為解決鋰離子電池中具揮發性及可燃性之有機電解液安全上的問題，使用固態電解質是目前鋰離子電池研究的目標。本研究致力於設計具有高能量密度，長循環壽命且安全性更高的鋰離子固態全電池。我們利用高分子聚乙二醇以及鋰鑭鋯鉈氧化物之複合材料作為固態電解質，其離子傳導率可達1.58 × 10－３ S cm－1。此外亦比較其與液態電解液在電性量測上的結果，皆顯示此複合電解質具有優良性質。隨著陶瓷氧化物在固態複合電解質中的比例增加，由熱重及熱差分析結果可觀察到熱穩定性提高，克服傳統有機電解液在安全上的疑慮。在鋰離子全電池電極部分，我們使用磷酸鋰鐵LiFePO4與富鋰之鋰鐵氧化物Li5FeO4混合物作為正極。Li5FeO4是一種惰性活物 (inactive material)，在初始充電過程中釋出大量鋰離子並提供785 mA h g-1之不可逆電容量，故藉由添加Li5FeO4，可彌補第一次充放電庫倫效率較低之負極材料在起始充放電時所產生之不可逆損失，進而得到具有高能量密度，長循環壽命且具高安全性的鋰離子電池。

In order to solve the safety issue of organic liquid electrolyte, many of the ionic battery researchers dedicated to replacing the volatile and flammable liquid electrolytes with solid-state electrolytes, which possess much higher stability. In this research, we devoted to developing a solid-state lithium ion battery that exhibited high energy density, long cycle stability, and high safety. For the electrolyte, we combined polymer poly(ethylene oxide) (PEO) and ceramic Li6.4La3Zr1.4Ta0.6O12 (LLZTO) to serve as ionic conductive solid electrolyte. The ionic conductivity could reach up to 1.58 × 10－３ S cm－1. Also, we conducted several material characterizations and electrochemical tests to compare composite solid electrolyte and organic liquid electrolyte. The result demonstrated that the PEO/LLZTO composite is an promising solid electrolyte for lithium ion batteries. Besides, thermogravimetric analysis and differential thermal analysis showed that the thermal stability was enhanced via increasing the content of LLZTO in the composite membrane. As for electrodes, LiFePO4 (LFP) incorporated with Li5FeO4 (LFO) was used as cathode material. LFO is an inactive material, it can release lot amounts of Li+ during the first charging process, exhibits capability of 785 mA h g-1. The released Li+ from LFO can compensate the irreversible capacity loss during solid electrolyte interface (SEI) formation, leading to the possibility of higher capacity and longer cycle life. With the innovative design of these components, the high energy density, long cycle life, and high safety solid-state lithium-ion battery can be obtained.

摘要 i
Abstract ii
致謝 iv
目錄 vi
圖目錄 xi
表目錄 xiv

第一章 緒論.....................1

第二章 文獻回顧及原理簡介........4
2.1 固態鋰離子電池介紹........4
2.2 鋰離子固態電解質之介紹....5
2.2.1 鋰離子陶瓷固態電解質......5
2.2.2 高分子固態/膠態電解質.....9
2.2.3 複合固態電解質...........11
2.3 交流阻抗之分析原理........11
2.4 鋰離子電池電極材料........14
2.4.1 鋰離子電池正極材料........14
2.4.2 富鋰之鋰鐵氧化物..........16

第三章 實驗步驟與研究方法........19
3.1 實驗架構 .................19
3.2 複合固態電解質膜之製備.....20
3.3 鋰離子電池正極.............22
3.3.1 Li5FeO4之合成.............22
3.3.2 正極LiFePO4/Li5FeO4之極片製作.....22
3.4 鈕扣電池之組裝.............23
3.5 材料特性分析...............25
3.5.1 X光繞射分析 (X-Ray Diffraction, XRD)......25
3.5.2 場發掃描式電子顯微鏡........25
3.5.3 熱重分析...................26
3.6 -材料電化學性質量測方法......27
3.6.1 交流阻抗分析................27
3.6.2 循環伏安法.................28
3.6.3 恆電流充放電...............29
3.6.4 線性掃描伏安法.............30

