硬桿式聚電解質sPBI-PS(Li+)，是一水溶性有優越離子導電度的全固態聚電解質。但由於硬桿式的主鏈，導致成膜時有分子取向，形成一個在薄膜橫截面為非等向性(out-of-the plane anisotropic)的微結構和導電度，因而嚴重地限制了其在全固態薄膜電池之應用。
本研究所合成鉸鏈型共聚電解質a-sPBI-PS(Li+)，是利用共聚合的縮聚反應，將磺基對苯二甲酸與磺基間苯二甲酸以5：1、15：1、25：1、50：1的比例加入分別進行共聚，使原本硬桿式的主鏈產生轉折，並接上硫化丙烷鋰離子懸垂基，成為新的水溶性鉸鏈型硬桿式聚電解質。化學合成反應的產物以多種方式判定各單體與聚合物之結構、純度。所合成出的鉸鏈型共聚電解質a-sPBI-PS(Li+)其黏度與導電度會隨著所加入的鉸鏈型基團的比例增加而依序降低，本研究對此導電度的現象提出一離子管道(ionic channel)理論來解釋。對於鉸鏈型共聚電解質而言，摻雜過氯酸鋰(LiClO4)後對導電度提升比使用碘化鋰(LiI)來得好。鉸鏈型共聚電解質a-sPBI-PS(Li+)之固態薄膜的常溫導電度可達4.71╳10-3 S/cm。以X光散射分析與電子顯微鏡的影像觀測，得知所合成的鉸鏈型共聚電解質a-sPBI-PS(Li+)薄膜為俱有三維等向性(three-dimensionally isotropic)的均質微結構。

A water-soluble rigid-rod polyelectrolyte sPBI-PS(Li+) could be
doped with LiI and cast as a freestanding film from aqueous solution
showing a room-temperature in-plane DC conductivity (�������n) of 8.3╳10-3 S/cm. However, the cast film assumed an anisotropic microstructure due to nematic liquid-crystalline rigid-rod backbone leading to an out-of-the plane DC conductivity (����) which was three orders smaller than those of the ������, and severely limited its applications as a solid polyelectrolyte for thin-film battery.
2-Sulfo-terephthalic acid and 5-sulfo-isophthalic acid in ratios of 5：1, 15：1, 25：1, or 50：1 were synthesized via copolycondensation reaction making the rigid-rod backbone of sPBI-PS(Li+) become articulated. Further reaction with 1,3-propanesultone pendants, the rigid-rod polyelectrolyte was changed into a new water-soluble articulated rigid-rod polyelectrolyte a-sPBI-PS(Li+). Various analyses were applied to ascertain chemical structure and purities of synthesized monomers and polymers. The copolymer conductivity and intrinsic viscosity would decrease with increasing the articulation ratio. For a-sPBI-PS(Li+), LiClO4 was a better dopant, compared to LiI, to enhance conductivity. a-sPBI-PS(Li+) (25:1) doped LiI had a room-temperature conductivity as high as 4.7´10-3 S/cm. No layered structure was revealed by wide-angle X-ray scattering and scanning electron microscope. The cast thin-film thus had 3-dimensionally isotropic structure and electrical conductivity.

目錄…………………………………………………………..……….... I

圖目錄………………………………………………………..……......IV

表目錄…………………………………………………..……..…….VIII

壹、前言..…………………………………………………………..…....1

貳、文獻回顧………………………………………………..……..…....3

2-1 固態聚電解質簡介……………………………………..……..3

2-2 硬桿式高分子簡介…………….………………………..…….4

2-3 導電機制………………………………………………..……..9

參、研究動機……………………………………………………..……12

3-1 高分子主體的改質……………………………………..……12

3-2 摻雜劑的種類…………………………………………..……16

肆、實驗………………………………………………………..………20

4-1 單體之合成…………………………………………..………20

4-1-1 1,2,4,5-Tetraaminobenzene tetrahydrochloride
(簡稱TABTHC)的合成反應………………………..20

(a) 4,6-Dinitro-1,3-dichlorobenzene………………..…...…21

(b) 4,6-Dinitro-1,3-benzenediamine………………...……..22

(c) 1,2,4,5-Tetraaminobenzene tetrahydrochloride………...22

4-1-2 磺基對苯二甲酸(2-sulfo-terephthalic acid)
(簡稱STPA)的合成反應…………………...…….…....23

4-2 硬桿式高分子合成反應介質………………………………..25

4-2-1 聚磷酸的製備………………………………….....……25

4-3 硬桿式聚合物……………………………………………..…26

4-3-1 Poly[1,7-dihydrobenzo[1,2-d:4,5-d’]diimidazo-2,6-
diyl[2-(2-sulfo)-p-phenylene]](簡稱sPBI)的合成
反應………….…………………………………………27

