Proton-conducting membranes based on side-chain-type sulfonated poly(ether ketone/ether benzimidazole)s via one-pot condensation

Abstract A series of side-chain-type sulfonated poly(ether ketone/ether benzimidazole)s containing side-chain sulfonate groups and main-chain benzimidazole rings were successfully synthesized via benzimidazolization and acylation in a one-pot method. By varying the amount of sulfonate monomers, the ratio of sulfonate acid unit to benzimidazole base unit was easily controlled. 1 H NMR and IR spectra were used to characterize the polymer structure. The resulting membranes exhibited excellent mechanical properties (11–45 MPa tensile stress and 9–23% elongation at break) and good thermal stability. The proton conductivity of SPEKEBI-4 was136 mS cm −1 at 30 °C, much higher than Nafion ® 115 membrane; while the methanol permeabilities of all the membranes were lower than Nafion ® 115 membrane. Moreover, the passive direct methanol fuel cells (DMFCs) with SPEKEBI-2 membrane exhibited a maximum power density of 39.3 mW cm −2 at 25 °C, which show great potential for application in polymer electrolyte membrane fuel cells.

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

[2]  Ronghuan He,et al.  PBI‐Based Polymer Membranes for High Temperature Fuel Cells – Preparation, Characterization and Fuel Cell Demonstration , 2004 .

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

[4]  Tongwen Xu,et al.  One-pot acylation/benzimidazolization copolymerization approach to side-chain-type proton conductive membranes , 2013 .

[5]  D. Yan,et al.  Synthesis and properties of soluble sulfonated polybenzimidazoles , 2006 .

[6]  D. Yan,et al.  Synthesis and characterization of thermally stable sulfonated polybenzimidazoles obtained from 3,3′‐disulfonyl‐4,4′‐dicarboxyldiphenylsulfone , 2005 .

[7]  D. Yan,et al.  Synthesis and properties of soluble sulfonated polybenzimidazoles from 3,3′-disulfonate-4,4′-dicarboxylbiphenyl as proton exchange membranes , 2009 .

[8]  Liang Wu,et al.  Novel sulfonated polyimides proton-exchange membranes via a facile polyacylation approach of imide monomers , 2014 .

[9]  J. Reynolds,et al.  Water-soluble polybenzimidazole-based polyelectrolytes , 1992 .

[10]  Qinghong Huang,et al.  Cathode Catalyst Layer with Stepwise Hydrophobicity Distribution for a Passive Direct Methanol Fuel Cell , 2012 .

[11]  N. Ogata,et al.  Synthesis and proton conductivity of sulfopropylated poly(benzimidazole) films , 2000 .

[12]  Jesse S. Wainright,et al.  High–temperature membranes , 2010 .

[13]  Liang Wu,et al.  Novel aromatic proton-exchange polyelectrolytes via polyacylation of pre-sulfonated monomers , 2012 .

[14]  C. Marvel,et al.  Polybenzimidazoles, new thermally stable polymers , 1961 .

[15]  Jesse S. Wainright,et al.  Acid-doped polybenzimidazoles : a new polymer electrolyte , 1995 .

[16]  Deborah J. Jones,et al.  Synthesis of novel proton‐conducting highly sulfonated polybenzimidazoles for PEMFC and the effect of the type of bisphenyl bridge on polymer and membrane properties , 2011 .

[17]  Brian C. Benicewicz,et al.  Sulfonated Polybenzimidazoles for High Temperature PEM Fuel Cells , 2010 .

[18]  Deborah J. Jones,et al.  Synthesis and characterisation of sulfonated polybenzimidazole: a highly conducting proton exchange polymer , 1997 .

[19]  Deborah J. Jones,et al.  Non-Fluorinated Polymer Materials for Proton Exchange Membrane Fuel Cells , 2003 .

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

[21]  P. Gómez‐Romero,et al.  Proton‐conducting polymers based on benzimidazoles and sulfonated benzimidazoles , 2002 .

[22]  Pedro Gómez-Romero,et al.  Proton-conducting membranes based on benzimidazole polymers for high-temperature PEM fuel cells. A chemical quest. , 2010, Chemical Society reviews.

[23]  Jianli Wang,et al.  Characterization of molecular interaionic and intraionic crosslinkable sulfonated poly(ether ether ketone-alt-benzimidazole) membrane , 2012 .

[24]  Masahiro Watanabe,et al.  Synthesis and properties of a polyimide containing pendant sulfophenoxypropoxy groups , 2007 .

[25]  Jia Liu,et al.  Novel cardo poly(arylene ether sulfone)s with pendant sulfonated aliphatic side chains for proton ex , 2011 .

[26]  Li Sheng,et al.  Synthesis and properties of novel sulfonated polybenzimidazoles from disodium 4,6-bis(4-carboxyphenoxy)benzene-1,3-disulfonate , 2011 .

[27]  Zhibin Ye,et al.  Alternating Copolymer of Sulfonated Poly(ether ether ketone-benzimidazole)s (SPEEK-BI) Bearing Acid and Base Moieties , 2008 .