臺灣博碩士論文加值系統

本論文是鋰電池高分子PVdF-HFP(Poly(vinylidene difluoride)-co- Hexafluoropylene)之固態電解質的改質研究。在高分子電解質中添加多孔洞沸石Zeolite A、Zeolite Y、ZSM-5、Mordenite與中孔洞分子篩MCM-41以形成複合材料，將可幫助電解質吸附更多的塑化劑，進而幫助鋰離子傳導，增加電解質的導電度。
本研究的高分子電解質以製程最簡便的溶劑鑄成法(Solvent Casting Method)製備，添加物種類依處理方式可以分成三種，第一種是添加未經過任何處理的沸石與中孔洞分子篩MCM-41，第二種為添加經過鋰離子交換的沸石，最後一種則是先將沸石以矽烷((3,3,3—trifluoropropyl)trimethoxysilane)經由初濕含浸法處理過後再當作電解質的添加物。經由一連串的實驗結果發現，Zeolite A與Zeolite Y比其他種類沸石或MCM-41添加物對電解質導電度的助益較大，而且矽烷的加入幫助了沸石在電解質中的均勻分佈，有效改善了電解質的導電度。在室溫下(25oC)本研究所合成不含添加物之電解質經由交流阻抗分析所測出的導電度為3.69×10-4(±0.20×10-4)S/cm，當在此基本組成電解質中加入添加物為經由矽烷處理過的沸石Zeolite A，最高將可得到1.20×10-3 S/cm的導電度，是未加任何添加物之電解質導電度的3.5倍，與加入Zeolite A添加物的電解質相較，也是其電解質導電度的1.5倍之多。
除了導電度之外，本研究也測試電解質在承受固定壓力下阻抗的損失對時間之關係，藉以瞭解電解質的尺寸穩定性。我們發現電解質的尺寸穩定性質與添加物的添加量成正比關係。經由LSV測試，本研究所合成的電解質之分解電壓範圍在4.7~5.2V之間，均高於鋰電池的平均工作電壓3.6V，亦即我們所合成之電解質將可在鋰電池的高工作電壓下穩定的操作。

This study is focus on the melioration of PVdF-HFP(Poly (vinylidene defluoride)-co-Hexafluoropylene) polymer electrolyte. By adding some porous zeolite A、Y、ZSM-5、mordenite and MCM-41 in the electrolyte, the conductivity of it can be improved. Because the additives can adsorb a great quantity of plasticizer(EC/PC), which is a more valuable medium for the transmission of lithium ion in electrolyte.
We synthesized the solid polymer electrolyte by solvent casting method. The additives in the electrolyte can be classified into three groups by the methods of pretreatment. The first group includes the fresh zeolite A、Y、ZSM-5、mordenite and MCM-41. The second contains zeolite A and Y after lithium ion exchanging procedure. The last kind of additives are these zeolites which are surface modified with CF3CH2CH2Si(OCH3)3. From a series of our study, we found that the additives zeolite A and Y can facilitate the conductivity of electrolyte more well than other additives. By the silane pre-treating procedure, the zeolites can even enhance the conducting ability of lithium ion in electrolyte, since the silane promote the dispersion of zeolites well in the organic polymer medium. At room temperature(25oC), the conductivity of the prototype electrolyte(without any additives) that we synthesized is 3.69×10-4(±0.20×10-4)S/cm. After surface modifying the fresh zeolite A by silane, the maximum conductivity we obtained is 1.20×10-3S/cm, about 3.5 times of the conductivity of the prototype electrolyte.
Except electrolyte conductivity, we also investigated the mechanical strength of electrolyte by testing the relation between resistance loss and time, we found that the mechanical strength of electrolyte and the amount of additives are in direct proportion. By linear scanning voltage (LSV) testing, we can check the decomposing voltage of electrolytes. The decomposing voltage of the electrolytes that we synthesized is from 4.7V to 5.2V, which is above the average working voltage of lithium battery. That is, the electrolytes we synthesized can charge and discharge stably in the high working voltage environment of lithium battery.

目錄 I
致謝 V
中文摘要 VI
英文摘要 VIII
圖索引 IX
表索引 XIV
第一章 緒論與文獻回顧 1
1.1緒論 1
1.1.1固態高分子電解質之材料與選擇 4
1.2文獻回顧 15
1.2.1固態高分子電解質之發展 15
1.2.2鋰高分子電池之性能 19
1.2.2.1導電度 21
1.2.2.2機械性質 25
1.2.2.3其他性能 25
1.3研究動機 27
第二章 實驗方法與原理 28
2.1儀器 28
2.2藥品 29
2.3實驗裝置、步驟與原理 30
2.3.1高分子電解質混合液的攪拌實驗裝置 30
2.3.2實驗程序 32
2.3.2.1離子交換程序 32
2.3.2.2沸石與矽烷的合成處理 34
2.3.2.3沸石與MCM-41之結構穩定度測試 34
2.3.2.4固態高分子電解質之合成程序 35
2.4沸石的元素分析方法 36
2.5固態高分子電解質導電度量測 37
2.6尺寸穩定性 40
2.7分解電位 40
第三章 結果與討論 42
3.1本研究之綱要 42
3.2以各種類沸石與MCM-41為添加物合成之電解質 44
3.2.1各添加物之結構穩定度測試 44
3.2.2含各添加物之電解質的導電度分析 51
3.3以離子交換沸石為添加物合成之電解質 54
3.3.1 ZeoliteA與ZeoliteY離子交換前後之結構比較 54
3.3.2沸石ZeoliteA與ZeoliteY離子交換前後之元素分析 57
3.3.3以Li-A與Li-Y為添加物電解質之導電度分析 59
3.4添加物為以矽烷處理過之沸石所合成的電解質 64
3.4.1以矽烷與Li-Y反應後為添加物之電解質 64
3.4.1.1 Li-Y與矽烷反應後之晶體結構 65
3.4.1.2含矽烷與Li-Y之電解質的導電度分析 67
3.4.2以矽烷與Li-A反應後為添加物之電解質 70
3.4.2.1 Li-A與矽烷反應後之晶體結構 70
3.4.2.2含矽烷與Li-A之電解質的導電度分析 72
3.4.3以矽烷與Zeolite A反應後為添加物之電解質 74
3.4.3.1 Zeolite A與矽烷反應後之晶體結構 74
3.4.3.2含矽烷與Zeolite A之電解質的導電度分析 76
3.5各電解質之綜合比較 78
3.5.1導電度之綜合比較 78
3.5.2尺寸穩定性─固定壓力下之膜厚變化 80
3.5.3電化學穩定度─分解電壓之量測 85
第四章 結論 95
第五章 未來發展方向 97
第六章 參考文獻 98

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