4-3-2 Poly[1,7-dipropylsulfobenzo[1,2-d:4,5-d’]diimidazo-
2,6-diyl[2-(2- sulfo)-p-phenylene]](簡稱sPBI-PS(Li+))
的合成反應……………………………….………..…..29

4-3-3 鉸鏈型硬桿式高分子(簡稱a-sPBI)的合成反應……...30

4-3-4 鉸鏈型硬桿式聚電解質(簡稱a-sPBI-PS(Li+))
的合成反應…………………………..……………..….33

4-4 甲基磺酸(Methanesulfonic acid，MSA)的純化…………..…34

4-5 化學分析……………………………………………..………35

4-5-1 傅立葉轉換紅外線(Fourier Transform Infrared，FTIR)
光譜……………………………………..………..….…36

4-5-2 核磁共振(Nuclear Magnetic Resonance，NMR)………36

4-5-3 元素分析儀(Elemental Analyzer，EA)……………..…..37

4-6 聚合物分子量的量測…………………………………..……38

4-7 澆鑄成膜……...…….…………………………………..……40

4-8 導電度的量測……………………………………………..…41

4-9 X光散射分析…………………………………………..……42

4-10 掃描式電子顯微鏡(Scanning Electron Microscopy，SEM) ..43

伍、實驗結果與討論……………………………………..……………46

5-1 單體之合成分析……………………………………..………46

5-1-1 1,2,4,5-Tetraaminobenzene tetrahydrochloride
(簡稱TABTHC)的合成分析………………………..46

(a) 4,6-Dinitro-1,3-dichlorobenzene之化學分析…………46

(b) 4,6-Dinitro-1,3-benzenediamine之化學分析….……...48

(c) 1,2,4,5-Tetraaminobenzene tetrahydrochloride
之化學分析……………………………….......…..…...49

5-1-2 磺基對苯二甲酸(STPA)的合成分析………………….52

5-2 聚電解質之合成與分析……………………………………..54

5-2-1 Poly[1,7-dihydrobenzo[1,2-d:4,5-d’]diimidazo-2,6-
diyl[2-(2-sulfo)-p-phenylene]] (簡稱sPBI)的合成
分析……………………………….…………….…..….54