第四章 結果與討論.................32
4.1 固態電解質之性質分析........32
4.1.1 交流阻抗分析...............32
4.1.2 熱重分析...................34
4.1.3 掃描式電子顯微鏡影像........37
4.1.4 X光結晶繞射圖譜.............38
4.1.5 LSV........................39
4.1.6 40 wt% LLZTO/PEO膠態電解質之半電池測試.....41
4.1.6.1循環伏安法..................41
4.1.6.2恆電流充放電................42
4.2 LFO合成以及性質分析.........44
4.2.1 XRD圖譜分析................45
4.2.2 LFO充放電測試...............45
4.3 LFP+LFO正極與{Mo72V30}負極全電池之電性表現.....49
4.3.1 LiFePO4/LFO半電池...........49
4.3.2 {Mo72V30}半電池充放電測試....52
4.3.3 LiFePO4/LFO//{Mo72V30}液態全電池......54
4.3.4 固態全電池...................57

第五章 結論........................60

參考文獻............................63

1. Moosbauer D, Zugmann S, Amereller M, Gores HJ. Effect of ionic liquids as additives on lithium electrolytes: conductivity, electrochemical stability, and aluminum corrosion. Journal of Chemical & Engineering Data, 55 (5): 1794-1798; 2010.
2. Wang Y, Zhong WH. Development of Electrolytes towards Achieving Safe and High‐Performance Energy‐Storage Devices: A Review. ChemElectroChem, 2 (1): 22-36; 2015.
3. Stephan AM. Review on gel polymer electrolytes for lithium batteries. European polymer journal, 42 (1): 21-42; 2006.
4. Zhang SS. A review on electrolyte additives for lithium-ion batteries. Journal of Power Sources, 162 (2): 1379-1394; 2006.
5. Reddy MJ, Kumar JS, Rao US, Chu PP. Structural and ionic conductivity of PEO blend PEG solid polymer electrolyte. Solid state ionics, 177 (3-4): 253-256; 2006.
6. Tao C, Gao M-H, Yin B-H, Li B, Huang Y-P, Xu G, Bao J-J. A promising TPU/PEO blend polymer electrolyte for all-solid-state lithium ion batteries. Electrochimica Acta, 257: 31-39; 2017.
7. Ma Q, Zhang H, Zhou C, Zheng L, Cheng P, Nie J, Feng W, Hu YS, Li H, Huang X. Single lithium‐ion conducting polymer electrolytes based on a super‐delocalized polyanion. Angewandte Chemie International Edition, 55 (7): 2521-2525; 2016.
8. Liang S, Yan W, Wu X, Zhang Y, Zhu Y, Wang H, Wu Y. Gel polymer electrolytes for lithium ion batteries: Fabrication, characterization and performance. Solid State Ionics, 318: 2-18; 2017.
9. Zheng F, Kotobuki M, Song S, Lai MO, Lu L. Review on solid electrolytes for all-solid-state lithium-ion batteries. Journal of Power Sources, 389: 198-213; 2018.
10. Dokko K, Hoshina K, Nakano H, Kanamura K. Preparation of LiMn2O4 thin-film electrode on Li1+xAlxTi2−x(PO4)3 NASICON-type solid electrolyte. Journal of Power Sources, 174 (2): 1100-1103; 2007.
11. Ren Y, Chen K, Chen R, Liu T, Zhang Y, Nan CW. Oxide electrolytes for lithium batteries. Journal of the American Ceramic Society, 98 (12): 3603-3623; 2015.
12. Aatiq A, Ménétrier M, Croguennec L, Suard E, Delmas C. On the structure of Li3Ti2(PO4)3. Journal of Materials Chemistry, 12 (10): 2971-2978; 2002.
13. Fu J. Fast Li+ ion conducting glass-ceramics in the system Li2O–Al2O3–GeO2–P2O5. Solid State Ionics, 104 (3-4): 191-194; 1997.
14. Xu X, Wen Z, Wu X, Yang X, Gu Z. Lithium Ion‐Conducting Glass–Ceramics of Li1.5Al0.5Ge1.5(PO4)3–xLi2O (x= 0.0–0.20) with Good Electrical and Electrochemical Properties. Journal of the American Ceramic Society, 90 (9): 2802-2806; 2007.
15. Sebastian L, Gopalakrishnan J. Lithium ion mobility in metal oxides: a materials chemistry perspective. Journal of materials chemistry, 13 (3): 433-441; 2003.
