臺灣博碩士論文加值系統

　　本研究論文將以 PVDF/PAN/TPU 與 PVDF/PAN/PS 三成分組成，利用靜電紡絲法 (Electrospinning) 製備膠態高分子電解質 (Gel polymer electrolyte, GPE)。利用傳統實驗法製備三成分膠態高分子電解質並且探討其吸液率、離子電導率 (Ionic conductivity, σ) 、分解電壓與機械性質，再利用混合物實驗法配合 SAS 統計分析探討 PVDF/PAN/TPU 與 PVDF/PAN/PS 系統的最佳組成；並將其組成無陽極半電池，探討其充放電性質。
　　在傳統實驗法中，找出三成分各自的上限值後，改變 PVDF/PAN/TPU 與 PVDF/PAN/PS 的組成比例，製備膠態高分子電解質，利用交流阻抗 (AC impedance) 分析量測離子電導率。結果發現 PVDF/PAN/TPU 與 PVDF/PAN/PS 組成皆為 0.2 / 0.6 / 0.2 時，，具有最佳的離子電導率，分別為 3.52 × 10-3 與 3.89 × 10-3 S cm-1。
　　利用具成分上限之混合物實驗設計法，配合統計分析，探討分別以離子電導率、分解電壓與機械應力為回應值之最佳組成，實驗結果發現 PVDF/PAN/TPU 膠態高分子電解質，以離子電導率為回應值與擬成分間之關係式為 y = 3.010 u1 + 3.000 u2 + 3.712 u3 + 4.481 u1u2 – 4.181 u1u3 + 45.51 u1u2u3，其中 u1、u2 與 u3 各為 PVDF、PAN 與 TPU 之擬組成。而 PVDF/PAN/PS 膠態高分子電解質，以離子電導率為回應值與擬成分間之關係式為 y = 2.478 u1 + 3.977 u2 + 3.284 u3 + 3.368 u1u2 – 5.137 u2u3 – 26.40 u1u2u3 ，其中 u1、u2 與 u3 各為 PVDF、PAN 與 PS 之擬組成。在 PVDF/PAN/TPU 膠態高分子電解質中，具最佳離子電導率為 4.94 × 10-3 S cm-1 之組成為 0.232 / 0.621 / 0.147；而以混合物實驗法製備的最佳 PVDF/PAN/PS 膠態高分子電解質中，具最佳離子電導率為 4.07 × 10-3 S cm-1 之組成為 0.245 / 0.555 / 0.200。
　　以最佳組成的 PVDF/PAN/TPU 與 PVDF/PAN/PS 膠態高分子電解質，組裝為 Cu foil / PVDF/PAN/TPU(膜厚 = 0.300 mm) / Li 與 Cu foil / PVDF/PAN/PS (膜厚 = 0.300 mm) / Li 電池的最佳庫侖效率皆為 95.63 %，持續充放電至第 50 圈時之庫侖效率則分別為 84.51 與 83.10 %，而充放電循環壽命分別為 259 與 161 圈。將銅箔更換為泡沫銅後，兩半電池的最佳庫侖效率分別為 94.58 與 95.49 %，在第 50 圈時之庫侖效率則分別為 87.74 與 86.77%，而充放電循環壽命分別為 283 與 183 圈。

　　The PVDF/PAN/TPU and PVDF/PAN/PS ternary gel polymer electrolytes (GPE) are prepared in this research by the electrospinning technique. The liquid electrolyte adsorption rate, ionic conductivity, decomposed voltage and mechanical properties of three components GPEs prepared by the traditional experiment method are analyzed. The optimal compositions of PVDF/PAN/TPU and PVDF/PAN/PS gel polymer electrolytes are obtained by the mixture design accompanied with Statistical Analysis Software (SAS). Using GPEs prepared in this work as the electrolyte, the charge/discharge properties of anode-free lithium half-cell are also investigated.
　　The upper limits of components in ternary GPEs including PVDF/PAN/TPU and PVDF/PAN/PS are obtained by the conventional experiment technique, and the ionic conductivities measured by the AC impedance. The maximum ionic conductivity of the PVDF/PAN/TPU and PVDF/PAN/PS GPEs prepared by the conventional experiment technique are found to be 3.52×10-3 and 3.89×10-3 S cm-1, respectively, with composition of 0.2/0.6/0.2.
　　Using the mixture design method with the upper limit of ingredients and statistical analysis, the optimal compositions are studied with the ionic conductivity, decomposed voltage and mechanical stress as responses, respectively. The experimental results show that the relationship between the ionic conductivity (as response y) of PVDF/PAN/TPU ternary GPE and the pseudo-compositions is

