Synthesis of sulfonated poly(fluorenyl ether thioether ketone)s with bulky-block structure and its application in vanadium redox flow battery

Abstract High-molecular-weight bulky-block poly(fluorenyl ether thioether ketone)s were successfully synthesized by a two steps one-pot protocol using N,N′ -dimethy- S -carbamate masked dithiols for vanadium redox flow battery (VRB) application. The followed sulfonation procedure gave birth to novel sulfonated block poly(fluorenyl ether thioether ketone)s (SPFETKs) with controlled ionic exchange capacities (IEC). Membranes with proton conductivities higher than (IEC > 1.66 mequiv. g −1 ) or comparable to (IEC  −1 ) that of Nafion117 membrane were achieved. The VO 2+ permeabilities of SPFETKs membranes were much lower than that of Nafion117 membrane. The thermal properties, mechanical properties, oxidative stability, water uptake, proton conductivity, VO 2+ permeability and cell performance were investigated in detail.

[1]  I. Oh,et al.  Enhanced electromechanical performance of carbon nano-fiber reinforced sulfonated poly(styrene-b-[ethylene/butylene]-b-styrene) actuator , 2009 .

[2]  Antonino S. Aricò,et al.  Investigation of a direct methanol fuel cell based on a composite Nafion®-silica electrolyte for high temperature operation , 1999 .

[3]  R. Lichtenthaler,et al.  Transport properties of vanadium ions in cation exchange membranes:: Determination of diffusion coefficients using a dialysis cell , 1998 .

[4]  Xianfeng Li,et al.  Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application , 2011 .

[5]  Min Xiao,et al.  Synthesis and characterization of novel sulfonated poly(arylene thioether) ionomers for vanadium redox flow battery applications , 2010 .

[6]  Maria Skyllas-Kazacos,et al.  Recent advances with UNSW vanadium‐based redox flow batteries , 2010 .

[7]  S. Badwal,et al.  High purity oxygen production with a polymer electrolyte membrane electrolyser , 2010 .

[8]  Jianguo Liu,et al.  A significantly improved membrane for vanadium redox flow battery , 2010 .

[9]  M. Xiao,et al.  Synthesis and characterization of sulfonated fluorene-containing poly(arylene ether ketone) for high temperature proton exchange membrane , 2006 .

[10]  K. Miyatake,et al.  Synthesis and properties of sulfonated block copolymers having fluorenyl groups for fuel-cell applications. , 2009, ACS applied materials & interfaces.

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

[12]  Michael A. Hickner,et al.  Ionomeric Poly(phenylene) Prepared by Diels−Alder Polymerization: Synthesis and Physical Properties of a Novel Polyelectrolyte , 2005 .

[13]  Min Xiao,et al.  Preparation and properties of sulfonated poly(fluorenyl ether ketone) membrane for vanadium redox flow battery application , 2010 .

[14]  Jing Peng,et al.  Performance of vanadium redox flow battery with a novel amphoteric ion exchange membrane synthesized by two-step grafting method , 2009 .

[15]  Lawrence F. Drummy,et al.  Synthesis and Characterization of Multiblock Sulfonated Poly(arylenethioethersulfone) Copolymers for Proton Exchange Membranes , 2008 .

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

[17]  Y. Elabd,et al.  Polymer electrolyte membranes for the direct methanol fuel cell: A review , 2006 .

[18]  A. S. Hay,et al.  Novel synthesis of poly(arylene thioether)s via one-pot polymerization of bis(N,N′-dimethyl-S-carbamate)s with activated dihalo aromatic compounds , 1997 .

[19]  J. Maier,et al.  Sulfonated Poly(phenylene sulfone) Polymers as Hydrolytically and Thermooxidatively Stable Proton Conducting Ionomers , 2007 .

[20]  Wenzheng Li,et al.  Nafion/Zeolite Nanocomposite Membrane by in Situ Crystallization for a Direct Methanol Fuel Cell , 2006 .

[21]  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 .

[22]  Xinping Qiu,et al.  Nafion/organic silica modified TiO2 composite membrane for vanadium redox flow battery via in situ sol–gel reactions , 2009 .

[23]  P. Jannasch,et al.  Sulfonated poly(arylene ether sulfone) ionomers containing di- and tetrasulfonated arylene sulfone segments , 2011 .

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

[25]  K. Miyatake,et al.  Novel Sulfonated Poly(arylene ether): A Proton Conductive Polymer Electrolyte Designed for Fuel Cells , 2003 .

[26]  Xinping Qiu,et al.  Self-assembled polyelectrolyte multilayer modified Nafion membrane with suppressed vanadium ion crossover for vanadium redox flow batteries , 2008 .

[27]  M. Xiao,et al.  Fluorene-containing block sulfonated poly(ether ether ketone) as proton-exchange membrane for PEM fuel cell application , 2010 .

[28]  Ram Devanathan,et al.  Recent developments in proton exchange membranes for fuel cells , 2008 .

[29]  Tomonori Saito,et al.  Morphology and transport properties of midblock-sulfonated triblock copolymers , 2010 .

[30]  Hongchao Mao,et al.  Synthesis of highly sulfonated poly(arylene ether sulfone)s with sulfonated triptycene pendants for proton exchange membranes , 2011 .

[31]  M. Xiao,et al.  Poly (fluorenyl ether ketone) ionomers containing separated hydrophilic multiblocks used in fuel cells as proton exchange membranes , 2010 .