Aromatic Copolymers Containing Ammonium-Functionalized Oligophenylene Moieties as Highly Anion Conductive Membranes
Aromatic Copolymers Containing Ammonium-Functionalized Oligophenylene Moieties as Highly Anion Conductive Membranes
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DOI：
10.1021/ma5019878
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发表时间：
2014-12-09
期刊：
影响因子：
5.5
通讯作者：
Miyatake, Kenji
中科院分区：
文献类型：
--
作者：
Yokota, Naoki;Shimada, Manai;Miyatake, Kenji
报道了以低聚亚苯基为骨架的季铵基芳香族阴离子导电共聚物的合成及性能。我们的新型亲水性组分由化学稳定的低聚亚苯基主链组成，该主链经高密度离子基团修饰。采用部分氟化的低聚（亚芳基醚）作为疏水嵌段。目标共聚物（QPE-bl-9）通过镍介导的偶联聚合、随后的氯甲基化、季铵化和离子交换反应合成。QPE-bl-9通过溶液浇铸提供了坚韧的、可弯曲的膜。所得膜具有最高的离子交换容量（IEC = 2.0 mequiv g（-1）），在80 ℃的水中表现出高的氢氧离子电导率（138 mS cm（-1））。QPE-bl-9膜在40 ° C下在IM KOH水溶液中持续1000小时的合理的碱性稳定性得到证实。使用QPE-bl-9作为膜和电极粘合剂的不含贵金属的燃料电池成功地运行。在电流密度为1.20 A·cm~（-2）时，以肼为燃料，O-2为氧化剂，获得了510 mW·cm~（-2）的最大功率密度。
The synthesis and properties of anion conductive aromatic copolymers containing oligophenylene moieties as a scaffold for quaternized ammonium groups are reported. Our new hydrophilic components consist of a chemically robust oligophenylene main chain modified with a high density of ionic groups. A partially fluorinated oligo(arylene ether) was employed as a hydrophobic block. The targeted copolymers (QPE-bl-9) were synthesized via nickel-mediated coupling polymerization, followed by chloromethylation, quaternization, and ion exchange reactions. QPE-bl-9 provided tough, bendable membranes by solution casting. The resulting membrane with the highest ion exchange capacity (IEC = 2.0 mequiv g(-1)) exhibited high hydroxide ion conductivity (138 mS cm(-1)) in water at 80 degrees C. Reasonable alkaline stability of QPE-bl-9 membrane was confirmed in 1 M KOH aqueous solution for 1000 h at 40 degrees C. A noble metal-free fuel cell with QPE-bl-9 used as the membrane and electrode binder was successfully operated. A maximum power density of 510 mW cm(-2) was achieved at a current density of 1.20 A cm(-2) with hydrazine as the fuel and O-2 as the xidant.