　　y = 3.010 u1 + 3.000 u2 + 3.712 u3 + 4.481 u1u2 – 4.181 u1u3 + 45.51 u1u2u3

where u1、u2 and u3 are the pseudo-compositions of PVDF, PAN and TPU. For the PVDF/PAN/PS ternary GPE, the relationship between the ionic conductivity (as response y) and the pseudo-compositions u1, u2 and u3 corresponding to PVDF, PAN and PS is

　　y = 2.478 u1 + 3.977 u2 + 3.284 u3 + 3.368 u1u2 – 5.137 u2u3 – 26.40 u1u2u3

For PVDF/PAN/TPU and PVDF/PAN/PS ternary GPEs, the compositions for maximum ionic conductivities of 4.94 × 10-3 and 4.07 × 10-3 S cm-1 are obtained to be 0.232/0.621/0.147 and 0.245/0.555/0.200, respectively.
　　Using the optimal compositions of PVDF/PAN/TPU and PVDF/PAN/PS as GPEs, the maximum coulomb efficiencies of both Cu foil/PVDF/PAN/TPU (0.300 mm)/Li and Cu foil/PVDF/PAN/PS (0.300 mm)/Li batteries are 95.63 %, and the coulomb efficiencies slightly decrease to 84.51 and 83.10 % for 50th charge/discharge cycle, the charge/discharge cycle lifes are 259 and 161 cycles, respectively. Replacing Cu foil by Cu foam, the maximum coulomb efficiencies of the two batteries are found to be 94.58 and 95.49 %, and the coulomb efficiencies at 50th charge/discharge cycle are 87.74 and 86.77 %, respectively, and the charge/discharge cycle lifes are 283 and 183 cycles, respectively.

