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不同增塑的聚环氧乙烷/聚偏氟乙烯-六氟丙烯共混固体聚合物电解质中的载流子弛豫

Charge Carrier Relaxation in Different Plasticized PEO/PVDF-HFP Blend Solid Polymer Electrolytes.

作者信息

Das S, Ghosh A

机构信息

Department of Solid State Physics, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700032, India.

出版信息

J Phys Chem B. 2017 Jun 1;121(21):5422-5432. doi: 10.1021/acs.jpcb.7b02277. Epub 2017 May 19.

Abstract

In this article, we report first the effect of concentration of ethylene carbonate plasticizer on conduction and relaxation of charge carriers in PEO/PVDF-HFP-LiClO blend electrolytes. Second, the results for different plasticizers, such as ethylene carbonate, propylene carbonate, and dimethyle carbonate, on the conductivity and relaxation in these blend electrolytes are compared. We have followed a new approach for the analysis of the conductivity data. The frequency dependent conductivity is analyzed using random free-energy barrier model, taking into consideration the low frequency polarization effect. The temperature dependences of the ionic conductivity and the relaxation time obtained from the model exhibit Vogel-Tammann-Fulcher behavior. Using the scaling of the ac conductivity spectra it is observed that the relaxation dynamics of charge carriers in blend electrolytes are independent of temperature but depend on the nature of plasticizers. The electric modulus is studied using Havriliak-Negami function for the understanding of ionic relaxation. The modulus data are also analyzed using nonexponential Kohlrausch-Williams-Watts function. The temperature dependence of the relaxation time obtained from modulus analysis follows Vogel-Tammann-Fulcher relation for all plasticized electrolytes. It is observed that the stretched exponent is much lower than unity, which suggests that charge carrier relaxation is highly nonexponential in these plasticized electrolytes.

摘要

在本文中,我们首先报道了碳酸亚乙酯增塑剂浓度对PEO/PVDF-HFP-LiClO混合电解质中载流子传导和弛豫的影响。其次,比较了不同增塑剂,如碳酸亚乙酯、碳酸亚丙酯和碳酸二甲酯,对这些混合电解质电导率和弛豫的影响。我们采用了一种新的方法来分析电导率数据。利用随机自由能垒模型分析频率依赖电导率,并考虑低频极化效应。从该模型得到的离子电导率和弛豫时间的温度依赖性呈现出Vogel-Tammann-Fulcher行为。通过交流电导率谱的标度关系观察到,混合电解质中载流子的弛豫动力学与温度无关,但取决于增塑剂的性质。使用Havriliak-Negami函数研究电模量以理解离子弛豫。模量数据也使用非指数Kohlrausch-Williams-Watts函数进行分析。从模量分析得到的弛豫时间的温度依赖性对于所有增塑电解质都遵循Vogel-Tammann-Fulcher关系。观察到伸展指数远低于1,这表明在这些增塑电解质中载流子弛豫是高度非指数的。

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