本研究首先著重於聚苯胺複合膜之製備及其性質之探討，利用不同添加劑(DMcT，對苯二胺，DABSA)修飾聚苯胺，使用循環伏安法與含浸法製備聚苯胺複合膜電極，再利用循環伏安分析、交流阻抗分析、SEM照相、BET分析、紅外線光譜分析及元素分析來探討聚苯胺複合膜之性質。最後將製備所得之聚苯胺與其複合膜組裝為鋰/1M LiClO4碳酸丙烯/聚苯胺複合膜與鋰/固態高分子電解質/聚苯胺複合膜電池，進行充放電測試。
在循環伏安分析中發現PANI/PPDA複合膜與PANI/DABSA複合膜經過100次衰退測試,摻雜反應波峰電流，各衰退33.97%與34.08%，小於聚苯胺之41.42%，證明二者添加劑能抑制膜之老化。在交流阻抗分析中則發現，PANI/ PPDA複合膜在摻雜與去摻雜過程中，其電荷轉移阻力與擴散阻力遠小於聚苯胺膜，可知對苯二胺能促進摻雜與去摻雜反應。而PANI/DABSA則具有層面珊瑚狀表面組態，在所有複合膜中具有最大之表面積，其值為32.96 m2/g。
三種不同製備方式所得之PANI/DMcT複合膜，電荷傳遞阻抗均較純聚苯胺小，可知DMcT具有活化聚苯胺摻雜/去摻雜反應之功用，由SEM組態分析得知，各種製備之PANI/DMcT均呈現纖維狀之鬆散結構。
在組裝之鋰/1M LiClO4碳酸丙烯溶液/聚苯胺複合膜電池中，0.4mA之充放電電流，以方法一製備之PANI/DMcT電容量最大，其值為101.82 mAh/g，而PANI/DABSA在60次之循環後可得最小之電容量衰退率，其值僅為0.74%。而在1.2mA下進行150次循環，對苯二胺與苯胺所形成之複合膜則顯示有91.62 mAh/g之最大電容量及100%之庫侖效率。
組裝為鋰/固態高分子電解質/聚苯胺複合膜電池，PANI/PPDA顯示具有最大電容量為78.6 mAh/g經60次充放電後，電容量衰退了27.56％。

The polyaniline (PANI) composite films were prepared and the characteristics of the PANI composite film were studied in this thesis. Using cyclic voltammetry and impregnation, PANI was modified by the various additives (DMcT, PPDA and DABSA). The PANI composite films prepared in this work were characterized by the methods of cyclic voltammetry, AC impedance, SEM, BET, FTIR and elemental analysis, respectively. Finally, the charge/discharge properties of the Li/1 M LiClO4 propylene carbonate(PC) solution/PANI composite film and Li/solid polymer electrolyte (SPE)/PANI composite film batteries were investigated.
The doping peak current of PANI/PPDA and PANI/DABSA were declined 33.97 and 34.08% less than 41.42% for PANI after 100 cycles cyclic voltammetry. The experimental results indicated that the agent of PANI was inhibited by the modifications of PPDA and DABSA, respectively. The charge transfer and diffusion resistances of PANI/PPDA evaluated by the AC impedance were also much less than that of PANI. This result revealed that the doping/undoping reaction was promoted by the addition of PPDA in PANI/PPDA. Comparing with other composite films, the coral type morphology found by SEM photograph for PANI/DABSA showed the maximum surface area of 32.96 m2/g.
The less charge transfer resistance of PANI/DMcT composite films prepared by three different methods compared with PANI indicated that the doping/undoping reaction of PANI was activated by the addition of DMcT. The fibrous and loose structures was found by the SEM photographs in the PANI/DMcT composite films.
Using PANI/DMcT composite film prepared by method 1 as cathode, the maximum discharge capacity of 101.82 mAh/g was found in Li/1 M LiClO4 PC solution/PANI/DMcT battery for 0.4 mA charge/discharge current. Comparing with the other composite films, the minimum decline ratio of discharge capacity of 0.74% was obtained for PANI/DABSA used in the Li/1 M LiClO4 PC solution/PANI/DABSA battery after 60 charge/discharge cycles. Using 1.2 mA charge/discharge current, Li/1 M LiClO4 PC solution/PANI/PPDA battery showed the maximum discharge capacity of 91.62 mAh/g for 150 charge/discharge cycles compared with the other composite films and the coulomb efficiency was found as 100%.
For Li/SPE/PANI composite film batteries the maximum discharge capacity was obtained as 78.6 mAh/g for PANI/PPDA composite film and the decline ratio of discharge capacity was 27.56% for 60 charge/discharge cycles.

