含有氧代氮代苯并環己烷之可交聯磺酸化聚電解質應用於直接甲醇燃料電池

Synthesis and Characterization of Benzoxazine-Containing Sulfonated Polyelectrolytes for Direct Methonal Fuel Cell

陳南勳(Nan-Shiun Chen)

指導教授 ： 劉英麟

中原大學/工學院/化學工程研究所/碩士(2012年)

https://doi.org/10.6840/cycu201200764

摘要

中文摘要
本研究之目的在開發含磺酸根之高分子材料，以製成聚電解質膜應用於直接甲醇燃料電池( Direct Methonal Fuel Cell )。
首先利用4,4’-bis(4-aminophenoxy)biphenyl (BAPB)製備出具磺酸根以及雙馬來醯亞胺官能基之新穎單體BAPBDS-BMI，經過基本的元素以及結構鑑定其結構後，再與含有benzoxazine官能基之雙呋喃單體BPA-FBz以，迪爾斯-阿爾德反應( Diels-Alder reaction )聚合成主鏈含有氧代氮代苯并環己烷以及磺酸根官能基的線性高分子BA-DA。經由熱壓法及氧代氮代苯并環己烷的熱開環反應，將此高分子交聯製成一具有可僥性的膜材以應用於燃料電池。
BA-DA膜材與杜邦商業膜Nafion-117磺酸化程度接近，但由於其具有交聯結構，在水與甲醇的膨潤度以及尺寸安定性等性質，優於Nafion-117。特別是甲醇滲透率方面，BA-DA膜材的甲醇滲透率只有Nafion-117的六分之一。
BA-DA膜材的質子傳導度為5 x10-2 S/cm，低於Nafion-117的數值(9.1 x10-2 S/cm)；但由於其阻擋甲醇滲透能力優於Nafion-117，所以選擇比上為Nafion-117的3倍左右，因此預期BA-DA膜材在直接甲醇燃料電池的校能表現可以優於Nafion-117。

關鍵字

燃料電池 ； 直接甲醇滲透燃料電池 ； 氧代氮代苯并環己烷 ； 交聯

並列摘要

Abstract
The purpose of this study is to develop a polymer material containing sulfonic acid functional groups, which are further used as polyelectrolyte membrane in direct methanol fuel cells.
A novel new monomer BAPBDS-BMI containing sulfonic acid and bismaleimide groups was synthesized from 4,4’-bis(4-aminophenoxy)biphenyl (BAPB) and characterized. This new monomer was further reacted with benzoxazine and furan containing BPA-FBz monomer via Diels-Alder reaction to prepare a linear polymer BA-DA. This newly synthesized polymer containing benzoxazine and sulfonic acid groups was hot-pressed and cured into free standing flexible thin film. The curing process induces the ring opening reaction of benzoxazine groups, resulting in crosslinking effect in the polymer. The membranes are then further applied in fuel cell.
Although the degree of sulfonation of BA-DA membrane and commercialized membrane Nafion-117 is very close, but due to the crosslinking effect inside the BA-DA membrane, this membrane shows improved swelling property, dimensional stability and methanol permeability compared with Nafion-117.
The proton conductivity of BA-DA membrane is 5×10-2 S/cm, which is lower than that of Nafion-117 (9.1×10-2 S/cm), but the methanol permeability is 6 times higher than that of Nafion-117, and hence the selectivity is 3 times better than Nafion-117. For this reason, we predicted that BA-DA membrane will show better performance than Nafion-117 in DMFC.

並列關鍵字

fuel cell ； crosslink ； benzoxazine ； DMFC

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