Copoly(arylene ether)s Containing Pendant Sulfonic Acid Groups as Proton Exchange Membranes † NRCC Publication No. 50899.

Abstract

/npsi/ctrl?action=rtdoc&an=3538010&lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=3538010&lang=frAccess and use of this website and the material on it are subject to the Terms and Conditions set forth at http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://dx.doi.org/10.1021/ma802192y Macromolecules, 42, 4, pp. 957-963, 2009 Copoly(arylene ether)s containing pendant sulfonic acid groups as proton exchange membranes Kim, Dae Sik; Robertson, Gilles P.; Kim, Yu Seung; Guiver, Michael D. ReceiVed September 28, 2008; ReVised Manuscript ReceiVed December 19, 2008 ABSTRACT: A poly(arylene ether) (PAE) with high fluorine content and a poly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The PAE and PAEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2-phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. The sulfonic acid groups were introduced by mild postsulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sPAE and sPAEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (DS) of 1.0 had high ion exchange capacities (IEC v (wet) (volume-based, wet state)) of 1.77 and 2.55 mequiv/cm 3 , high proton conductivities of 135.4 and 140.1 mS/cm at 80°C, and acceptable volume-based water uptake of 44.5-51.9 vol %at80°C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the upper left-hand corner in the tradeoff plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based), i.e., high proton conductivity and low water uptake. Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion. Copoly(arylene ether)s Containing Pendant Sulfonic Acid Groups as IntroductionFuel cells are being pushed toward the brink of commercialization because they offer the potential of long operating lifetimes and the ability to refuel rather than recharge, as in the case of batteries typically used in portable power applications.

Polymer Electrolyte Membranes Derived from New Sulfone Monomers with Pendent Sulfonic Acid Groups

“…Our earlier work has shown that pendent phenyl rings attached to electron-donating polymer chain sites can be preferentially sulfonated at the para position, without obvious chain degradation occurring during sulfonation. [39][40][41][42][43] In the present study, the copolymers 2-PAES-60 and 4-PAES-20, having pendent phenyl groups on the electron-withdrawing site of the polymer chain were sulfonated on the para-phenyl position with chlorosulfonic acid to produce PS2-PAES-60 and PS4-PAES-20, respectively ("postsulfonation" is distinguished by PS). On the basis of experimental IEC w values, a 5-fold molar excess of chlorosulfonic acid was necessary for complete sulfonation.…”

Sulfonated Polystyrene Copolymer: Synthesis, Characterization and Its Application of Membrane for Direct Methanol Fuel Cell (DMFC)

“…The roughness of membrane before treatment showed rougher than that the membrane after treatment. This properties exposing the membrane to higher proton even for shorter times, indicating that this process depends mainly on the total amount of ionomer (proton) deposited to the system during the process treatment [15]. …”

Development of imidazolium-type alkaline anion exchange membranes for fuel cell application

“…This trend can be explained for two reasons: (1) The polymeric main chains will increase in flexibility at elevated temperatures (providing a larger free volume in favor of enhanced ion transport); 30 (2) Faster diffusion and thermal motion of hydroxide ions promote ion conduction at elevated temperatures (overcoming the activation energy for ion transport). 39,40 Of particular note, M-5 exhibited ionic conductivities above 100 mS cm -1 at 80°C: This shows that the alkali anion conductivities of AAEMs can approach the magnitude of H + conduction in PEMs.…”