Sulfonated Poly(arylene sulfide sulfone nitrile) Multiblock Copolymers with Ordered Morphology for Proton Exchange Membranes

Ordered morphologies in disulfonated poly(arylene sulfide sulfone nitrile) (SPSN) copolymers were generated via thermal annealing followed by multiblock copolymer synthesis. While SPSN random copolymers (R-SPSN) showed featureless morphologies, the SPSN multiblock copolymers (B-SPSN) exhibited cocontinuous lamellar morphologies with a center-to-center interdomain size of up to 40 nm. In spite of the well-ordered, interconnected hydrophilic domains, the water self-diffusion coefficient (e.g., D = (0.7–2.0) × 10–10 m2 s–1) and proton conductivity (e.g., σ = 0.16–0.20 S cm–1 in deionized water at 30 °C) through B-SPSN were lower than those of the corresponding R-SPSN (e.g., D = (3.5–3.9) × 10–10 m2 s–1 and σ = 0.21 S cm–1) due to the relatively lower water uptake of the B-SPSN after thermal annealing. The reduced water uptake of B-SPSN was beneficial to reduction of peroxide degradation rate. Thermal annealing produced significant gains in morphological ordering and finer control over desired membrane proper...

[1]  Dong Won Shin,et al.  Durable Sulfonated Poly(arylene sulfide sulfone nitrile)s Containing Naphthalene Units for Direct Methanol Fuel Cells (DMFCs) , 2013 .

[2]  Yanxiang Li,et al.  Viscometric behavior of disulfonated poly(arylene ether sulfone) random copolymers used as proton exchange membranes , 2008 .

[3]  H. Kita,et al.  Synthesis and properties of novel sulfonated polyimides derived from naphthalenic dianhydride for fuel cell application , 2008 .

[4]  T. D. Dang,et al.  Direct Synthesis of Fully Sulfonated Polyarylenethioether Sulfones as Proton‐Conducting Polymers for Fuel Cells , 2006 .

[5]  S. Paddison,et al.  Transport in proton conductors for fuel-cell applications: simulations, elementary reactions, and phenomenology. , 2004, Chemical reviews.

[6]  J. E. Tanner,et al.  Spin diffusion measurements : spin echoes in the presence of a time-dependent field gradient , 1965 .

[7]  R. Guo,et al.  Synthesis and Characterization of Phenolphthalein-based Poly(arylene ether sulfone) Hydrophilic−Hydrophobic Multiblock Copolymers for Proton Exchange Membranes , 2010 .

[8]  Dong Won Shin,et al.  Fluorene-Based Poly(arylene ether sulfone)s Containing Clustered Flexible Pendant Sulfonic Acids as Proton Exchange Membranes , 2011 .

[9]  Feng Zhang,et al.  Preparation and evaluation of a proton exchange membrane based on oxidation and water stable sulfonated polyimides , 2007 .

[10]  J. Mcgrath,et al.  Directly copolymerized poly(arylene sulfide sulfone) disulfonated copolymers for PEM‐based fuel cell systems. I. Synthesis and characterization , 2005 .

[11]  Dong Won Shin,et al.  Polymer Electrolyte Membranes Derived from New Sulfone Monomers with Pendent Sulfonic Acid Groups , 2010 .

[12]  Jae‐Suk Lee,et al.  Synthesis of Highly Fluorinated Poly(arylene ether sulfide) for Polymeric Optical Waveguides , 2006 .

[13]  R. Guo,et al.  Partly fluorinated poly(arylene ether ketone sulfone) hydrophilic–hydrophobic multiblock copolymers for fuel cell membranes , 2012 .

[14]  Robert B. Moore,et al.  Effects of block length and solution-casting conditions on the final morphology and properties of disulfonated poly(arylene ether sulfone) multiblock copolymer films for proton exchange membranes , 2009 .

[15]  Hongwei Zhang,et al.  Recent development of polymer electrolyte membranes for fuel cells. , 2012, Chemical reviews.

[16]  G. Robertson,et al.  Comb-Shaped Poly(arylene ether sulfone)s as Proton Exchange Membranes† , 2008 .

[17]  Dong Won Shin,et al.  Morphological transformation during cross-linking of a highly sulfonated poly(phenylene sulfide nitrile) random copolymer , 2012 .

[18]  Yanxiang Li,et al.  Purity characterization of 3,3′-disulfonated-4,4′-dichlorodiphenyl sulfone (SDCDPS) monomer by UV–vis spectroscopy , 2008 .

[19]  Y. Elabd,et al.  Block Copolymers for Fuel Cells , 2011 .

[20]  Meilin Liu,et al.  A Durable Alternative for Proton‐Exchange Membranes: Sulfonated Poly(Benzoxazole Thioether Sulfone)s , 2011 .

