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基于聚合物 PVdF-HFP 和离子液体 [BMIM][BF4] 的聚合物凝胶膜的热稳定性、络合行为和离子传输。

Thermal stability, complexing behavior, and ionic transport of polymeric gel membranes based on polymer PVdF-HFP and ionic liquid, [BMIM][BF4].

机构信息

Department of Physics, Banaras Hindu University, Varanasi-221005, India.

出版信息

J Phys Chem B. 2013 Jan 24;117(3):897-906. doi: 10.1021/jp307694q. Epub 2013 Jan 10.

Abstract

PVdF-HFP + IL(1-butyl-3-methylimidazolium tetrafluoroborate; [BMIM][BF(4)]) polymeric gel membranes containing different amounts of ionic liquid have been synthesized and characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared (FTIR), differential scanning calorimetry, thermogravimetric analysis (TGA), and complex impedance spectroscopic techniques. Incorporation of IL in PVdF-HFP polymer changes different physicochemical properties such as melting temperature (T(m)), thermal stability, structural morphology, amorphicity, and ionic transport. It is shown by FTIR, TGA (also first derivative of TGA, "DTGA") that IL partly complexes with the polymer PVdF-HFP and partly remains dispersed in the matrix. The ionic conductivity of polymeric gel membranes has been found to increase with increasing concentration of IL and attains a maximum value of 1.6 × 10(-2) S·cm(-1) for polymer gel membrane containing 90 wt % IL at room temperature. Interestingly, the values of conductivity of membranes with 80 and 90 wt % of IL were higher than that of pure IL (100 wt %). The polymer chain breathing model has been suggested to explain it. The variation of ionic conductivity with temperature of these gel polymeric membranes follows Arrhenius type thermally activated behavior.

摘要

已合成并通过 X 射线衍射、扫描电子显微镜、傅里叶变换红外(FTIR)、差示扫描量热法、热重分析(TGA)和复阻抗光谱技术对含有不同含量离子液体的 PVdF-HFP+IL(1-丁基-3-甲基咪唑四氟硼酸盐;[BMIM][BF4])聚合凝胶膜进行了表征。IL 的加入改变了 PVdF-HFP 聚合物的不同物理化学性质,如熔融温度(Tm)、热稳定性、结构形态、非晶性和离子传输。FTIR、TGA(也即 TGA 的一阶导数,“DTGA”)表明,IL 部分与聚合物 PVdF-HFP 络合,部分仍分散在基质中。发现聚合凝胶膜的离子电导率随 IL 浓度的增加而增加,在室温下,含 90wt%IL 的聚合物凝胶膜的电导率达到 1.6×10-2S·cm-1的最大值。有趣的是,含 80wt%和 90wt%IL 的膜的电导率值高于纯 IL(100wt%)的电导率值。提出了聚合物链呼吸模型来解释这一点。这些凝胶聚合物膜的离子电导率随温度的变化遵循阿伦尼乌斯型热激活行为。

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