Anion-Conductive Multiblock Aromatic Copolymer Membranes: Structure–Property Relationships

Anion-conductive multiblock copoly(arylene ether sulfone)s (mPES) were synthesized with different block lengths and ion-exchange capacities (IEC) to maximize ion conductivity and explore the relationship between chemical structure and morphology in anion-exchange membranes (AEM). Nuclear magnetic resonance (NMR) relaxometry was used to probe water mobility and domain size. The multiblock copolymers were synthesized by polycondensation of separately prepared hydroxy-terminated oligomers with fluoro-terminated oligomers. The polymers were made ion-conductive through selective chloromethylation of one of the two block types, followed by quaternization and hydroxide ion exchange. The resulting block structure, in which one type is hydrophilic and one type is hydrophobic, was designed to ensure a nanophase-separated morphology. The multiblock copolymers exhibited higher anion conductivity than their random copolymer counterparts at the same IEC. The multiblock copolymer that exhibited the highest anion conduct...

[1]  P. Kohl,et al.  Anionic polysulfone ionomers and membranes containing fluorenyl groups for anionic fuel cells , 2009 .

[2]  Tomoya Higashihara,et al.  Locally and Densely Sulfonated Poly(ether sulfone)s as Proton Exchange Membrane , 2009 .

[3]  Manabu Tanaka,et al.  Anion conductive block poly(arylene ether)s: synthesis, properties, and application in alkaline fuel cells. , 2011, Journal of the American Chemical Society.

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

[5]  J. Fauvarque,et al.  Characterization and use of anionic membranes for alkaline fuel cells , 2001 .

[6]  Koji Yamada,et al.  A platinum-free zero-carbon-emission easy fuelling direct hydrazine fuel cell for vehicles. , 2007, Angewandte Chemie.

[7]  J. Mcgrath,et al.  Hydrophilic–hydrophobic multiblock copolymers based on poly(arylene ether sulfone)s as novel proton exchange membranes – Part B , 2008 .

[8]  K. Miyatake,et al.  Aromatic ionomers with superacid groups. , 2009, Chemical communications.

[9]  Robert B. Moore,et al.  State of understanding of nafion. , 2004, Chemical reviews.

[10]  Jing Pan,et al.  High‐Performance Alkaline Polymer Electrolyte for Fuel Cell Applications , 2010 .

[11]  James Larminie,et al.  Fuel Cell Systems Explained: Larminie/Fuel Cell Systems Explained , 2003 .

[12]  Masahiro Watanabe,et al.  Sulfonated Poly(arylene ether sulfone ketone) Multiblock Copolymers with Highly Sulfonated Block. Synthesis and Properties , 2010 .

[13]  Timothy J. Peckham,et al.  Main-chain, statistically sulfonated proton exchange membranes: the relationships of acid concentration and proton mobility to water content and their effect upon proton conductivity , 2007 .

[14]  Ken Yoshimura,et al.  Aromatic Polymer with Pendant Perfluoroalkyl Sulfonic Acid for Fuel Cell Applications , 2009 .

[15]  Timothy J. Peckham,et al.  Structure‐Morphology‐Property Relationships of Non‐Perfluorinated Proton‐Conducting Membranes , 2010, Advanced materials.

[16]  G. Ranieri,et al.  NMR investigation of the dynamics of confined water in nafion-based electrolyte membranes at subfreezing temperatures. , 2009, The journal of physical chemistry. B.

[17]  Lianjun Wang,et al.  Graft-crosslinked copolymers based on poly(arylene ether ketone)-gc-sulfonated poly(arylene ether sulfone) for PEMFC applications. , 2011, Macromolecular rapid communications.

[18]  J. Mcgrath,et al.  Hydrophilic–hydrophobic multiblock copolymers based on poly(arylene ether sulfone) via low-temperature coupling reactions for proton exchange membrane fuel cells , 2008 .

[19]  Dc Kitty Nijmeijer,et al.  Anion exchange membranes for alkaline fuel cells: A review , 2011 .

[20]  Hyea Kim,et al.  Solvent processible, high-performance partially fluorinated copoly(arylene ether) alkaline ionomers , 2011 .

[21]  O. Diat,et al.  Proton channels. , 2008, Nature materials.

[22]  K. Kreuer On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells , 2001 .

[23]  T. Cosgrove,et al.  Microscopic Signature of a Microgel Volume Phase Transition , 2005 .

[24]  Zhenhua Jiang,et al.  Sequence analysis of poly (ether sulfone) copolymers by 13C NMR , 2005 .

[25]  B. Améduri,et al.  Polymeric materials as anion-exchange membranes for alkaline fuel cells , 2011 .

[26]  Hiroyuki Uchida,et al.  Proton-conductive aromatic ionomers containing highly sulfonated blocks for high-temperature-operable fuel cells. , 2010, Angewandte Chemie.

[27]  Zhiqing Shi,et al.  Nanostructure, Morphology, and Properties of Fluorous Copolymers Bearing Ionic Grafts , 2009 .

[28]  Xianfeng Li,et al.  Morphological investigations of block sulfonated poly(arylene ether ketone) copolymers as potential proton exchange membranes , 2011 .

[29]  Phatiphat Thounthong,et al.  Control strategy of fuel cell/supercapacitors hybrid power sources for electric vehicle , 2006 .

[30]  R. Shankar,et al.  1D and 2D NMR studies of isobornyl acrylate – Methyl methacrylate copolymers , 2011 .

[31]  P. Kohl,et al.  Hybrid polymer electrolyte fuel cells: alkaline electrodes with proton conducting membrane. , 2010, Angewandte Chemie.

[32]  James Larminie,et al.  Fuel Cell Systems Explained , 2000 .

[33]  K. Sanui,et al.  Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers , 2000 .

[34]  Gang Zhang,et al.  Block sulfonated poly(arylene ether ketone) containing flexible side-chain groups for direct methanol fuel cells usage , 2012 .

[35]  Rongrong Chen,et al.  Developing a polysulfone-based alkaline anion exchange membrane for improved ionic conductivity , 2009 .