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首页> 外文期刊>Chemphyschem: A European journal of chemical physics and physical chemistry >Fluoride-ion-conducting Polymers: Ionic Conductivity and Fluoride Ion Diffusion Coefficient in Quaternized Polysulfones
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Fluoride-ion-conducting Polymers: Ionic Conductivity and Fluoride Ion Diffusion Coefficient in Quaternized Polysulfones

机译:氟离子导电聚合物:季铵化聚砜中的离子电导率和氟离子扩散系数

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摘要

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.
机译:我们描述了基于完全芳族聚合物聚砜(PSU)的新型聚合物氟离子导体的三步合成。第一步,使用毒性低于标准程序中所用的试剂(即氯化锡,多聚甲醛和三甲基氯硅烷)对PSU进行氯甲基化(CM-PSU)。在第二步中,CM-PSU与叔胺(三甲胺或1,4-二氮杂双环[2.2.2]辛烷)反应,形成固定在PSU主链和移动氯离子抗衡阴离子上的季铵基团。在第三步骤中,通过将离聚物浸入NaF​​溶液中,可以使氯离子与氟离子交换。氟离子的电导率在25摄氏度时达到3-5 mScm(-​​1),在40摄氏度时达到5-10 mScm(-​​1)。我们通过脉冲梯度自旋回波(PGSE)确定了这些离聚物的F-扩散系数高分辨率魔角旋转(HRMAS)核磁共振(NMR)光谱,以及使用Nernst-Einstein关系的阻抗光谱。两种方法确定的扩散系数吻合良好,范围从2到4 x 10(-10)m(2)s(-1)。可以估计离聚物膜的孔隙率和曲折度。

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