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| 研究生： |
藍翊心 Yi-Hsin Lan |
|---|---|
| 論文名稱： |
新型含溴側基之聚并咪唑高分子共聚物合成及表徵應用於高溫質子交換膜燃料電池之研究 Synthesis and Characterization of Bromine-containing Polybenzimidazole Copolymers for High-temperature Proton Exchange Membrane Fuel Cells |
| 指導教授： |
陳志堅
Jyh-Chien Chen |
| 口試委員: |
游進陽
Chin-Yang Yu 王英靖 none |
| 學位類別： |
碩士 Master |
| 系所名稱： |
工程學院 - 材料科學與工程系 Department of Materials Science and Engineering |
| 論文出版年： | 2014 |
| 畢業學年度： | 102 |
| 語文別： | 中文 |
| 論文頁數： | 71 |
| 中文關鍵詞： | 聚并咪唑 、質子交換膜燃料電池 、單電池功率密度 |
| 外文關鍵詞： | Polybenzimidazole、Proton exchange membrane fuel |
| 相關次數： | 點閱：397 下載：1 |
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本研究將溴基導入含有二苯醚基的二酸中，成功合成出一種新型的二酸單體2,2’-dibromo-4,4’-oxybis(benzoic acid) (1)，並利用此新型二酸單體與聯苯四胺(3,3’-diaminobenzidine)在聚磷酸(PPA)中進行高溫關環反應，合成新型聚并咪唑(OPBI-Br, PBI-1)，除此之外，並利用此新型二酸分別和間-苯二酸(Isophthalic acid)和對-苯二酸(Terephthalic acid)為二酸單體，依不同比例混合，與聯苯四胺(3,3’-diaminobenzidine)，合成新型聚并咪唑共聚物(PBI-2~PBI-7)，並且對高分子進行表徵，PBI-1~PBI-7的固有黏度(分子量)在0.60~1.58之間，並且具有良好的熱穩定性，其熱裂解溫度Td10%介於459~514℃，在800℃時的char yield為55~71%。此外，利用有機溶劑進行成膜加工並進行磷酸摻雜，由於側基的導入使溶解度增加，除了PBI-7，皆可製備柔軟而透明之薄膜，且薄膜的氧化穩定性良好，在長時間的Fenton test後殘餘重量介於67~91%。PBI-1~PBI-6薄膜的磷酸摻雜水準(ADL)介於7.1~14.4，在160℃下的質子傳導率介於0.58~1.67 S/cm，單電池之功率密度最高可達到140~290 mW/cm2，開路電壓介於0.36~0.45 V，皆為質子交換膜燃料電池可使用範圍。
To start with, an novel dicarboxylic acid containing bromine as side group and ether linkage was synthesized from the bromination of 4,4’-oxybis(benzoic acid). Next, a bromine-containing polybenzimidazole was synthesized from 2,2’-dibromo-4,4’-oxybis(benzoic acid)(1) and 3,3’-diaminobenzidine. In addition, a series of poly(aryl ether benzimidazole) copolymers bearing different m-phenylene /p-phenylene linkage contents were synthesized by condensation polymerization in polyphosphoric acid (PPA) by varying the feed ratio of isophthalic acid/ terephthalic acid to 2,2’-dibromo-4,4’-oxybis(benzoic acid)(1). Finally, the characterization of the pristine polymer and the other copolymers were discussed. The inherent viscosities of PBI-1~PBI-7 between 0.60~1.58, and they have good thermal stabilities. The 10% weight loss temperature of the polymers were between 459~514℃, and the results show char yield at 800 ℃ were in the range of 55~71%.
On the other hand, the synthesized PBIs samples except PBI-7 present good solubility in polar aprotic solvents. They are easy to form the transparent, flexible and tough films by solution casting due to introduction of side groups. It was found that these membranes show good oxidative stabilities. The residual weight of these samples were 67~91% after immersing the membrane samples in 68 ℃ hot 3% H2O2 aqueous solution containing 4 ppm Fe2+ before the membranes were broken. The acid doping levels of PBI-1~PBI-6 were between 7.1~14.4. PBI-1~PBI-6 have a conductivity between 0.58~1.67 S/cm at 160℃. The maximum power densities could reach 140 to 290 mW/cm2. The single cell test exhibits a open circuit voltage of 0.36~0.45 V. The PBI membranes with high proton conductivities show potential application as the high temperature proton exchange membrane in fuel cell.
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全文公開日期 2019/07/25 (校內網路)全文公開日期 本全文未授權公開 (校外網路)
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