Ladder-type aromatic block copolymers containing sulfonated triphenylphosphine oxide moieties as proton conductive membranes

Zhang, Yaojian; Miyake, Junpei; Akiyama, Ryo; Miyatake, Kenji

doi:10.1016/j.polymer.2015.09.034

Cited by 5 publications

(4 citation statements)

References 22 publications

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“…Due to the higher IEC value, CSPPSU‐4S showed slightly larger ionic clusters (ca., 3 nm in diameter) than that (ca., 1.5 nm in diameter) of CSPPSU‐2S. It is well‐known that such distinct phase‐separated morphology promotes proton conductivity, which is accountable for higher proton conductivity of CSPPSU‐4S than that of CSPPSU‐2S. Relatively small ionic clusters could cause some dead‐end channels at low RH to cause the low conductivity as discussed above (Figure ).…”

Section: Resultsmentioning

confidence: 88%

Effect of thermal crosslinking on the properties of sulfonated poly(phenylene sulfone)s as proton conductive membranes

Zhang

Kim

Miyatake

2016

J of Applied Polymer Sci

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The synthesis and characterization of crosslinked aromatic polymer membranes with high ion exchange capacity (IEC) values are reported. Through aromatic nucleophilic substitution polycondensation and the subsequent sulfonation reaction, the highly sulfonated polymers SPPSU‐2S and SPPSU‐4S with high molecular weight (Mn = 138–145 kDa, Mw = 200–279 kDa) and well‐defined structures were synthesized. By solution casting and thermal annealing treatment, flexible crosslinked membranes with high solvent insolubility were obtained. The membranes exhibited mechanical and chemical stability as confirmed by dynamic mechanical analysis (DMA) and conductivity measurement. The crosslinked SPPSU‐4S membrane with IEC = 3.20 meq/g showed the highest proton conductivity of 0.163 S/cm at 120 °C, 90% RH, and improved thermal stability compared with its precursor (uncrosslinked) membrane. The results show that simple annealing method could improve significantly membranes properties of highly sulfonated aromatic polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44218.

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Section: Resultsmentioning

confidence: 88%

Effect of thermal crosslinking on the properties of sulfonated poly(phenylene sulfone)s as proton conductive membranes

Zhang

Kim

Miyatake

2016

J of Applied Polymer Sci

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“…In-plane and through-plane swellings of SQF-4 membrane were 3.7 and 5.4 times higher than those of the SQF-2 membrane (Table S2). Compared to the SPP-QP membrane, the SQF-3 membrane with comparable IEC value showed lower water uptake and λ value probably because of the distinct well-developed phase-separated morphology mentioned above (the absorbed water molecules would be mostly present in the vicinity of sulfonic acid groups in the hydrophilic domain) …”

Section: Resultsmentioning

confidence: 96%

“…Compared to the SPP-QP membrane, the SQF-3 membrane with comparable IEC value showed lower water uptake and λ value probably because of the distinct welldeveloped phase-separated morphology mentioned above (the absorbed water molecules would be mostly present in the vicinity of sulfonic acid groups in the hydrophilic domain). 18 The proton conductivity of the SQF membranes was measured at 80 °C and plotted as a function of RH in Figure 5a. The SQF-4 membrane showed the highest proton conductivity, reaching 405 mS cm −1 , ca.…”

Section: Synthesis Of Sqfmentioning

confidence: 99%

Sulfonated Phenylene/Quinquephenylene/Perfluoroalkylene Terpolymers as Proton Exchange Membranes for Fuel Cells

Zhang

Miyake

Akiyama

et al. 2018

ACS Appl. Energy Mater.

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A novel series of terpolymers (SQF) containing sulfophenylene, quinquephenylene, and perfluoroalkylene groups in the polymer main chain were designed and synthesized as proton exchange membranes for fuel cells. The terpolymers with high molecular weight (M w = 179–207 kDa, M n = 41–50 kDa) and different ion exchange capacity (IEC) values (1.70, 2.56, and 3.34 mequiv g–1) gave flexible self-standing membranes by solution casting. Compared to the two-component (sulfophenylene and quinquephenylene segments) copolymer membranes, the incorporation of the third component, perfluoroalkylene groups, resulted in better water utilization for the proton conduction, while it did not alter the other properties such as gas permeability and mechanical strength. The selected membrane (SQF-3 with IEC = 2.56 mequiv g–1) exhibited high fuel cell performance under high- and low-humidity conditions with maximum power density reaching 0.97 W cm–2 at 100% RH (relative humidity) and 0.82 W cm–2 at 30% RH, respectively, at a current density of 1.51 A cm–2 with oxygen. A good interfacial compatibility between the SQF-3 membrane and catalyst layers resulted in mass activity of the cathode catalyst comparable to that obtained with the Nafion membrane NRE 211. During the open circuit voltage (OCV) hold test with air and hydrogen at 80 °C and 30% RH for 1000 h, the OCV showed a slight decrease from 0.97 to 0.88 V. Post-test analyses revealed that the SQF-3 membrane retained its initial high fuel cell performance due to its high chemical stability as well as low gas permeability.

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“…[17][18][19][20] We have also demonstrated that introducing ladder structure based on the intra-polymer Heck reaction increased the rigidity of the polymer chain resulting in the improved mechanical stability of aromatic PEMs. 21,22 Those methods required additional functional groups (carboxyl, bromo groups, etc. ), or metal catalysts for the post-cross-linking reactions, which resulted in the high production cost and/or synthetic complexity of the PEMs.…”

Section: Introductionmentioning

confidence: 99%

Ladder-type sulfonated poly(arylene perfluoroalkylene)s for high performance proton exchange membrane fuel cells

2020

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Ladder-type aromatic block copolymers containing sulfonated triphenylphosphine oxide moieties as proton conductive membranes

Cited by 5 publications

References 22 publications

Effect of thermal crosslinking on the properties of sulfonated poly(phenylene sulfone)s as proton conductive membranes

Effect of thermal crosslinking on the properties of sulfonated poly(phenylene sulfone)s as proton conductive membranes

Sulfonated Phenylene/Quinquephenylene/Perfluoroalkylene Terpolymers as Proton Exchange Membranes for Fuel Cells

Ladder-type sulfonated poly(arylene perfluoroalkylene)s for high performance proton exchange membrane fuel cells

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