title: 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 mS cm(-1) at 25 °C and 5-10 mS cm(-1) at 40 °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 4×10(-10)  m(2)  s(-1) . The porosity and tortuosity of the ionomer membranes can be estimated.
authors.affiliation: Aix Marseille University, CNRS, MADIREL (UMR 7246), Campus St Jerome, F-13397, Marseille, France.|University of Rome Tor Vergata, Department of Chemical Sciences and Technologies, Via della Ricerca Scientifica 1, 00133, Roma, Italy.
authors.forename: Luca
authors.initials: L
authors.lastname: Pasquini
authors.affiliation: Aix Marseille University, Centrale Marseille, CNRS, Fédération des Sciences Chimiques de Marseille (FR 1739), Campus St Jerome, F-13397, Marseille, France.
authors.forename: Fabio
authors.initials: F
authors.lastname: Ziarelli
authors.affiliation: Aix Marseille University, CNRS, Institut de Chimie Radicalaire (UMR 7273), Campus St Jerome, F-13397, Marseille, France.|Institut Universitaire de France, 75000, Paris, France.
authors.forename: Stéphane
authors.initials: S
authors.lastname: Viel
authors.affiliation: University of Rome Tor Vergata, Department of Chemical Sciences and Technologies, Via della Ricerca Scientifica 1, 00133, Roma, Italy.
authors.forename: Maria Luisa
authors.initials: ML
authors.lastname: Di Vona
authors.affiliation: Aix Marseille University, CNRS, MADIREL (UMR 7246), Campus St Jerome, F-13397, Marseille, France. philippe.knauth@univ-amu.fr.
authors.forename: Philippe
authors.initials: P
authors.lastname: Knauth
keywords: NMR spectroscopy; fluoride ions; impedance spectroscopy; ionic conductors; polymers