臺灣博碩士論文加值系統

本研究成功以溶膠-凝膠法合成出二氧化矽與具環氧基的二氧化矽交聯劑，並將其導入polyetherdiamine與雙酚A環氧樹脂交聯高分子系統中，製成複合高分子電解質。由掃描式電子顯微鏡、接觸角、熱重分析與線性掃描伏安法測試，可得知導入二氧化矽與具環氧基二氧化矽之複合膜，能有效提升熱穩定性、電化學穩定性及高分子與電解液的濕潤性，其熱裂解溫度約370 ℃，且電化學穩定性達4.5 V以上。從DSC的觀察可發現polyetherdiamine與二氧化矽交聯，在低於室溫16.9 ℃時產生一結晶峰；複合高分子電解質的polyetherdiamine受-OH影響，使導入環氧基二氧化矽的膠態高分子電解質之鋰離子遷移數提升至0.5，進而提升鋰離子電池3C快速放電下的電容值，保有接近118.6 mAh g-1放電電容值。而在循環壽命測試中，導入二氧化矽能夠降低電池內阻抗與穩定鋰金屬鈍化層，使0.2C/0.2C長效半電池於100次循環充放電的測試後，庫倫效率達到99%與維持159 mAh g-1放電電容值。

Synthesis of silica and silica with epoxide functional group via sol-gel method has been accomplished and characterized with FTIR and 29Si-NMR. The functional silica is added to polyetherdiamine/bisphenol A diglycidyl ether network approach to form composite polymer electrolytes based on cross-linked polyether – bisphenol A diglycidyl ether. From SEM analysis, contact angle, TGA test and LSV, we found out composite polymer electrolytes not only have great wettability, thermal and electrochemical stability up to 370 ℃ and 4.5 V (vs. Li/Li+) but also increase gel polymer electrolytes uptake and inhibit liquid electrolytes evaporation at high temperature. DSC results indicate that melting temperature of composite polymer electrolytes has crystallization peat at 16.9 ℃ which is below room temperature. Because of polyetherdiamine is sealed between functional silica. Hydroxyl group is lead to enhance lithium-ion transference number up to 0.5 on silica surface. For battery application, the half-cell specific discharge capacity of gel polymer electrolyte increase from 67.1 mAh g-1 to 118.6 mAh g-1 at 3C discharge with the addition of functional silica. Moreover, the addition of functional silica can reduce internal resistance and form steady solid electrolyte interface in half-cell. In cycle life test, it can reach 99% coulombic efficiency and keep 159 mAh g-1 capacity in 0.2C/0.2C charge-discharge rate after 100 cycles test. The above advantages of functional silica cross-linked polyetherdiamine polyelectrolytes allow it to enhance stability and performance in lithium-ion battery.

中文摘要 I
Abstract II
誌謝 XI
目錄 XII
圖目錄 XVI
表目錄 XIX

第壹章 緒論 1
1-1 簡介 1
1-2 文獻回顧 4
1-2-1 鋰離子電池基本原理 4
1-2-2導電鋰鹽 8
1-2-3塑化劑 10
1-2-4高分子電解質 12
1-2-4-1固態高分子電解質 13
1-2-4-2膠態高分子電解質 14
1-2-4-3複合式高分子電解質 15
1-2-5溶膠-凝膠法 18
1-2-6固態電解質介面膜 (Solid electrolyte interphase, SEI) 21
第貳章 研究方向 22
2-1 研究動機 22
2-2 研究架構 23
第參章 實驗 24
3-1 實驗藥品與材料 24
3-2 儀器設備 25
3-3 樣品製備 26
3-3-1 二氧化矽製備與表面改質 26
3-3-2 高分子膜製備 27
3-3-3 膠態高分子電解質製備 29
3-3-4 正極極片製作 29
3-3-5 鈕扣型電池組裝 30
3-4實驗鑑定與分析 30
3-4-1 傅立葉轉換紅外線光譜儀 (FTIR) 30
3-4-2 固態核磁共振光譜 (29Si-NMR) 31
3-4-3 環氧當量測定 (Epoxide equivalent weight, EEW) 31
