appreciable increase of ionic conductivity of 1.16 × 10 -3 S / cm at room temperature. In the composite electrolyte samples, ion conductivity of 4.52 × 10 -3 S / cm at 80 °C can be achieved with addition of 3% TiO2 nanoparticles.
    Although the mobility of the polymer is still not high at room temperature, the ordered arrangement created by E-F poling, and the high dielectric constants originated from the nano particles establishes favorable ionic liquid conduction mechanism. In combination with the superb PVDF/PMMA adhesion properties with the electrodes, the interface resistance is substantially reduced. Lithium battery half cells using the solid polymer electrolytes containing ionic liquids and TiO2 particles, with lithium iron phosphate as cathode, show stable cyclic capacity maintain at 140 mAh / g at 0.2 C discharge rate, after 100 charged and discharge cycle.

    摘要 vi Abstract vii 謝誌 ix 圖目錄 xv 表目錄 xviii 第一章 緒論 1 1-1研究背景 1 1-2鋰離子電池簡介與發展 3 1-3研究動機 7 第二章 文獻回顧 9 2-1全固態電解質 9 2-1-1全固態電解質之發展 9 2-1-2全固態電解質的種類 12 2-1-3全固態電解質的性質 14 2-1-4全固態電解質的傳導機制 16 2-1-5全固態電解質混摻系統的發展 17 2-2 PVDF-HFP及PMMA系統介紹與應用 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) 21 2-2-3 PVDF-HFP與PMMA混摻系統探討 22 2-3 離子液體 24 2-3-1離子液體簡介與特性 24 2-3-2離子液體在高分子系統內的作用 26 2-4奈米陶瓷材料性質 28 2-4-1奈米陶瓷材料發展與簡介 28 2-4-2奈米陶瓷材料的傳導機制 30 2-4-3奈米陶瓷材料高分子薄膜的應用 31 2-5外加電場的影響 32 2-5-1電場對高分子的影響 32 2-5-2電場對奈米陶瓷材料的影響 32 第三章 實驗方法 34 3-1實驗藥品與儀器 34 3-1-1實驗藥品 34 3-1-2實驗儀器 36 3-2實驗流程和操作 37 3-2-1實驗流程 37 3-2-2鈕扣型半電池的製備 39 第四章 實驗結果與討論 41 4-1電場誘導效應 42 4-2 薄膜結晶性探討 43 4-2-1 電場誘導PVDF-HFP結晶性探討 43 4-2-2 PMMA混摻系統結晶性探討 47 4-2-3離子液體添加之結晶性變化 49 4-3 TiO2添加對系統的影響 53 4-3-1 TiO2添加對薄膜構型的影響 53 4-3-2 TiO2和離子液體的作用力 58 4-3-3 TiO2在薄膜中的分散性 60 4-4薄膜性能以及導電度探討 61 4-4-1熱穩定度 61 4-4-2薄膜離子導電度探討 64 4-5半電池電性測試 67 4-5-1交流阻抗測試 67 4-5-2變速率充放電 70 4-5-3長圈數充放電 72 第五章 結論與未來展望 77 5-1結論 77 5-2未來展望 78 參考文獻 79

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