Synthesis and characterization of novel sulfonated poly(arylene thioether) ionomers for vanadium redox flow battery applications

High-molecular-weight poly(arylene thioether ketone) (PTK) and poly(arylene thioether ketone ketone) (PTKK) polymers were successfully synthesized by one-pot polymerization of N,N′-dimethy-S-carbamate masked dithiols with activated dihalo compounds, followed by post-sulfonation using chlorosulfonic acid as the sulfonation agent in dichloromethane solution to give the production of sulfonated poly(arylene thioether ketone) (SPTK) and sulfonated poly(arylene thioether ketone ketone) (SPTKK) with appropriate ion-exchange capacities. The chemical structures were confirmed by 1H NMR, FT-IR and elemental analysis (EA). The thermal properties were fully investigated by TGA-IR. The synthesized SPTK and SPTKK polymers are soluble in aprotic solvents such as N,N′-dimethylacetamide (DMAc), N,N′-dimethylformamide and dimethyl sulfoxide, and can be cast into membranes on a glass plate from their DMAc solution. The proton conductivities of these membranes are comparable to Nafion117 membranes under the same conditions. Cell performance tests showed that the vanadium redox flow batteries (VRBs) assembled with SPTK and SPTKK membranes possessed higher Coulombic efficiencies than VRBs assembled with Nafion117 membranes at the current density of 50 mA cm−2, because of their one-order-of magnitude lower VO2+ permeabilities. In conclusion, these ionomers could be promising candidates as proton-exchange membranes for vanadium redox flow battery (VRB) applications.

[1]  D. Yan,et al.  Synthesis and characterization of sulfonated poly(phthalazinone ether phosphine oxide)s by direct polycondensation for proton exchange membranes , 2008 .

[2]  Maria Skyllas-Kazacos,et al.  Fabrication and activation studies of conducting plastic composite electrodes for redox cells , 1991 .

[3]  Tomoya Higashihara,et al.  Star-Shaped Sulfonated Block Copoly(ether ketone)s as Proton Exchange Membranes , 2008 .

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

[5]  Toraj Mohammadi,et al.  Use of polyelectrolyte for incorporation of ion-exchange groups in composite membranes for vanadium redox flow battery applications , 1995 .

[6]  I. Vankelecom,et al.  Poly(sulfone)/sulfonated poly(ether ether ketone) blend membranes: Morphology study and application in the filtration of alcohol based feeds , 2008 .

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

[8]  G. Whitesides,et al.  Membraneless Vanadium Redox Fuel Cell Using Laminar Flow [J. Am. Chem. Soc. 2002, 124, 12930−12931]. , 2003 .

[9]  Y. Meng,et al.  Membranes from Poly(aryl ether)-Based Ionomers Containing Randomly Distributed Nanoclusters of 6 or 12 Sulfonic Acid Groups , 2009 .

[10]  M. Guiver,et al.  Comparative effect of phthalazinone units in sulfonated poly(arylene ether ether ketone ketone) copolymers as proton exchange membrane materials , 2008 .

[11]  B. Tian,et al.  Proton conducting composite membrane from Daramic/Nafion for vanadium redox flow battery , 2004 .

[12]  S. Holdcroft,et al.  Ionomers for Proton Exchange Membrane Fuel Cells with Sulfonic Acid Groups on the End Groups: Novel Branched Poly(ether−ketone)s , 2008 .

[13]  E. Higuchi,et al.  Tuned polymer electrolyte membranes based on aromatic polyethers for fuel cell applications. , 2007, Journal of the American Chemical Society.

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

[15]  M. Xiao,et al.  Fluorene-containing sulfonated poly(arylene ether 1,3,4-oxadiazole) as proton-exchange membrane for PEM fuel cell application , 2007 .

[16]  Haruhiko Ohya,et al.  Preparation of cation exchange membrane as a separator for the all-vanadium redox flow battery , 1996 .

[17]  Maria Skyllas-Kazacos,et al.  Modification of membranes using polyelectrolytes to improve water transfer properties in the vanadium redox battery , 2003 .

[18]  Huabing Yin,et al.  Separation of humic acid from a model surface water with PSU/SPEEK blend UF/NF membranes , 2002 .

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

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

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

[22]  M. Mulder,et al.  Characterization of polymer blends of polyethersulfone/sulfonated polysulfone and polyethersulfone/sulfonated polyetheretherketone for direct methanol fuel cell applications , 2002 .

[23]  Jian Chen,et al.  Modification of Nafion membrane using interfacial polymerization for vanadium redox flow battery applications , 2008 .

[24]  Maria Skyllas-Kazacos,et al.  Performance Characteristics of Carbon Plastic Electrodes in the All‐Vanadium Redox Cell , 1989 .

[25]  Y. Meng,et al.  Synthesis and characterization of sulfonated fluorene-containing poly(arylene ether ketone) for proton exchange membrane , 2005 .