臺灣博碩士論文加值系統

本研究主要目的為開發新的質子交換膜，應用於直接甲醇燃料電池中(DMFC)，目前商用 Nafion薄膜有價格昂貴，不適合高溫使用，有高的甲醇滲透率等缺點，所以需要進一步尋找替代材料。在本研究中，主要是導入雜環來提升高分子膜的熱安定性及水解安定性，合成主鏈含磺酸基之聚醯亞胺共聚物，這一系列磺酸基聚醯亞胺有好的溶解性，能溶於NMP、DMAc及m-cresol等溶劑，都能經溶液塗佈成具韌性薄膜，所合成NTDA-P-SX聚合物薄膜的質子傳導度都在50-80℃時接近Nafion117，薄膜的質子傳導度會隨著溫度及薄膜的含水率增加而提高，而這些共聚物薄膜的耐水解安定性比由常用含磺酸基二胺(BDSA)所導出聚合物在相似IEC的耐水解安定性好很多。

Abstract
The aim of this study was to develop new proton exchange membranes(PEM) for DMFC (direct methanol fuel cell) for the substitution of the Nafion membrane showing high cost and poor barrier to methanol crossover. A series of sulfonated polyimides containing heterocylic groups were synthesized. The sulfonated polyimides generally showed good solubility in N-methyl-2-pyrrolidone(NMP), N,N-dimethylacetamide(DMAc) and m-cresol. They could be solution-cast into the tough films. Proton conductivities of these copolyimides membranes were measured as the function of temperature. At the temperature (50-80℃), the proton conductivities of NTDA-P-SX copolyimide was similar to those of Nafion117. At the temperature(50-80℃), the AP-based copolyimide (P-SX) membranes showed proton conductivities similar to those of Nafion117. The proton conductivity of these films increased with increase in temperature and degree of water uptake. In addition, P-SX-based copolyimide membranes exhibited much better water stability than those derived from a widely used sulfonated diamine, 2,2’-benzinedisulfonic acid (BDSA), with similar IEC.

摘要………………………………………………..………………….. Ⅰ
Abstract………………………………………………………..………. Ⅱ
Table索引……………………………………………………………….Ⅴ
Figure索引……………………………………………………………...Ⅵ

第一章 緒論………………………………………………………..……1
1.1 前言……………………………………………………………..1
1.2 燃料電池簡介…………………………………………………..2
1.3 各種燃料電池介紹……………………………………………..8
1.4 甲醇燃料電池的電解質隔膜…………………………………14
1.5 文獻回顧………………………………………………………16
1.6 研究動機………………………………………………………21
第二章 實驗……………………………………………………………22
2.1實驗藥品………………………………………………………22
2.2實驗程序………………………………………………………25
2.2.1 單體製備…………………………………………………25
2.2.2 合成含磺酸基之聚醯亞胺共聚合物……………………26
2.3 聚合物之物性與化性分析………………………….………..28
第三章 結果與討論……………………………………………………34
3.1 固有黏度之測試……………………………………………...34
3.2 溶解度之測試………………………………………………...35
3.3 熱性質測試…………………………………………………...36
3.4 吸濕率、離子交換能力(IEC, ion exchange capacity）
和質子傳導度分析……………………………………………………..39
3.5 水解安定性與氧化安定性測試……………………………...48
3.6 機械性質測試………………………………………………...52
3.7 甲醇滲透率量測………………………………………...……54
第四章 結論……………………………………………………………56
文獻參考………………………………………………………………57

Table索引
Table 1. 常見燃料電池基本特性之比較………………………….……9
Table 2. 燃料電池成分對燃料電池的影響……………………….…..11
Table 3. The inherent viscosities of P-/SX copolymer……………….…34
Table 4. Solubility of P-/SX copolymer…………………………….…..35
Table 5. Thermal Properties of P-/SX copolymer………………………37
Table 6. Proton conductivities and water uptake of P-/SX copolymers in water…………………………………………………………………….42
Table 7. The activity energy of P-/SX copolymers……………………..45
Table 8. Proton conductivities of P-/SX copolymers in different
humidity and different temperature…………………………………..…47
Table 9. Oxidative stability and hydrolytic stability of P-/SX copolymers……………………………………………………………...50
Table 10. Hydrolytic Stability of P-/SX and ODADS copolymer……....53
Table 11. Methanol permeability of P-/SX copolymer………………….55

Figure索引
Figure .1燃料電池工作原理………………………………………….…4
Figure .2電池的極化………………………………………………….…5
Figure .3不同燃料電池所對應之燃料處理程度…………………...…10
Figure .4 Chemical structures of BSPhB、BDSA and ODADS……........18
Figure .5 Chemical structure of copolyimides (a)reference【15】
(b) reference【16】 (c) reference【17】(d) reference【18】………………19
Figure .6 Chemical structures of P-/SX/NH2/SO3H、 F/NH2、AP/CF3/NH2 and 2,3NA/CF3/NH2……………………………….………………..…..25
Figure .7 Synthesis of sulfonated copolymer………………………..….27
Figure .8量測甲醇滲透率夾具圖…………………………………...…31
Figure .9 TGA curve of P-/SX+2,3NA+NTDA(8:2) copolymer at a
heating rate of 10℃/min……………………………………..………….39
Figure .10 TMA curve of P-/SX+2,3NA+NTDA(8:2) copolymer at a
heating rate of 10℃/min………………………………………………...39
Figure .11 IEC v.s Water uptake of P-/SX………………………………40
Figure .12 Proton conductivites v.s temperature of P-/SX……………...43
Figure .13 ln(σ)v.s 1/K valuves of P-SX/F……………………………...44
Figure .14 ln(σ)v.s 1/K valuves of P-SX/AP……………………………44
Figure .15 ln(σ)v.s 1/K valuves of P-SX/2,3NA and P-SX/homo………45
Figure .16 Chemical structures of ODADS and BDSA copolymers【8】51
Figure .17 IEC v.s. methanol permeability of P-/SX copolymers……....55

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