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关于聚醋酸乙烯酯-高氯酸锂聚合物电解质中锂离子相互作用的激光拉曼光谱和傅里叶变换红外光谱研究。

Laser Raman and FTIR studies on Li+ interaction in PVAc-LiClO4 polymer electrolytes.

作者信息

Selvasekarapandian S, Baskaran R, Kamishima O, Kawamura J, Hattori T

机构信息

Solid State and Radiation Physics Laboratory, Department of Physics, Bharathiar University, Coimbatore-641 046, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2006 Dec;65(5):1234-40. doi: 10.1016/j.saa.2006.02.026. Epub 2006 Mar 2.

Abstract

The polymer electrolytes composed of poly(vinyl acetate) (PVAc) with various stoichiometric ratios of lithium perchlorate (LiClO(4)) salt have been prepared by solution casting method. The techniques Fourier transform infra-red (FTIR) and Laser Raman spectroscopy have been used to monitor polymer-salt complex formation, ion-ion and ion-polymer interactions as a function of salt concentration. Significant changes in both Laser Raman and FTIR spectra are observed which reveals an interaction between ester oxygens with lithium cation coordination. These results strongly suggest the interaction of lithium cation and network polymer chains. When the salt content is increased, the intensity of the internal Raman modes of the ClO(4)(-) increases. The ClO(4)(-) stretching mode observed at 934 cm(-1) in Laser Raman shows some additional shoulder peaks with increase in salt concentration. This reveals the presence of free anions, ion contact pairs and higher order ionic clusters. From the FTIR and Laser Raman results the transport mechanism of ions in PVAc:LiClO(4) polymer electrolytes has been discussed.

摘要

通过溶液浇铸法制备了由聚醋酸乙烯酯(PVAc)与不同化学计量比的高氯酸锂(LiClO₄)盐组成的聚合物电解质。傅里叶变换红外(FTIR)和激光拉曼光谱技术已被用于监测聚合物-盐络合物的形成、离子-离子和离子-聚合物相互作用随盐浓度的变化。观察到激光拉曼光谱和FTIR光谱都有显著变化,这揭示了酯氧与锂阳离子配位之间的相互作用。这些结果有力地表明了锂阳离子与网络聚合物链之间的相互作用。当盐含量增加时,ClO₄⁻的内部拉曼模式强度增加。在激光拉曼光谱中934 cm⁻¹处观察到的ClO₄⁻伸缩模式随着盐浓度的增加出现了一些额外的肩峰。这揭示了游离阴离子、离子接触对和高阶离子簇的存在。根据FTIR和激光拉曼结果,讨论了离子在PVAc:LiClO₄聚合物电解质中的传输机制。

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