TY - JOUR
T1 - Anion conductive block poly(arylene ether)s
T2 - Synthesis, properties, and application in alkaline fuel cells
AU - Tanaka, Manabu
AU - Fukasawa, Keita
AU - Nishino, Eriko
AU - Yamaguchi, Susumu
AU - Yamada, Koji
AU - Tanaka, Hirohisa
AU - Bae, Byungchan
AU - Miyatake, Kenji
AU - Watanabe, Masahiro
PY - 2011/7/13
Y1 - 2011/7/13
N2 - Anion conductive aromatic multiblock copolymers, poly(arylene ether)s containing quaternized ammonio-substituted fluorene groups, were synthesized via block copolycondensation of fluorene-containing (later hydrophilic) oligomers and linear hydrophobic oligomers, chloromethylation, quaternization, and ion-exchange reactions. The ammonio groups were selectively introduced onto the fluorene-containing units. The quaternized multiblock copolymers (QPEs) produced ductile, transparent membranes. A well-controlled multiblock structure was responsible for the developed hydrophobic/hydrophilic phase separation and interconnected ion transporting pathway, as confirmed by scanning transmission electron microscopic (STEM) observation. The ionomer membranes showed considerably higher hydroxide ion conductivities, up to 144 mS/cm at 80 °, than those of existing anion conductive ionomer membranes. The durabilities of the QPE membranes were evaluated under severe, accelerated-aging conditions, and minor degradation was recognized by 1H NMR spectra. The QPE membrane retained high conductivity in hot water at 80 ° for 5000 h. A noble metal-free direct hydrazine fuel cell was operated with the QPE membrane at 80 °. The maximum power density, 297 mW/cm2, was achieved at a current density of 826 mA/cm2.
AB - Anion conductive aromatic multiblock copolymers, poly(arylene ether)s containing quaternized ammonio-substituted fluorene groups, were synthesized via block copolycondensation of fluorene-containing (later hydrophilic) oligomers and linear hydrophobic oligomers, chloromethylation, quaternization, and ion-exchange reactions. The ammonio groups were selectively introduced onto the fluorene-containing units. The quaternized multiblock copolymers (QPEs) produced ductile, transparent membranes. A well-controlled multiblock structure was responsible for the developed hydrophobic/hydrophilic phase separation and interconnected ion transporting pathway, as confirmed by scanning transmission electron microscopic (STEM) observation. The ionomer membranes showed considerably higher hydroxide ion conductivities, up to 144 mS/cm at 80 °, than those of existing anion conductive ionomer membranes. The durabilities of the QPE membranes were evaluated under severe, accelerated-aging conditions, and minor degradation was recognized by 1H NMR spectra. The QPE membrane retained high conductivity in hot water at 80 ° for 5000 h. A noble metal-free direct hydrazine fuel cell was operated with the QPE membrane at 80 °. The maximum power density, 297 mW/cm2, was achieved at a current density of 826 mA/cm2.
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U2 - 10.1021/ja204166e
DO - 10.1021/ja204166e
M3 - Article
C2 - 21657275
AN - SCOPUS:79960046703
VL - 133
SP - 10646
EP - 10654
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 27
ER -