Sulfonated poly(aryl ether ether ketone ketone)s containing fluorinated moieties as proton exchange membrane materials

Liu, Baijun; Robertson, Gilles P.; Guiver, Michael D.; Sun, Yi-Ming; Liu, Yinling; Lai, Juin‐Yih; Mikhailenko, Serguei D.; Kaliaguine, Serge

doi:10.1002/polb.20867

Cited by 33 publications

(27 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Our earlier work has shown that pendent phenyl rings attached to electron-donating polymer chain sites can be preferentially sulfonated at the para position, without obvious chain degradation occurring during sulfonation. [39][40][41][42][43] In the present study, the copolymers 2-PAES-60 and 4-PAES-20, having pendent phenyl groups on the electron-withdrawing site of the polymer chain were sulfonated on the para-phenyl position with chlorosulfonic acid to produce PS2-PAES-60 and PS4-PAES-20, respectively ("postsulfonation" is distinguished by PS). On the basis of experimental IEC w values, a 5-fold molar excess of chlorosulfonic acid was necessary for complete sulfonation.…”

Section: Methodsmentioning

confidence: 99%

Polymer Electrolyte Membranes Derived from New Sulfone Monomers with Pendent Sulfonic Acid Groups

et al. 2010

Self Cite

View full text Add to dashboard Cite

New monomers containing two or four pendent phenyl groups were synthesized by bromination of bis(4-fluorophenyl) sulfone, followed by Suzuki coupling with benzeneboronic acid. The resulting monomers were converted to the corresponding sulfonated monomers having two or four pendent sulfonic acid groups, predominately at the p-phenyl position. Aromatic nucleophilic substitution (SNAr) polycondensation using the di- and tetrasulfonated monomers provided sulfonated poly(arylene ether sulfone) copolymers S2-PAES-xx and S4-PAES-xx, respectively, where xx refers to the molar ratio of the sulfonated to non-sulfonated pendent phenyl monomer. Copoly(arylene ether sulfone)s based on the corresponding non-sulfonated monomers were also synthesized for a parallel study on postpolymerization sulfonation of these copolymers. Postsulfonation occurred predominately at the para-pendent phenyl site, and the reactions were complete within a short time (about 30 min), without evidence of chain degradation. Flexible and tough membranes having high mechanical strength were obtained by solution casting of all four series of copolymers. The copolymers with two or four pendent sulfonic acid groups had high proton conductivities in the range of 44−142 mS/cm for S2-PAES-xx and 51−158 mS/cm for S4-PAES-xx at room temperature, respectively. The methanol permeabilities of these copolymers were in the range of 0.8 × 10−8−15.0 × 10−7 cm2/s, which is lower than Nafion (16.7 × 10−7 cm2/s). The S4-PAES-xx membranes displayed better properties (lower water uptake and higher proton conductivities) than the S2-PAES-xx membranes, which can be attributed to the more blocky architecture of the sulfonic acid groups in the S4 membranes. A combination of high proton conductivities, low water uptake, and low methanol permeabilities for some of the obtained copolymers indicated that they are good candidate materials for proton exchange membrane in fuel cell applications.

show abstract

Section: Methodsmentioning

confidence: 99%

Polymer Electrolyte Membranes Derived from New Sulfone Monomers with Pendent Sulfonic Acid Groups

et al. 2010

Self Cite

View full text Add to dashboard Cite

show abstract

“…SPAEEKK based membranes still dissolved into the Fenton reagent in about 1 h because of its high degree of sulfonation [32]. However, the oxidation of hydrocarbon-based membranes in Fenton reagent is not necessarily indicative or a good predictor of their durability under fuel cell operation, since sulfonated poly(ether ether ketone) membranes have shown lifetimes over 1000 h in either PEMFC and DMFC tests [55,56].…”

Section: Proton Conductivity Of the Membranesmentioning

confidence: 99%

“…The fluorinated moieties in sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK) increase the hydrophobicity of polymer and enhance the formation of separated hydrophobic and hydrophilic domains in its microstructure, thereby providing the proton conducting domains [32]. Addition of silica to SPAEEKK membranes through the sol-gel process formed hybrid membranes, which showed decreased methanol crossover.…”

Section: Introductionmentioning

confidence: 99%

Increases in the proton conductivity and selectivity of proton exchange membranes for direct methanol fuel cells by formation of nanocomposites having proton conducting channels

Liu

Wang

et al. 2009

Journal of Power Sources

Self Cite

View full text Add to dashboard Cite

We explore an approach to effectively enhance the properties of cost-effective hydrocarbon protonexchange membranes for application in the direct methanol fuel cell (DMFC). This approach utilizes sulfonated silica nanoparticles (SA-SNP) as additives to modify sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK). The interaction between the sulfonic acid groups of SA-SNP and those of SPAEEKK combined with hydrophilic-hydrophobic phase separation induce the formation of proton conducting channels, as evidenced by TEM images, which contribute to increases in the proton conductivity of the SPAEEKK/SA-SNP nanocomposite membrane. The presence of SA-SNP nanoparticles also reduces methanol crossover in the membrane. Therefore, the SPAEEKK/SA-SNP nanocomposite membrane shows a high selectivity, which is 2.79-fold the selectivity of Nafion ® 117. The improved selectivity of the SPAEEKK/SNP nanocomposite membrane demonstrates potential of this approach in providing hydrocarbon-based PEMs as alternatives to Nafion in direct methanol fuel cells.

show abstract

“…Sulfonated poly(aryl ether ether ketone ketone)s (SPEEKKxx, where xx = 40, 50, 60, 70, 80, and 100 with DS = 0.8, 1.0, 1.2, 1.4, 1.6, and 2.0) were prepared by Liu et al (34). The structures of the polymer containing the 6F or 6FP groups are shown in Scheme 1 (1-1).…”

Section: Sulfonated Fluorinated Random Copoly(arylene Ether)smentioning

confidence: 99%

Sulfonated fluorinated-aromatic polymers as proton exchange membranes

Ghosh¹,

Banerjee

2014

E-Polymers

View full text Add to dashboard Cite

Abstract:In recent years, extensive research on the preparation and properties of proton exchange membranes (PEMs) has been realized. This article focusses on the recent studies on new PEM materials based on aromatic hydrocarbon polymers with sulfonated groups as hydrophilic domains and fluorinated groups as hydrophobic domains as alternatives to conventional perfluorinated polymers. It is necessary to improve the proton conductivity especially under low-humidity conditions and at high operating temperatures to break through the current aromatic PEM system. Hence, there is a need to develop new high-conductivity fuel cell ionomers with improved thermal, chemical, and electrochemical stability by designing a suitable polymer structure for PEM application.

show abstract

Sulfonated poly(aryl ether ether ketone ketone)s containing fluorinated moieties as proton exchange membrane materials

Cited by 33 publications

References 32 publications

Polymer Electrolyte Membranes Derived from New Sulfone Monomers with Pendent Sulfonic Acid Groups

Polymer Electrolyte Membranes Derived from New Sulfone Monomers with Pendent Sulfonic Acid Groups

Increases in the proton conductivity and selectivity of proton exchange membranes for direct methanol fuel cells by formation of nanocomposites having proton conducting channels

Sulfonated fluorinated-aromatic polymers as proton exchange membranes

Contact Info

Product

Resources

About