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Fluoride-ion-conducting Polymers: Ionic Conductivity and Fluoride Ion Diffusion Coefficient in Quaternized Polysulfones

Abstract : We describe the three-step synthesis of a new polymeric fluoride ion conductor based on the fully aromatic polymer polysulfone (PSU). In the first step, PSU is chloromethylated (CM-PSU) using reagents (i.e., stannic chloride, paraformaldehyde, and trimethylchlorosilane) that are less toxic than those used in the standard procedure. In the second step, CM-PSU reacts with a tertiary amine (trimethylamine or 1,4-diazabicyclo[2.2.2]octane) to form quaternary ammonium groups fixed on the PSU backbone and mobile chloride counter-anions. The chloride ions can, in a third step, be exchanged with fluoride ions by immersion of the ionomer in NaF solution. The fluoride ion conductivity reaches 3-5 mScm(-1) at 25 degrees C and 5-10 mScm(-1) at 40 degrees C. We determined the F- diffusion coefficient in these ionomers by pulsed gradient spin-echo (PGSE) high-resolution magic angle spinning (HRMAS) nuclear magnetic resonance (NMR) spectroscopy and by impedance spectroscopy using the Nernst-Einstein relation. The diffusion coefficients determined by the two methods are in good agreement, ranging from 2 to 4 x 10(-10) m(2) s(-1). The porosity and tortuosity of the ionomer membranes can be estimated.
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https://hal-amu.archives-ouvertes.fr/hal-01415953
Contributor : Laurence Tortet <>
Submitted on : Tuesday, December 13, 2016 - 5:50:09 PM
Last modification on : Tuesday, January 30, 2018 - 12:28:02 PM

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Luca Pasquini, Fabio Ziarelli, Stéphane Viel, Maria Luisa Di vona, Philippe Knauth. Fluoride-ion-conducting Polymers: Ionic Conductivity and Fluoride Ion Diffusion Coefficient in Quaternized Polysulfones. ChemPhysChem, Wiley-VCH Verlag, 2015, 16 (17), pp.3631 - 3636. ⟨10.1002/cphc.201500643⟩. ⟨hal-01415953⟩

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