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  • 學位論文

含五苯荑骨架之聚苯胺之合成與作為超電容器電極材料之研究

Synthesis of Pentiptycene-incorporated Polyanilines for Application as the Electrode Materials of Supercapacitors

指導教授 : 楊吉水

摘要


超級電容相較於電池具備較好的功率密度和穩定性,並且比起電容具有更高的能量密度,因此成為新一代的能源儲存元件。以聚苯胺作為電極材料,因為具有環境汙染較少、導電機制易於控制、具良好加工性及價格低在之優點,但其循環穩定度不夠高,乃因為薄膜體積膨脹的問題所造成。在本研究中,我們將聚苯胺的骨架引入具有三維立體結構的五苯荑分子,利用其本身特殊的立體結構將聚苯胺高分子鏈隔開,設計並合成出線性的APPANI及星狀的TAPPANI兩種高分子,探討其應用於超電容器電極材料的潛力。 結果顯示,由於五苯荑分子的引入,在苯胺成核的時期會作為模板參與聚合反應,並且得到不同於聚苯胺的表面形貌。TAPPANI和APPANI隨著摻入的比例不同而產生不同大小的球形聚集,相較於聚苯胺形成較紊亂的顆粒狀堆積,五苯荑分子的引入其特殊的孔洞讓聚苯胺長鏈之間可以有很好的分散效果。並且藉由電化學測量其循環穩定度,可以發現在經過1000次循環穩定度測試後,聚苯胺衰退了40 %,但是線性的APPANI和星狀的TAPPANI分子因為五苯荑的摻入使得衰退僅僅只有13 %及7 %,穩定度有明顯的提升。 透過APPANI及TAPPANI兩系列聚合物,我們也可以進而推論聚苯胺的膨脹效應受到空間排列的影響相當密切。藉由五苯荑分子的引入幫助我們了解有關其在超電容器材料之中的反應情形,有助於之後有關超電容器材料上的改良之研究。

並列摘要


Supercapacitors have superior power density and stability as compared with batteries and higher energy density than conventional capacitors, making them attractive for energy storage applications. Polyaniline has been considered as promising supercapacitor electrode materials due to its high environmental stability, controllable electrical conductivity, easy processability and low cost. However, serious mechanical decay during the cycling test occurs for polyaniline devices. We have introduced the rigid and nonplanar pentiptycene scaffold to polyaniline, linear APPANI and star-shaped TAPPANI, to overcome this problem. The results indicate that pentiptycene-containing starting materials act as a reaction template and replace the nucleation step in the chemical polymerization. Both APPANI and TAPPANI display sphere morphology of different size depending on the ratio of pentiptycene anilines versus anilines, which might account for the increased stability on the basis of the electrochemical analysis of cyclic voltammetry. After 1000 cycles, the pristine polyaniline film retains about 63 % of capacity whereas APPANI and TAPPANI retain 87 and 93% , respectively. This work allows one to understand the reaction associated with charging/discharging, and we believe that the stability of polyaniline is intimately related to the morphology. Our results may be helpful for future modification and application of model polyanilines as the electrode materials of supercapacitors.

並列關鍵字

supercapacitors pentiptycene stability

參考文獻


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