Anion Conductive Aromatic Copolymers from Dimethylaminomethylated Monomers: Synthesis, Properties, and Applications in Alkaline Fuel Cells

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• 作者：Ryo Akiyama ; Naoki Yokota ; Eriko Nishino ; Koichiro Asazawa ; Kenji Miyatake
• 刊名：Macromolecules
• 出版年：2016
• 出版时间：June 28, 2016
• 年：2016
• 卷：49
• 期：12
• 页码：4480-4489
• 全文大小：718K
• 年卷期：0
• ISSN：1520-5835

文摘

A novel series of anion conductive aromatic copolymers were synthesized from preaminated monomers (2,5-, 3,5-, or 2,4-dichloro-N,N-dimethylbenzylamine), and their properties were investigated for alkaline fuel cell applications. The targeted copolymers (QPE-bl-11a, -11b, and -11c) were synthesized via nickel-mediated Ullmann coupling polymerization, followed by quaternization and ion exchange reactions. Unlike the conventional method involving chloromethylation or bromination, this method provided copolymers with well-defined chemical structure. The hydrophilic components of the copolymers were composed of chemically stable phenylene main chain modified with high-density ammonium groups. Oligo(arylene ether sulfone ketone)s were employed as a hydrophobic block. QPE-bl-11a gave tough and bendable membranes by solution casting. The obtained membrane with the highest ion exchange capacity value (IEC = 2.47 mequiv g^–1) showed high hydroxide ion conductivity (130 mS cm^–1) in water at 80 °C. The QPE-bl-11a membrane showed reasonable alkaline stability in 1 M KOH aqueous solution for 1000 h at 60 °C. A platinum-free fuel cell was successfully operated with hydrazine as a fuel, the QPE-bl-11a as a membrane, and an electrode binder. The maximum power density of 380 mW cm^–2 was achieved at a current density of 1020 mA cm^–2 with O₂.