5-2-2 鉸鏈型硬桿式高分子(簡稱a-sPBI)的合成分析…...…56

(a) a-sPBI(5:1)…………………………….…………..…...57

(b) a-sPBI(15:1)………………………………….………...58

(c) a-sPBI(25:1)………………………….………………...61

(d) a-sPBI(50:1)………………………….…………….......62

5-3 導電度的量測………………………………………………..64

5-4 X光散射分析………………………………………………..82

5-5 掃描式電子顯微鏡分析……………………………………..84

5-6 總結…………………………………………………………..88

陸、結論…..……………………………………………..…………..…92

柒、參考文獻………………………………………………………..…94




圖目錄
圖2-1 先進電解質的導電度與溫度關係圖..………..…..…..……..5
圖2-2 sPBI-PS硬桿式聚電解質分子結構……...….………………6
圖2-3 雜環芳香烴硬桿式高分子PBX的化學結構…………….…6
圖2-4 sPBI-PS硬桿式聚電解質薄膜結構示意圖：
(a)俯視和(b)橫截面………………………………………….8
圖2-5 PEO與金屬陽離子錯合之示意圖……………….……..….10
圖2-6 鋰離子在PEO高分子電解質中之傳導行為…………...….11
圖3-1 sPBI-PS硬桿式聚電解質包含(a) 氮上的氫取代為
磺酸化懸垂基，及(b) 單體合成時所加入的磺酸化
基團的分子結構………………………………..…………..14
圖3-2 磺基間苯二甲酸分子結構…………………………………15
圖3-3 鉸鏈型硬桿式分子的主鏈示意圖…………………………15
圖3-4 間苯二甲酸分子結構………………………………………16
圖4-1 1,2,4,5-Tetraaminobenzene tetrahydrochloride
(TABTHC)分子結構……………………...…………….....21
圖4-2 磺基對苯二甲酸(STPA)分子結構…………………………23
圖4-3 磺基對苯二甲酸(STPA)的保護及
去保護機制示意圖…………………………………………24
圖4-4 sPBI與sPBI-PS(Li+)縮聚合成的反應流程……………..…28
圖4-5 sPBI硬桿式高分子結構…………………………….……...29
圖4-6 sPBI-PS(Li+)硬桿式聚電解質分子結構……...……………29
圖4-7 鉸鏈型硬桿式共聚電解質合成的反應流程………………32
圖4-8 Poly[1,7-dihydrobenzo[1,2-d:4,5-d’]diimidazo-2,6-diyl [2-(2-sulfo)-p-phenylene]-co-1,7-dihydrobenzo-[1,2- d:4,5d’]diimidazo-2,6-diy[2-(3-sulfo)-m-phenylene)]
共聚物的分子結構……………………….…………...…..33
圖4-9 Poly[1,7-dipropylsulfobenzo[1,2-d:4,5-d’]diimadazo-2,6-
diyl[2-(2-sulfo)-p-phenylene]-co-1,7-dipropylsulfo-benzo-
[1,2-d:4,5d’]diimidazo-2,6-diyl[2-(3-sulfo)-m-phenylene)]
共聚物的分子結構…….…………………………….....…..34
圖4-10 純化甲基磺酸(MSA)的裝置圖……………………...…..…35
圖4-11 八點探針法示意……………...……………….……………42
圖5-1 4,6-Dinitro-1,3-dichlorobenzene之FTIR吸收光譜………..47
圖5-2 4,6-Dinitro-1,3-dichlorobenzene之1H NMR質譜圖.…...…48
圖5-3 4,6-Dinitro-1,3-benzenediamine之FTIR吸收光譜…….....49
圖5-4 4,6-Dinitro-1,3-benzenediamine之1H NMR質譜圖.………50
圖5-5 TABTHC之FTIR吸收光譜………..……………………...51
圖5-6 TABTHC之1H NMR質譜圖……………………...………51
圖5-7 STPA之FTIR光譜圖………...……………………………53
圖5-8 STPA之1H NMR質譜圖…………..………..……………...54
圖5-9 硬桿式高分子sPBI之1H NMR質譜圖……..………….…55
圖5-10 硬桿式高分子sPBI的比濃黏度�喣ed與固有黏度
�喭nh對濃度作圖………..…………………………………...57
圖5-11 鉸鏈型硬桿式高分子a-sPBI(5:1)的比濃黏度�喣ed
與固有黏度�喭nh對濃度作圖…….………………..………...59
圖5-12 鉸鏈型硬桿式高分子a-sPBI(15:1)的比濃黏度�喣ed
與固有黏度�喭nh對濃度作圖…………….…………….…...60
圖5-13 鉸鏈型硬桿式高分子a-sPBI(25:1)的比濃黏度�喣ed
與固有黏度�喭nh對濃度作圖………….…………….……...62
圖5-14 鉸鏈型硬桿式高分子a-sPBI(50:1)的比濃黏度�喣ed
與固有黏度�喭nh對濃度作圖………….………….………...64
圖5-15 硬桿式高分子中磺基對苯二甲酸、磺基間苯二甲酸
的比率(x:y)對特性黏度[�傒作圖……………...….………..65
圖5-16 不同種類的鉸鏈型聚電解質a-sPBI-PS(X+)(x:y)薄膜
之電壓-電流曲線……………………...…………………..67
圖5-17 摻雜LiI的鉸鏈型聚電解質a-sPBI-PS(Li+)(5:1)薄膜
之電壓-電流曲線………………………………………….68
圖5-18 摻雜LiI的鉸鏈型聚電解質a-sPBI-PS(Li+)(15:1)薄膜
之電壓-電流曲線………………………………………….69
圖5-19 摻雜LiI的鉸鏈型聚電解質a-sPBI-PS(Li+)(25:1)薄膜
之電壓-電流曲線………………………………………….70
圖5-20 摻雜LiI的鉸鏈型聚電解質a-sPBI-PS(Li+)(50:1)薄膜
之電壓-電流曲線………………………………………….71
圖5-21 摻雜LiClO4的鉸鏈型聚電解質a-sPBI-PS(Li+)(5:1)
薄膜之電壓-電流曲線…………………………………….72
圖5-22 摻雜LiClO4的鉸鏈型聚電解質a-sPBI-PS(Li+)(5:1)
薄膜之電壓-電流曲線…………………………………….73
圖5-23 摻雜LiI的鉸鏈型聚電解質a-sPBI-PS(H+)(15:1)
薄膜之電壓-電流曲線…………………………………….74
圖5-24 摻雜LiI的鉸鏈型聚電解質a-sPBI-PS(H+)(50:1)
薄膜之電壓-電流曲線…………………………………….75
圖5-25 不同比例的鉸鏈型聚電解質a-sPBI-PS(Li+)(x:y)
薄膜的LiI摻雜濃度與導電度……………...……………..76
圖5-26 不同比例的鉸鏈型聚電解質a-sPBI-PS(Li+)(x:y)
薄膜的LiClO4摻雜濃度與導電度…..……...…...………..76
圖5-27 不同比例的鉸鏈型聚電解質a-sPBI-PS(H+)(x:y)
薄膜的LiI摻雜濃度與導電度…………………...………..77
圖5-28 摻雜不同鹽類的鉸鏈型聚電解質a-sPBI-PS(Li+)(5:1)
薄膜的摻雜濃度與導電度…….…...……………………...77
圖5-29 不同懸垂基的鉸鏈型聚電解質a-sPBI-PS(Li+)/( H+)
的LiI摻雜濃度與導電度……………………………….....78
圖5-30 sPBI-PS高分子形成離子通道的示意圖………………....80
圖5-31 未含摻雜劑的硬桿式聚電解質sPBI-PS(Li+)
薄膜正面的廣角X光散射圖譜………………….………..85
圖5 32 未含摻雜劑的鉸鏈型硬桿式聚電解質a-sPBI-PS(Li+)
(15:1)薄膜正面的廣角X光散射圖譜…………...…………85
圖5-33 未含摻雜劑的硬桿式聚電解質sPBI-PS(Li+)
薄膜橫截面的廣角X光散射圖譜……...…………..……..86
圖5-34 未含摻雜劑的硬桿式聚電解質sPBI-PS(Li+)薄膜
橫截面的廣角X光散射依垂直膜面(equatorial)和
平行於膜面(meridional)兩方向擇取其散射強度…………86
圖5-35 未含摻雜劑的鉸鏈型硬桿式聚電解質a-sPBI-PS(Li+)
(15:1)薄膜橫截面的廣角X光散射圖譜…..……...………..87
圖5-36 未含摻雜劑的鉸鏈型硬桿式聚電解質a-sPBI-PS(Li+)
(15:1)薄膜橫截面的廣角X光散射依垂直膜面(equatorial)
和平行於膜面(meridional)兩方向擇取其散射強度..……..87
圖5-37 硬桿式聚電解質sPBI-PS(Li+)薄膜橫截面SEM圖……....89
圖5-38 鉸鏈型硬桿式聚電解質a-sPBI-PS(Li+)(50:1)
薄膜橫截面SEM圖……………………………………….89