摘要 i
Abstract iii
目錄 v
表目錄 xiv
圖目錄 xviii
第一章 緒論 1
1-1前言 1
1-2鋰離子電池簡介 2
1-2-1鋰離子電池產業發展現況 4
1-2-2鋰離子電池之工作原理 5
1-3鋰離子電池之電解質 7
1-3-1液態電解質 (Liquid electrolyte, L.E. ) 9
1-3-2固態電解質 (Solid-state electrolyte, SSE) 10
1-3-3膠態電解質 (Gel polymer electrolyte, GPE) 11
1-3-3-1 膠態電解質之製備方法 12
1-3-3-2 製備膠態高分子電解質之高分子材料 26
1-3-3-3 製備膠態高分子電解質之複合高分子材料 33
1-3-3-4 製備膠態高分子電解質中的無機填料 38
1-4研究動機及實驗架構 44
第二章 原理 46
2-1 實驗設計法 46
2-2 混合物實驗法原理 47
2-2-1 混合物實驗法之原理 47
2-2-2 混合物實驗法之擬組成法 48
2-2-2 A. 組成存在下限條件之情形 48
2-2-2 B. 組成存在上限條件之情形 51
第三章 實驗程序與設備 54
3-1 本研究所使用之實驗藥品及儀器 54
3-1-1 實驗藥品 54
3-1-2 實驗儀器 56
3-2 實驗程序 58
3-2-1 膠態高分子電解質薄膜的製備 58
3-2-1-1 PVDF 膠態高分子電解質薄膜 58
3-2-1-2 PAN 膠態高分子電解質薄膜 58
3-2-1-3 利用傳統實驗法製備三成分膠態高分子電解質薄膜 59
3-2-1-4 利用混合物實驗法製備三成分膠態高分子電解質 60
3-2-1-5 含無機填料的膠態高分子電解質薄膜製備 62
3-2-2 膠態高分子電解質材料性質分析 64
3-2-2-1 以掃描式電子顯微鏡 (Scanning electron microscope, SEM) 分析表面型態 64
3-2-2-2 以 X 射線散射光譜儀 (Energy-dispersive X-ray spectroscopy, EDS) 分析膠態高分子電解質之元素 64
3-2-2-3 膠態高分子薄膜吸液率之量測 64
3-2-2-4 膠態高分子薄膜之孔隙度 (Porosity, P) 量測 65
3-2-2-5膠態高分子薄膜機械性質測定 66
3-2-3 膠態高分子電解質電化學性質量測 67
3-2-3 A. 以交流阻抗 (AC impedance) 分析膠態高分子電解質之離子電導率(Ionic conductivity, σ) 67
3-2-3 B. 以線性掃描伏安法 (Linear Sweep Voltammetry, LSV) 分析膠態高分子電解質之電化學性質 70
3-2-4 鈕扣型鋰離子電池組裝與充放電 72
3-2-4 A. 鈕扣型鋰離子電池之組裝 72
3-2-4 B. 鈕扣型鋰離子電池之充放電 74
第四章 結果與討論 75
4-1 PVDF 膠態高分子電解質的製備與性質 75
4-1 A. 表面組態分析 75
4-1 B. 液態電解液吸收率及對薄膜厚度的影響 78
4-1 C. 孔隙度 81
4-1 D. 機械性質 83
4-1 E. 離子電導率 86
4-1 F. 電化學窗口與分解電壓 89
4-2 PAN 膠態高分子電解質的製備與性質 93
4-2 A. 表面組態分析 93
4-2 B. 液態電解液吸收率及對薄膜厚度的影響 96
4-2 C. 孔隙度 99
4-2 D. 機械性質 101
4-2 E. 離子電導率 104
4-2 F. 電化學窗口與分解電壓 107
4-3 傳統實驗法製備 PVDF/PAN/TPU 膠態高分子電解質與性質 110
4-3-1 TPU 之上限 110
4-3-2 設定 TPU 組成為 0.2 時 PVDF 與 PAN 組成之影響 112
4-3-2 A. 液態電解液吸收率及對薄膜厚度的影響 112
4-3-2 B. 離子電導率 116
4-4 傳統實驗法製備 PVDF/PAN/PS 膠態高分子電解質與性質 119
4-4-1 PS 之上限 119
4-4-2 設定 PS 組成為 0.2 時 PVDF 與 PAN 組成之影響 121
4-4-2 A. 液態電解液吸收率及對薄膜厚度的影響 121
4-4-2 B. 離子電導率 125
4-5 利用混合物實驗法製備 PVDF/PAN/TPU 膠態高分子電解質與其性質 128
4-5-1 混合物實驗法製備PVDF/PAN/TPU 膠態高分子電解質薄膜及其性質 128
4-5-1 A. 離子電導率 131
4-5-1 B. 電化學窗口與分解電壓 134
4-5-1 C. 機械性質 136
4-5-2 各回應值之最佳組成 138
4-5-2 A. 最佳離子電導率組成 138
4-5-2 B. 最佳分解電壓組成 142
4-5-2 C. 最佳機械性質組成 146
4-6 利用混合物實驗法製備 PVDF/PAN/PS 膠態高分子電解質與其性質 150
4-6-1 混合物實驗法製備之 PVDF/PAN/PS 膠態高分子電解質薄膜及其性質 150
4-6-1 A. 離子電導率 150
4-6-1 B. 電化學窗口與分解電壓 154
4-6-1 C. 機械性質 156
4-6-2 各回應值之最佳組成 158
4-6-2 A. 最佳離子電導率組成 158
4-6-2 B. 最佳分解電壓組成 162
4-6-2 C. 最佳機械性質組成 166
4-7 最佳組成 PVDF/PAN/TPU 膠態高分子電解質添加無機奈米粒子之影響 170
4-7 A. 表面組態分析 170
4-7 B. 孔隙度 182
4-7 C. 離子電導率 184
4-7 D. 電化學窗口與分解電壓 186
