Aromatic copolymers containing ammonium-functionalized oligophenylene moieties as highly anion conductive membranes

Naoki Yokota; Manai Shimada; Hideaki Ono; Ryo Akiyama; Eriko Nishino; Koichiro Asazawa; Junpei Miyake; Masahiro Watanabe; Kenji Miyatake

doi:10.1021/ma5019878

Aromatic copolymers containing ammonium-functionalized oligophenylene moieties as highly anion conductive membranes

Naoki Yokota, Manai Shimada, Hideaki Ono, Ryo Akiyama, Eriko Nishino, Koichiro Asazawa, Junpei Miyake, Masahiro Watanabe, Kenji Miyatake^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

62 Citations (Scopus)

Abstract

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 °C. Reasonable alkaline stability of QPE-bl-9 membrane was confirmed in 1 M KOH aqueous solution for 1000 h at 40 °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 O₂ as the oxidant.

Original language	English
Pages (from-to)	8238-8246
Number of pages	9
Journal	Macromolecules
Volume	47
Issue number	23
DOIs	https://doi.org/10.1021/ma5019878
Publication status	Published - 2014 Dec 9
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "Aromatic copolymers containing ammonium-functionalized oligophenylene moieties as highly anion conductive membranes",

abstract = "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 °C. Reasonable alkaline stability of QPE-bl-9 membrane was confirmed in 1 M KOH aqueous solution for 1000 h at 40 °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 O2 as the oxidant.",

author = "Naoki Yokota and Manai Shimada and Hideaki Ono and Ryo Akiyama and Eriko Nishino and Koichiro Asazawa and Junpei Miyake and Masahiro Watanabe and Kenji Miyatake",

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T1 - Aromatic copolymers containing ammonium-functionalized oligophenylene moieties as highly anion conductive membranes

AU - Yokota, Naoki

AU - Shimada, Manai

AU - Ono, Hideaki

AU - Akiyama, Ryo

AU - Nishino, Eriko

AU - Asazawa, Koichiro

AU - Miyake, Junpei

AU - Watanabe, Masahiro

AU - Miyatake, Kenji

PY - 2014/12/9

Y1 - 2014/12/9

N2 - 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 °C. Reasonable alkaline stability of QPE-bl-9 membrane was confirmed in 1 M KOH aqueous solution for 1000 h at 40 °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 O2 as the oxidant.

AB - 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 °C. Reasonable alkaline stability of QPE-bl-9 membrane was confirmed in 1 M KOH aqueous solution for 1000 h at 40 °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 O2 as the oxidant.

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Aromatic copolymers containing ammonium-functionalized oligophenylene moieties as highly anion conductive membranes

Abstract

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