中文摘要………………………………………………………………Ⅴ
英文摘要………………………………………………………………Ⅶ
誌謝……………………………………………………………………Ⅸ
目錄……………………………………………………………………Ⅹ
表目錄………………………………………………………………ⅩⅢ
圖目錄………………………………………………………………ⅩⅤⅠ
第一章 緒論…………………………………………………………1
1-1 電池概述及發展現況……………………………………………1
1-2 鋰二次電池………………………………………………………6
1-3 共軛導電性高分子之特性………………………………………7
1-3-1 共軛導電性高分子之電子軌域………………………………9
1-3-2 共軛導電性高分子之導電機構………………………………9
1-4 導電性高分子聚苯胺…………………………………………12
1-4-1 聚苯胺之結構………………………………………………12
1-4-2 聚苯胺之摻雜與其結構……………………………………12
1-5 聚苯胺之合成…………………………………………………15
1-5-1 化學法製備聚苯胺……………………………………………15
1-5-2 電化學法製備聚苯胺…………………………………………15
1-6聚苯胺為陰極之二次電池系統…………………………………17
1-6-1A 未改質之聚苯胺於非鋰二次電池之充放電特性…………17
1-6-1B 未改質之聚苯胺於鋰二次電池之充放電特性……………18
1-7 應用有機硫高分子於聚苯胺之改質…………………………23
1-7-1 有機硫聚合物之結構與特性………………………………23
1-7-2 有機硫高分子於鋰二次電池之應用………………………26
1-7-2-1A. 有機硫高分子之特性研究……………………………26
1-7-2-1B. 有機硫高分子之充放電特性…………………………30
1-8 對苯二胺與DABSA修飾聚苯胺電極於鋰二次電池之應用…33
1-9 研究動機………………………………………………………35
第二章 實驗設備、方法與程序…………………………………37
2-1 儀器……………………………………………………………37
2-2 藥品……………………………………………………………39
2-3 實驗裝置與程序………………………………………………41
2-3-1 聚苯胺及其複合膜電極之製備與特性之分析……………41
2-3-1-1 聚苯胺及其複合膜電極之製備…………………………41
2-3-1-2 聚苯胺複合膜電極之電化學性質分析…………………44
2-3-1-3 聚苯胺及其複合膜電極之表面結構分析………………47
2-3-1-4 聚苯胺及其複合膜電極之表面積測定…………………47
2-3-1-5 聚苯胺及其複合膜電極之元素分析……………………47
2-3-1-6 聚苯胺及其複合膜電極之紅外線光譜分析……………48
2-3-2 鋰/液態有機電解質 /聚苯胺及其複合膜電極之之充放電
實驗…………………………………………………………48
2-3-3 高分子電解質膜之製備……………………………………50
2-3-4 鋰/固態高分子電解質 /聚苯胺複合膜電池之充放電
性質…………………………………………………………52
第三章 結果與討論………………………………………………56
3-1 聚苯胺複合膜電極之製備與特性分析……………………56
3-1-1 聚苯胺複合膜電極之製備……………………………… 56
3-1-1-1 PANI/DMcT複合膜電極之製備…………………………56
3-1-1-2 PANI/ PPDA複合膜電極之製備…………………………75
3-1-1-3 PANI/DABSA複合膜電極之製備………………………77
3-1-2 聚苯胺複合膜電極之特性………………………………79
3-1-2-1 PANI/DMcT複合膜電極之特性…………………………80
3-1-2-2 PANI/ PPDA複合膜電極之特性…………………………120
3-1-2-3 PANI/DABSA複合膜電極之特性………………………134
3-2 鋰/液態電解質/聚苯胺複合膜電池之充放電特性…………145
3-2-1 陰極材料之影響……………………………………………145
3-2-2 PANI/DMcT製備方法之影響………………………………154
3-2-3 充放電電流之影響…………………………………………167
3-2-3-1 充放電電流0.8mA………………………………………… 167
3-3 鋰/固態高分子電解質/聚苯胺複合膜電池之充放電特性
…………………………………………………………………202
3-4綜合討論…………………………………………………………214
第四章 結論與建議…………………………………………………224
參考文獻……………………………………………………………226
附錄…………………………………………………………………240

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