16. Suzuki N, Inaba T, Shiga T. Electrochemical properties of LiPON films made from a mixed powder target of Li3PO4 and Li2O. Thin Solid Films, 520 (6): 1821-1825; 2012.
17. Li G, Li M, Dong L, Li X, Li D. Low energy ion beam assisted deposition of controllable solid state electrolyte LiPON with increased mechanical properties and ionic conductivity. International Journal of Hydrogen Energy, 39 (30): 17466-17472; 2014.
18. Su Y, Falgenhauer J, Polity A, Leichtweiß T, Kronenberger A, Obel J, Zhou S, Schlettwein D, Janek J, Meyer BK. LiPON thin films with high nitrogen content for application in lithium batteries and electrochromic devices prepared by RF magnetron sputtering. Solid State Ionics, 282: 63-69; 2015.
19. Chen C, Amine K. Ionic conductivity, lithium insertion and extraction of lanthanum lithium titanate. Solid State Ionics, 144 (1-2): 51-57; 2001.
20. Zhao Y, Daemen LL. Superionic conductivity in lithium-rich anti-perovskites. Journal of the American Chemical Society, 134 (36): 15042-15047; 2012.
21. Braga M, Ferreira JA, Stockhausen V, Oliveira J, El-Azab A. Novel Li 3 ClO based glasses with superionic properties for lithium batteries. Journal of Materials Chemistry A, 2 (15): 5470-5480; 2014.
22. Murugan R, Thangadurai V, Weppner W. Fast lithium ion conduction in garnet‐type Li7La3Zr2O12. Angewandte Chemie International Edition, 46 (41): 7778-7781; 2007.
23. Ohta S, Kobayashi T, Asaoka T. High lithium ionic conductivity in the garnet-type oxide Li7− X La3 (Zr2− X, NbX) O12 (X= 0–2). Journal of Power Sources, 196 (6): 3342-3345; 2011.
24. Murugan R, Ramakumar S, Janani N. High conductive yttrium doped Li7La3Zr2O12 cubic lithium garnet. Electrochemistry Communications, 13 (12): 1373-1375; 2011.
25. Li Y, Han J-T, Wang C-A, Xie H, Goodenough JB. Optimizing Li+ conductivity in a garnet framework. Journal of Materials Chemistry, 22 (30): 15357-15361; 2012.
26. Larraz G, Orera A, Sanjuan M. Cubic phases of garnet-type Li7La3Zr2O12: the role of hydration. Journal of Materials Chemistry A, 1 (37): 11419-11428; 2013.
27. Xia W, Xu B, Duan H, Tang X, Guo Y, Kang H, Li H, Liu H. Reaction mechanisms of lithium garnet pellets in ambient air: The effect of humidity and CO2. Journal of the American Ceramic Society, 100 (7): 2832-2839; 2017.
28. Okumura T, Shikano M, Kobayashi H. Effect of bulk and surface structural changes in Li5FeO4 positive electrodes during first charging on subsequent lithium-ion battery performance. Journal of Materials Chemistry A, 2 (30): 11847-11856; 2014.
29. Aono H, Imanaka N, Adachi G-y. High Li+ conducting ceramics. Accounts of Chemical Research, 27 (9): 265-270; 1994.
30. Aziz SB, Abidin ZHZ. Ion-transport study in nanocomposite solid polymer electrolytes based on chitosan: Electrical and dielectric analysis. Journal of Applied Polymer Science, 132 (15): 2015.
31. Kumar M, Sekhon S. Role of plasticizer's dielectric constant on conductivity modification of PEO–NH4F polymer electrolytes. European Polymer Journal, 38 (7): 1297-1304; 2002.
32. Harvey S, Baidwan J. Thyrotrophin-releasing hormone (TRH)-induced growth hormone secretion in fowl: binding of TRH to pituitary membranes. Journal of Molecular Endocrinology, 3 (1): 23-32; 1989.