3-4-4 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 33
3-4-5 穿透式電子顯微鏡 (Transmitted Electron Microscope, TEM) 34
3-4-6 接觸角量測儀 (Contact Angle Meter) 34
3-4-7 熱重分析儀 (Thermogravimetric Analysis, TGA) 35
3-4-8 微差式掃描熱卡計 (Differential Scanning Calorimetry, DSC) 35
3-4-9 交流阻抗分析 (AC impedance) 35
3-4-10 電解液吸收量 (Electrolyte uptake) 38
3-4-11 離子傳導度測量 (Ionic conductivity) 38
3-4-12 線性掃描伏安法(Linear Sweep Voltammetry, LSV) 39
3-4-13 鋰離子遷移數之量測 (Lithium ion transference number) 39
3-4-14 電池效能與長效測試方法與步驟 41
第肆章 結果與討論 42
4-1具環氧基之二氧化矽製備鑑定 42
4-1-1傅立葉轉換紅外線估光譜分析 (FTIR) 42
4-1-2 固態核磁共振光譜 (29Si NMR) 43
4-1-3 環氧當量測定 (EEW) 46
4-1-4 穿透式電子顯微鏡 (TEM) 46
4-2 含二氧化矽之高分子膜表面分析 47
4-2-1 掃描式電子顯微鏡 47
4-2-2 接觸角測量 50
4-3 熱重分析 (TGA) 51
4-4 DSC熱轉移性質 (DSC Thermal transition property) 54
4-5 電解液吸收量 (Electrolyte uptake) 55
4-6 離子傳導度 (Ionic conductivity) 56
4-7 鋰離子遷移數 (Lithium ion transference number) 59
4-8 線性掃描伏安法 (Linear scanning voltammetry) 62
4-9 半電池性能測試 63
4-9-1半電池不同放電速率測試 63
4-9-2 電壓衰退分析 (IR drop) 66
4-10 半電池長效測試 67
4-10-1 半電池長效分析 68
4-10-2 交流阻抗分析 70
4-10-3 鋰金屬表面分析 73
第伍章 結論 76
第陸章 參考文獻 77

 
圖目錄
圖 1-1 鋰離子電池與其他二次電池能量密度比較圖 2
圖1-2 鋰枝晶生成示意圖 3
圖1-3 鋰離子電池工作原理 5
圖1-4 LiFePO4橄欖石結構圖 6
圖1-5 鋰枝晶的生成過程 7
圖1-6死鋰的形成 7
圖1-7 TFSI-離域化 10
圖1-8 常見的塑化劑 12
圖1-9 鋰離子於高分子間躍遷示意圖 14
圖1-10 複合式高分子電解質傳導度圖 16
圖1-11 奈米陶瓷顆粒表面基團對鋰鹽影響示意圖 18
圖1-12 矽氧化物於不同酸鹼度時的聚合性質 21
圖2-1 研究架構圖 23
圖3-1 二氧化矽製備 26
圖3-2 具環氧基之二氧化矽製備 26
圖3-3 複合式高分子膜製備 28
圖3-4 具環氧基二氧化矽交聯型高分子膜結構 28
圖3-5 CR2032鈕扣型電池組裝圖 30
圖3-6 惰性電極/電解質/惰性電極之等效電路 39
圖3-7 惰性電極/電解質/惰性電極之理論Nyquist diagram 39
圖4-1 改質二氧化矽成分 FTIR圖譜 43
圖4-2 29Si NMR T1 T2 T3 Q1 Q2 Q3 Q4示意圖 44
圖4-3 29Si NMR圖譜 45
圖4-4 SiO2-epoxy 29Si NMR T2 T3圖譜 45
圖4-5 SiO2-epoxy 29Si NMR Q3 Q4圖譜 46
圖4-6 改質與未改質二氧化矽之TEM圖 47
圖4-7 SiO2與SiO2-epoxy粒徑大小分佈圖 47
圖4-8高分子膜表面SEM圖譜 48
圖4-9 高分子膜表面Si-Mapping 49
圖4-10 高分子膜接觸角 50
圖4-11 高分子膜之TGA圖 52
圖4-12 膠態電解質膜之TGA圖 53
圖4-13 Polyetherdiamine與高分子膜DSC圖譜 55
圖4-14 膠態高分子電解質離子傳導度圖 58
圖4-15膠態高分子電解質比離子傳導度圖 58
圖4-16 固態高分子電解質離子傳導度圖 59
圖4-17 鋰離子遷移數極化曲線與交流阻抗圖 61
圖4-18 膠態高分子電解質電化學穩定性比較 62
圖4-19 EO半電池不同速率放電電容值 64
圖4-20 SGEP10不同放電速率電容值 64
圖4-21 SGEP20半電池不同放電速率電容值 65
圖4-22 SG10半電池不同放電速率電容值 65
圖4-23 SG20半電池不同放電速率電容值 66
圖4-24 各比例高分子電解質半電池電壓衰退圖 67
圖4-25 EO半電池長效充放電電容值 68
圖4-26 SGEP10半電池長效充放電電容值 69
圖4-27 SGEP20半電池長效充放電電容值 69
圖4-28 充放電1圈後交流阻抗圖 71
圖4-29 充放電10圈後交流阻抗圖 71
圖4-30 充放電100圈後交流阻抗圖 72
圖4-31 LiFePO4/GPE/Li metal等效電路圖 72
圖4-32 長效測試後放大倍率500下鋰金屬表面SEM圖 74
圖4-33長效測試後放大倍率5000下鋰金屬表面SEM圖 75
 
表目錄
表3-1 高分子膜命名 29
表3-2 電路元件 37
表4-1 與高分子膜之熱裂解溫度 52
表4-2 膠態電解質膜之電解液保留程度 53
表4-3 高分子膜之DSC數據 55
表4-4 膠態高分子電解質之電解液吸收量 56
表4-5 膠態高分子電解質之鋰離子遷移數 61
表4-6不同高分子電解質各圈數阻抗值 72

1.J.M. Tarascon and M. Armand, Issues and challenges facing rechargeable lithium batteries. Nature 414 (6861), 359-367 (2001).
