臺灣博碩士論文加值系統

本實驗第一部分，使用旋轉塗佈法製備固態電解質，此方法的優點為控制其薄膜的厚度、增加Li+ 的擴散通道，使Li+ 更加地容易傳送。固態電解質是由PEO、LiTFSI、Ga-doped LLZO混合而成的，而我們嘗試尋找旋轉塗佈法的最佳參數: 轉速1000 rpm、時間60秒、每滴溶劑150 μL、層數15層。而隨著固態電解質的濃度增加，可以有效地抑制電壓的抖動，故電解質的最佳比例則是PEO: LiTFSI : LLZO = 1:1:2。
我們沿用第一部分的最佳參數，第二部分則是比較五種LLZO製備固態電解質應用於鋰離子電池，而與其它種類的LLZO相比，Li6.25Ga0.25La3Zr2O12有最好的電化學性質，其0.1C下電容值約有120 mAh/g，庫倫效率約有97%，且發現粒徑大小會部分影響電化學性質，因為在固態電解質Li+ 傾向於在 LLZO 相中傳遞，所以我們降低固態電解質中的粒徑大小，便能夠使Li+ 更加容易地穿透，進而造成電化學性質提高。我們選擇填充物Al2O3取代LLZO，但卻得到很差的電化學性質，這邊推測為高分子主鏈運動不易，導致導電度不佳，故結過顯示填充物無法取代LLZO，固態電解質是必要的存在。
實驗第三部分，我們加入離子液體在固態電解質和鋰金屬之間，藉此降低其界面阻抗，並選擇三種不同摻雜的LLZO比較其電化學性質，而Li6.25Ga0.25La3Zr2O12加入離子液體1M LiTFSI/PMPTFSI有最好的電化學性質，其0.1C下電容值約有148 mAh/g，庫倫效率約有97%。以0.5C下作200圈循環壽命測試，維持率高達96% (137.48/143.21 mAh/g, 200th/1st )。

A single-phase Li7La3Zr2O12 (LLZO) solid electrolyte is synthesized using a solid-state reaction method. The influences of doping elements (Ga, Ta, and Mg) on the properties of LLZO are investigated. In addition, a hybrid electrolyte, composed of Ga-doped (or Ta-doped) LLZO, LiTFSI, and poly(ethylene oxide) was prepared, using the spin coating method. The LLZO/LiTFSI/PEO ratio of slurry and number of layers were changed to compare their electrochemical properties. As compared to LLZO pellet electrolyte, the hybrid electrolyte shows a higher ionic conductivity and a better charge-discharge performance in Li/LiFePO4 cells.
We compare different kinds of LLZO and find out that Li6.25Ga0.25La3Zr2O12 has the best electrochemical properties. The charge is about 120 mAh/g and coulombic efficiency is also 97%. It was found that the particle size will affect the electrochemical performance. The Li+ ion tends to pass through the LLZO phase in the solid electrolyte, by reducing the particle size Li+ ion can penetrate more easily.
The huge interface impedance still possesses a great challenge toward a better performance. We add the ionic liquid between the solid electrolyte and lithium metal to decrease the interface impedance. Li6.25Ga0.25La3Zr2O12-1M LiTFSI/PMPTFSI demonstrates good charge and discharge performance.The charge reaches up to 148 mAh/g and coulombic efficiency is also 97 %. The cycle retention at 0.5C is about 96% during the 200 cycles.

摘要 i
Abstract ii
誌謝 iii
總目錄 iv
圖目錄 viii
表目錄 xiv
第一章 緒論 1
1-1 研究背景 1
1-2 研究動機 2
第二章　文獻回顧 4
2-1 固態電解質 4
2-1-1傳導機制 4
2-1-2混合型的固態電解質 6
2-1-2-1 Polymer/Liquid Hybrid Electrolytes with Organic Liquids 6
2-1-2-2 Polymer/Liquid Hybrid Electrolytes with Ionic Liquids 9
2-1-2-3 Polymer/Polymer Coordinating Electrolytes 11
2-1-2-4 Polymer/Inorganic Composite Electrolytes 16
2-1-3固態陶瓷電解質結構 28
2-2 Li7La3Zr2O12 的發展與應用 30
2-2-1 Li7La3Zr2O12 分析 30
2-2-2 Li7La3Zr2O12 不同元素摻雜 34
2-3 Li7La3Zr2O12 應用於鋰電池 41
2-3-1錠狀(pellet)固態電解質 41
2-3-2混合的固態電解質(hybrid) 45
第三章　實驗方法與步驟 60
3-1 實驗藥品及材料 60
3-2 電池製備 63
3-2-1 工作電極塗佈 63
3-2-2 固態電解質薄膜製備 63
3-2-3 電解液的配置 64
3-2-4鈕扣型電池製備 64
3-3材料分析與鑑定 65
3-3-1 X光繞射分析 (X-ray diffraction，XRD) 65
3-3-2場發式掃描電子顯微鏡 (Field Emission Gun Scanning Electron Microscope, FEI, Inspect F50) 65
3-3-3 動態光散射粒徑分析儀 (Dynamic Light Scattering) 65
3-3-4線性掃描伏安法 (Linear scan voltammetry) 65
3-3-5連續循環充放電測試 (Charge and Discharge Test) 66
3-3-6交流阻抗 (electrochemical impedance spectroscopy, EIS) 66
第四章　結果與討論 67
4-1旋轉塗佈法(spin coating)的最佳參數 67
4-1-1 LiPF6-EC/DEC的基本性質 67
4-1-2 Spin coating 電解質的比例 72
4-2摻雜不同元素Li7La3Zr2O12的比較 80
4-2-1 摻雜不同元素Li7La3Zr2O12的基本性質 80
4-2-2 摻雜不同元素Li7La3Zr2O12的電化學性質 84
4-3固態電解質加入離子液體對電池性能的影響 99
4-3-1離子液體的基本性質 99
4-3-2 Li7La3Zr2O12 加入離子液體的電池性能 107
第五章 結論 125
第六章 附錄 126
第七章 參考文獻 129

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106 Yali Luo, Xueyan Li, Electrochemical Properties and Structural Stability of Ga- and Y- co-doping in Li7La3Zr2O12 Ceramic Electrolytes for Lithium-ion Batteries. Accepted Manuscript, 2019.

107. Maoyi Yi, Tao Liu, Xiangnan Wang, Jingyun Li, High densification and Li-ion conductivity of Al-free Li7-xLa3Zr2-xTaxO12 garnet solid electrolyte prepared by using ultrafine powders. Accepted Manuscript, 2019.
108. Yang Li, Wei Zhang, Qianqian Dou, Ka Wai Wong and Ka Ming Ng, Li7La3Zr2O12 ceramic nanofiber-incorporated composite polymer electrolytes for lithium metal batteries. Journal of Materials Chemistry A,2019.
109. Da Hye Kim, Min Young Kim, Fabrication and Electrochemical Characteristics of NCM-Based All-Solid Lithium Batteries using Nano-grade Garnet Al-LLZO Powder. Accepted Manuscript, 2019.
110. Zeya Huang, Wanying Pang, A dopamine modified Li6.4La3Zr1.4Ta0.6O12 /PEO solid-state electrolyte: enhanced thermal and electrochemical properties. Journal of Materials Chemistry A,2019.