4-7 E. 機械性質 188
4-8 最佳組成 PVDF/PAN/PS 膠態高分子電解質添加無機奈米粒子之影響 190
4-8 A. 表面組態分析 190
4-8 B. 孔隙度 201
4-8 C. 離子電導率 203
4-8 D. 電化學窗口與分解電壓 205
4-8 E. 機械性質 207
4-9 最佳組成 PVDF/PAN/TPU 膠態高分子電解質應用於無陽極鋰半電池的性質 209
4-9-1 PVDF/PAN/TPU 膠態高分子電解質膜厚之影響 217
4-9-1 A. Cu foil/ PVDF/PAN/TPU (0.214 ~ 0.238 mm) /Li 電池之充放電性質 217
4-9-1 B. Cu foil/ PVDF/PAN/TPU (0.300 ~ 0.329 mm) /Li 電池之充放電性質 224
4-9-1 C. Cu foil/ PVDF/PAN/TPU (0.415 ~ 0.421 mm) /Li 電池之充放電性質 231
4-9-1 D. Cu foil/ PVDF/PAN/TPU (0.513 ~ 0.526 mm) /Li 電池之充放電性質 238
4-9-2 PVDF/PAN/TPU 膠態高分子電解質添加無機填料對充放電性質影響 243
4-9-2 A. Cu foil/ PVDF/PAN/TPU(2 wt% TiO2) /Li 電池之充放電性質 243
4-9-2 B. Cu foil/ PVDF/PAN/TPU(2 wt% SiO2) /Li 電池之充放電性質 251
4-9-2 C. Cu foil/ PVDF/PAN/TPU/(2 wt% Al2O3) /Li 電池之充放電性質 258
4-9-3 Cu foam/ PVDF/PAN/TPU (0.305 ~ 0.311 mm) /Li 電池之充放電性質 265
4-10 最佳組成 PVDF/PAN/PS 膠態高分子電解質應用於無陽極鋰半電池的性質 272
4-10-1 PVDF/PAN/PS 膠態高分子電解質膜厚之影響 279
4-10-1 A. Cu foil/ PVDF/PAN/PS (0.225 ~ 0.234 mm) /Li 電池之充放電性質 279
4-10-1 B. Cu foil/ PVDF/PAN/PS (0.299 ~ 0.300 mm) /Li 電池之充放電性質 286
4-10-1 C. Cu foil/ PVDF/PAN/PS (0.397 ~ 0.412 mm) /Li 電池之充放電性質 293
4-10-2 PVDF/PAN/PS 膠態高分子電解質添加無機填料對充放電性質影響 297
4-10-2 A. Cu foil/ PVDF/PAN/PS(2 wt% TiO2) /Li 電池之充放電性質 297
4-10-2 B. Cu foil/ PVDF/PAN/PS(2 wt% SiO2) /Li 電池之充放電性質 304
4-10-2 C. Cu foil/ PVDF/PAN/PS(2 wt% Al2O3) /Li 電池之充放電性質 311
4-10-3 Cu foam/ PVDF/PAN/PS (0.290 ~ 0.312 mm) /Li 電池之充放電性質 317
第五章 綜合討論 324
5-1 以混合物實驗法製備之 PVDF/PAN/TPU 與 PVDF/PAN/PS系統的膠態高分子薄膜的比較 324
5-2 PVDF/PAN/TPU 與 PVDF/PAN/PS 系統之最佳組成組裝無陽極鋰半電池之充放電性質比較 326
第六章 結論與建議 328
第七章 參考文獻 332
第八章 附錄 343
8-1 以混合物實驗法製備之 PVDF/PAN/TPU 膠態高分子電解質以離子電導率為回應值之 SAS 統計系統程式碼 343
8-2 以混合物實驗法製備之 PVDF/PAN/TPU 膠態高分子電解質以離子電導率為回應值之 SAS 統計系統計算結果 344
8-3 混合物實驗法中以不同回應值之 C++ 軟體程式碼 [97] 349
8-3 A. 計算單一組成之程式碼 349
8-3 B. 計算 0.001 ~ 1.0 區間(多組成)之連續程式碼 352
8-4 以混合物實驗法製備之 PVDF/PAN/TPU 膠態高分子電解質以分解電壓為回應值之 SAS 統計系統程式碼 355
8-5 以混合物實驗法製備之 PVDF/PAN/TPU 膠態高分子電解質以分解電壓為回應值之 SAS 統計系統計算結果 356
8-6 以混合物實驗法製備之 PVDF/PAN/TPU 膠態高分子電解質以機械性質為回應值之 SAS 統計系統程式碼 360
8-7 以混合物實驗法製備之 PVDF/PAN/TPU 膠態高分子電解質以機械性質為回應值之 SAS 統計系統計算結果 361
8-8 以混合物實驗法製備之 PVDF/PAN/PS 膠態高分子電解質以離子電導率為回應值之 SAS 統計系統程式碼 366
8-9 以混合物實驗法製備之 PVDF/PAN/PS 膠態高分子電解質以離子電導率為回應值之 SAS 統計系統計算結果 367
8-10 以混合物實驗法製備之 PVDF/PAN/PS 膠態高分子電解質以分解電壓為回應值之 SAS 統計系統程式碼 372
8-11 以混合物實驗法製備之 PVDF/PAN/PS 膠態高分子電解質以分解電壓為回應值之 SAS 統計系統計算結果 373
8-12 以混合物實驗法製備之 PVDF/PAN/PS 膠態高分子電解質以機械性質為回應值之 SAS 統計系統程式碼 378
8-13 以混合物實驗法製備之 PVDF/PAN/PS 膠態高分子電解質以機械性質為回應值之 SAS 統計系統計算結果 379

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