33. Mohapatra SR, Thakur AK, Choudhary R. Effect of nanoscopic confinement on improvement in ion conduction and stability properties of an intercalated polymer nanocomposite electrolyte for energy storage applications. Journal of Power Sources, 191 (2): 601-613; 2009.
34. Xu K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chemical reviews, 104 (10): 4303-4418; 2004.
35. Kontos G, Soulintzis A, Karahaliou P, Psarras G, Georga S, Krontiras C, Pisanias M. Electrical relaxation dynamics in TiO2-polymer matrix composites. Express Polymer Letters, 1 (12): 781-9; 2007.
36. Wan Z, Lei D, Yang W, Liu C, Shi K, Hao X, Shen L, Lv W, Li B, Yang QH. Low Resistance–Integrated All‐Solid‐State Battery Achieved by Li7La3Zr2O12 Nanowire Upgrading Polyethylene Oxide (PEO) Composite Electrolyte and PEO Cathode Binder. Advanced Functional Materials, 29 (1): 1805301; 2019.
37. Chang B-Y, Park S-M. Electrochemical impedance spectroscopy. Annual Review of Analytical Chemistry, 3: 207-229; 2010.
38. Prosini PP, Zane D, Pasquali M. Improved electrochemical performance of a LiFePO4-based composite cathode. Electrochimica Acta, 46 (23): 3517-3523; 2001.
39. Padhi AK, Nanjundaswamy KS, Goodenough JB. Phospho‐olivines as positive‐electrode materials for rechargeable lithium batteries. Journal of the Electrochemical Society, 144 (4): 1188-1194; 1997.
40. Huang H, Yin S-C, Nazar Ls. Approaching theoretical capacity of LiFePO4 at room temperature at high rates. Electrochemical and Solid-State Letters, 4 (10): A170-A172; 2001.
41. Xu Y-N, Chung S-Y, Bloking JT, Chiang Y-M, Ching W. Electronic structure and electrical conductivity of undoped LiFePO4. Electrochemical and Solid-State Letters, 7 (6): A131-A134; 2004.
42. Industrial Technology Research Institute (ITRI). .
43. Thackeray MM, Kang S-H, Johnson CS, Vaughey JT, Benedek R, Hackney S. Li2MnO3-stabilized LiMO2 (M= Mn, Ni, Co) electrodes for lithium-ion batteries. Journal of Materials chemistry, 17 (30): 3112-3125; 2007.
44. Johnson C, Kang S-H, Vaughey J, Pol S, Balasubramanian M, Thackeray M. Li2O removal from Li5FeO4: A cathode precursor for lithium-ion batteries. Chemistry of Materials, 22 (3): 1263-1270; 2010.
45. Park MS, Lim YG, Hwang SM, Kim JH, Kim JS, Dou SX, Cho J, Kim YJ. Scalable Integration of Li5FeO4 towards Robust, High‐Performance Lithium‐Ion Hybrid Capacitors. ChemSusChem, 7 (11): 3138-3144; 2014.
46. Park MS, Lim YG, Kim JH, Kim YJ, Cho J, Kim JS. A Novel Lithium‐Doping Approach for an Advanced Lithium Ion Capacitor. Advanced Energy Materials, 1 (6): 1002-1006; 2011.
47. Park M-S, Lim Y-G, Park J-W, Kim J-S, Lee J-W, Kim JH, Dou SX, Kim Y-J. Li2RuO3 as an additive for high-energy lithium-ion capacitors. The Journal of Physical Chemistry C, 117 (22): 11471-11478; 2013.
48. Liang L, Luo J, Chen M, Wang L, Li J, He X. Synthesis and characterization of novel cathode material Li5FeO4 for Li-ion batteries. International Journal of Electrochemical Science, 8: 6393-6398; 2013.
49. Choi N-S, Yew KH, Lee KY, Sung M, Kim H, Kim S-S. Effect of fluoroethylene carbonate additive on interfacial properties of silicon thin-film electrode. Journal of Power Sources, 161 (2): 1254-1259; 2006.