2.N. Goldenfeld, Dynamics of dendritic growth. Journal of Power Sources 26 (1–2), 121-128 (1989).
3.Z.-I. Takehara and K. Kanamura, Historical development of rechargeable lithium batteries in Japan. Electrochimica Acta 38 (9), 1169-1177 (1993).
4.J.-i. Yamaki, et al., A consideration of the morphology of electrochemically deposited lithium in an organic electrolyte. Journal of Power Sources 74 (2), 219-227 (1998).
5.M.B. Armand, Intercalation electrodes. Materials for Advanced Batteries. Proceedings of a NATO Symposium on Materials for Advanced Batteries, 145-161 (1980).
6.U. von Sacken, et al., Comparative thermal stability of carbon intercalation anodes and lithium metal anodes for rechargeable lithium batteries. Solid State Ionics 69 (3–4), 284-290 (1994).
7.B. Dunn, H. Kamath, and J.-M. Tarascon, Electrical Energy Storage for the Grid: A Battery of Choices. Science 334 (6058), 928-935 (2011).
8.A.K. Padhi, K.S. Nanjundaswamy, and J.B. Goodenough, Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries. Journal of The Electrochemical Society 144 (4), 1188-1194 (1997).
9.S.-Y. Chung, J.T. Bloking, and Y.-M. Chiang, Electronically conductive phospho-olivines as lithium storage electrodes. Nat Mater 1 (2), 123-128 (2002).
10.S. Yang, et al., Performance of LiFePO4 as lithium battery cathode and comparison with manganese and vanadium oxides. Journal of Power Sources 119–121 (0), 239-246 (2003).
11.C. Julien, et al., Comparative Issues of Cathode Materials for Li-Ion Batteries. Inorganics 2 (1), 132-154 (2014).
12.G. Bieker, M. Winter, and P. Bieker, Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode. Physical Chemistry Chemical Physics 17 (14), 8670-8679 (2015).
13.J.O. Besenhard, The electrochemical preparation and properties of ionic alkali metal-and NR4-graphite intercalation compounds in organic electrolytes. Carbon 14 (2), 111-115 (1976).
14.S. Basu, et al., Synthesis and properties of lithium-graphite intercalation compounds. Materials Science and Engineering 38 (3), 275-283 (1979).
15.D. Guérard and H. Fuzellier, The Graphite Intercalation Compounds and their Applications, in Condensed Systems of Low Dimensionality, J.L. Beeby, et al., Editors. 1991, Springer US. p. 695-707.
16.V. Aravindan, et al., Lithium-Ion Conducting Electrolyte Salts for Lithium Batteries. Chemistry – A European Journal 17 (51), 14326-14346 (2011).
17.J.M. Tarascon and D. Guyomard, New electrolyte compositions stable over the 0 to 5 V voltage range and compatible with the Li1+xMn2O4/carbon Li-ion cells. Solid State Ionics 69 (3–4), 293-305 (1994).
18.G.H. Newman, et al., Hazard Investigations of LiClO4 / Dioxolane Electrolyte. Journal of The Electrochemical Society 127 (9), 2025-2027 (1980).
19.H. Yang, G.V. Zhuang, and P.N. Ross Jr, Thermal stability of LiPF6 salt and Li-ion battery electrolytes containing LiPF6. Journal of Power Sources 161 (1), 573-579 (2006).