[21]  K. Miyatake,et al.  Hydrolytically stable polyimide ionomer for fuel cell applications , 2004 .

[22]  M. Guiver,et al.  Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs) , 2011 .

[23]  Rodger Yuan,et al.  Effect of thermal history on the ionic conductivity of block copolymer electrolytes , 2013 .

[24]  G. Robertson,et al.  Sulfonated copoly(phthalazinone ether ketone nitrile)s as proton exchange membrane materials , 2006 .

[25]  Li-bin Wu,et al.  Effect of water on the changes in morphology and proton conductivity for the highly crystalline hydrocarbon polymer electrolyte membrane for fuel cells. , 2009, The journal of physical chemistry. B.

[26]  Mahlon Wilson,et al.  Scientific aspects of polymer electrolyte fuel cell durability and degradation. , 2007, Chemical reviews.

[27]  Yanxiang Li,et al.  Morphological investigations of disulfonated poly(arylene ether sulfone)-b-naphthalene dianhydride-based polyimide multiblock copolymers as potential high temperature proton exchange membranes , 2009 .

[28]  Ying‐Ling Liu.  Developments of highly proton-conductive sulfonated polymers for proton exchange membrane fuel cells , 2012 .

[29]  Jung-pil Lee,et al.  End-Group Cross-Linked Poly(arylene ether) for Proton Exchange Membranes , 2009 .

[30]  Nanwen Li,et al.  Enhancement of proton transport by nanochannels in comb-shaped copoly(arylene ether sulfone)s. , 2011, Angewandte Chemie.

[31]  B. Freeman,et al.  Disulfonated Poly(Arylene Ether Sulfone) Random Copolymer Thin Film Composite Membrane Fabricated Us , 2012 .

[32]  Y. Lee,et al.  Solvent-assisted thermal annealing of disulfonated poly(arylene ether sulfone) random copolymers for low humidity polymer electrolyte membrane fuel cells , 2012 .

[33]  L. Madsen,et al.  Anisotropy and Transport in Poly(arylene ether sulfone) Hydrophilic−Hydrophobic Block Copolymers , 2010 .

[34]  G. Robertson,et al.  Comparison of PEM Properties of Copoly(aryl ether ether nitrile)s Containing Sulfonic Acid Bonded to Naphthalene in Structurally Different Ways , 2007 .

[35]  Michael D. Guiver,et al.  Low-swelling proton-conducting copoly(aryl ether nitrile)s containing naphthalene structure with sulfonic acid groups meta to the ether linkage , 2006 .

[36]  M. Guiver,et al.  Toward Improved Conductivity of Sulfonated Aromatic Proton Exchange Membranes at Low Relative Humidity , 2008 .

[37]  Dong Won Shin,et al.  A capillary water retention effect to improve medium-temperature fuel cell performance , 2013 .

[38]  Moon Jeong Park,et al.  Increased water retention in polymer electrolyte membranes at elevated temperatures assisted by capillary condensation. , 2007, Nano letters.

[39]  P. Jannasch,et al.  Highly proton conducting electrolyte membranes based on poly(arylene sulfone)s with tetrasulfonated segments , 2013 .

[40]  Y. Lee,et al.  Sulfonated polyimide membranes grafted with sulfoalkylated side chains for proton exchange membrane fuel cell (PEMFC) applications , 2008 .

[41]  B. Pivovar,et al.  Moving beyond mass-based parameters for conductivity analysis of sulfonated polymers. , 2010, Annual review of chemical and biomolecular engineering.

[42]  Jing Li,et al.  Linear coupling of alignment with transport in a polymer electrolyte membrane. , 2011, Nature materials.

[43]  Chaoyang Wang,et al.  Transport properties and fuel cell performance of sulfonated poly(imide) proton exchange membranes , 2012 .

[44]  J. Mcgrath,et al.  Synthesis and characterization of multiblock semi-crystalline hydrophobic poly(ether ether ketone)–hydrophilic disulfonated poly(arylene ether sulfone) copolymers for proton exchange membranes , 2012 .

[45]  K. Sakurai,et al.  Crystal morphology and polymorphism of a wholly aromatic thermoplastic polymer, poly (ketone sulfide) , 1998 .

[46]  J. Maier,et al.  Highly Sulfonated Poly(phenylene sulfone): Preparation and Stability Issues , 2009 .

[47]  Y. Lee,et al.  Synthesis of Crosslinked Sulfonated Poly(phenylene sulfide sulfone nitrile) for Direct Methanol Fuel Cell Applications. , 2009, Macromolecular rapid communications.

[48]  M. Hickner,et al.  Alternative polymer systems for proton exchange membranes (PEMs). , 2004, Chemical reviews.

[49]  K. Miyatake,et al.  Effect of the Hydrophobic Component on the Properties of Sulfonated Poly(arylene ether sulfone)s , 2009 .