表目錄
表5-1 不同種類的鉸鏈型聚電解質a-sPBI-PS(X+)(x:y)之
電阻值、膜厚及導電度…………….………………………67
表5-2 摻雜LiI的鉸鏈型聚電解質a-sPBI-PS(Li+)(5:1)之
電阻值、膜厚及導電度……………….……………………68
表5-3 摻雜LiI的鉸鏈型聚電解質a-sPBI-PS(Li+)(15:1)之
電阻值、膜厚及導電度…………….………………………69
表5-4 摻雜LiI的鉸鏈型聚電解質a-sPBI-PS(Li+)(25:1)之
電阻值、膜厚及導電度………………….…………………70
表5-5 摻雜LiI的鉸鏈型聚電解質a-sPBI-PS(Li+)(50:1)之
電阻值、膜厚及導電度……….……………………………71
表5-6 摻雜LiClO4的鉸鏈型聚電解質a-sPBI-PS(Li+)(5:1)之
電阻值、膜厚及導電度…………………….………………72
表5-7 摻雜LiClO4的鉸鏈型聚電解質a-sPBI-PS(Li+)(50:1)之
電阻值、膜厚及導電度…………………….………………73
表5-8 摻雜LiI的硬桿式聚電解質a-sPBI-PS(H+)(15:1)之
電阻值、膜厚及導電度…………….………………………74
表5-9 摻雜LiI的硬桿式聚電解質a-sPBI-PS(H+)(50:1)之
電阻值、膜厚及導電度…………………….………………75

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