20.C.W. Walker, J.D. Cox, and M. Salomon, Conductivity and Electrochemical Stability of Electrolytes Containing Organic Solvent Mixtures with Lithium tris(Trifluoromethanesulfonyl)methide. Journal of The Electrochemical Society 143 (4), L80-L82 (1996).
21.B. Markovsky, et al., On the Electrochemical Behavior of Aluminum Electrodes in Nonaqueous Electrolyte Solutions of Lithium Salts. Journal of The Electrochemical Society 157 (4), A423-A429 (2010).
22.V. Etacheri, et al., Challenges in the development of advanced Li-ion batteries: a review. Energy ＆ Environmental Science 4 (9), 3243-3262 (2011).
23.Y. Yamada, et al., Unusual Stability of Acetonitrile-Based Superconcentrated Electrolytes for Fast-Charging Lithium-Ion Batteries. Journal of the American Chemical Society 136 (13), 5039-5046 (2014).
24.J.B. Goodenough and Y. Kim, Challenges for Rechargeable Li Batteries. Chemistry of Materials 22 (3), 587-603 (2010).
25.A. Manthiram, Materials Challenges and Opportunities of Lithium Ion Batteries. The Journal of Physical Chemistry Letters 2 (3), 176-184 (2011).
26.K. Xu, Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries. Chemical Reviews 104 (10), 4303-4418 (2004).
27.C. Berthier, et al., Microscopic investigation of ionic conductivity in alkali metal salts-poly(ethylene oxide) adducts. Solid State Ionics 11 (1), 91-95 (1983).
28.D.E. Fenton, J.M. Parker, and P.V. Wright, Complexes of alkali metal ions with poly(ethylene oxide). Polymer 14 (11), 589 (1973).
29.D. Bresser, S. Passerini, and B. Scrosati, Recent progress and remaining challenges in sulfur-based lithium secondary batteries - a review. Chemical Communications 49 (90), 10545-10562 (2013).
30.G. Feuillade and P. Perche, Ion-conductive macromolecular gels and membranes for solid lithium cells. Journal of Applied Electrochemistry 5 (1), 63-69 (1975).
31.J.E. Weston and B.C.H. Steele, Effects of inert fillers on the mechanical and electrochemical properties of lithium salt-poly(ethylene oxide) polymer electrolytes. Solid State Ionics 7 (1), 75-79 (1982).
32.J. Zhou and P.S. Fedkiw, Ionic conductivity of composite electrolytes based on oligo(ethylene oxide) and fumed oxides. Solid State Ionics 166 (3–4), 275-293 (2004).
33.F. Capuano, F. Croce, and B. Scrosati, Composite Polymer Electrolytes. Journal of The Electrochemical Society 138 (7), 1918-1922 (1991).
34.N.S.T. Do, et al., Influence of Fe2O3 Nanofiller Shape on the Conductivity and Thermal Properties of Solid Polymer Electrolytes: Nanorods versus Nanospheres. The Journal of Physical Chemistry C 116 (40), 21216-21223 (2012).
35.F. Croce, et al., Physical and Chemical Properties of Nanocomposite Polymer Electrolytes. The Journal of Physical Chemistry B 103 (48), 10632-10638 (1999).
36.F. Croce, et al., Role of the ceramic fillers in enhancing the transport properties of composite polymer electrolytes. Electrochimica Acta 46 (16), 2457-2461 (2001).
37.P.A.R.D. Jayathilaka, et al., Effect of nano-porous Al2O3 on thermal, dielectric and transport properties of the (PEO)9LiTFSI polymer electrolyte system. Electrochimica Acta 47 (20), 3257-3268 (2002).
38.F. Croce, L. Settimi, and B. Scrosati, Superacid ZrO2-added, composite polymer electrolytes with improved transport properties. Electrochemistry Communications 8 (2), 364-368 (2006).
39.K.S. Korf, et al., Piperidinium tethered nanoparticle-hybrid electrolyte for lithium metal batteries. Journal of Materials Chemistry A 2 (30), 11866-11873 (2014).
40.Y. Lu, et al., Ionic liquid-nanoparticle hybrid electrolytes. Journal of Materials Chemistry 22 (9), 4066-4072 (2012).
41.Y. Dai, et al., Electrical, thermal and NMR investigation of composite solid electrolytes based on PEO, LiI and high surface area inorganic oxides. Electrochimica Acta 43 (10–11), 1557-1561 (1998).
42.C.J. Brinker, Hydrolysis and condensation of silicates: Effects on structure. Journal of Non-Crystalline Solids 100 (1–3), 31-50 (1988).
43.R.K. Iler, The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties and Biochemistry of Silica. (1979).
44.E. Peled, The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model. Journal of The Electrochemical Society 126 (12), 2047-2051 (1979).
45.S. Rodrigues, N. Munichandraiah, and A.K. Shukla, AC impedance and state-of-charge analysis of a sealed lithium-ion rechargeable battery. Journal of Solid State Electrochemistry 3 (7-8), 397-405 (1999).
46.G.J. Brug, et al., The analysis of electrode impedances complicated by the presence of a constant phase element. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry 176 (1–2), 275-295 (1984).
47.D. Aurbach, Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries. Journal of Power Sources 89 (2), 206-218 (2000).
48.P.G. Bruce, Solid State Electrochemistry, ed. B. Dunn, J. Goodby, and A.R. West. 1995: CAMBRIDGE UNIVERSITY PRESS.
49.G.G. Cameron, Polymer electrolyte reviews-l edited by J. R. MacCallum and C. A. Vincent, Elsevier Applied Science Publishers, London, 1987. pp. x + 351, price £48.00. ISBN 1-85166-07 1-2. British Polymer Journal 20 (3), 299-300 (1988).
50.J. Evans, C.A. Vincent, and P.G. Bruce, Electrochemical measurement of transference numbers in polymer electrolytes. Polymer 28 (13), 2324-2328 (1987).
51.C. Schramm, W.H. Binder, and R. Tessadri, Durable Press Finishing of Cotton Fabric with 1,2,3,4-Butanetetracarboxylic Acid and TEOS/GPTMS. Journal of Sol-Gel Science and Technology 29 (3), 155-165 (2004).
52.M. Feng and H. Zhan, Facile preparation of transparent and dense CdS-silica gel glass nanocomposites for optical limiting applications. Nanoscale 6 (8), 3972-3977 (2014).
53.T.-H. Liou and C.-C. Yang, Synthesis and surface characteristics of nanosilica produced from alkali-extracted rice husk ash. Materials Science and Engineering: B 176 (7), 521-529 (2011).
54.S.R. Davis, A.R. Brough, and A. Atkinson, Formation of silica/epoxy hybrid network polymers. Journal of Non-Crystalline Solids 315 (1–2), 197-205 (2003).
55.M.G. da Fonseca and C. Airoldi, New layered inorganic-organic nanocomposites containing n-propylmercapto copper phyllosilicates. Journal of Materials Chemistry 10 (6), 1457-1463 (2000).
56.G. Ye, C.A. Hayden, and G.R. Goward, Proton Dynamics of Nafion and Nafion/SiO2 Composites by Solid State NMR and Pulse Field Gradient NMR. Macromolecules 40 (5), 1529-1537 (2007).
57.F. Babonneau, K. Thorne, and J.D. Mackenzie, Dimethyldiethoxysilane/tetraethoxysilane copolymers: precursors for the silicon-carbon-oxygen system. Chemistry of Materials 1 (5), 554-558 (1989).
58.F. Yagihashi, et al., Semiconductor interlayer-insulating film forming composition, preparation method thereof, film forming method, and semiconductor device. 2008, Google Patents.
59.L. Chen, et al., Enhanced Epoxy/Silica Composites Mechanical Properties by Introducing Graphene Oxide to the Interface. ACS Applied Materials ＆ Interfaces 4 (8), 4398-4404 (2012).
60.S. Zhang, J.Y. Lee, and L. Hong, Li+ conducting ‘fuzzy’ poly(ethylene oxide)–SiO2 polymer composite electrolytes. Journal of Power Sources 134 (1), 95-102 (2004).
61.Y. Liu, J.Y. Lee, and L. Hong, In situ preparation of poly(ethylene oxide)–SiO2 composite polymer electrolytes. Journal of Power Sources 129 (2), 303-311 (2004).
62.M.M. Hiller, et al., Salt-In-Polymer Electrolytes Based on Polysiloxanes for Lithium-Ion Cells: Ionic Transport and Electrochemical Stability. ECS Transactions 33 (28), 3-15 (2011).
63.H.C. Shin, W.I. Cho, and H. Jang, Electrochemical properties of the carbon-coated LiFePO4 as a cathode material for lithium-ion secondary batteries. Journal of Power Sources 159 (2), 1383-1388 (2006).
64.J.P. Schmidt, et al., Studies on LiFePO4 as cathode material using impedance spectroscopy. Journal of Power Sources 196 (12), 5342-5348 (2011).