On the extraction of ion association data and transference numbers from ionic diffusivity and conductivity data in polymer electrolytes
On the extraction of ion association data and transference numbers from ionic diffusivity and conductivity data in polymer electrolytes
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从聚合物电解质中离子扩散率和电导率数据中提取离子缔合数据和迁移数
DOI：
10.1016/j.electacta.2013.04.028
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发表时间：
2013
影响因子：
6.6
通讯作者：
M. Schönhoff
中科院分区：
文献类型：
--
作者：
N. Stolwijk;J. Kösters;M. Wiencierz;M. Schönhoff
聚合物电解质中的离子缔合程度通常由能斯特-爱因斯坦偏差参数Δ表征，该参数量化了通过电学方法直接测量的真实离子电导率与根据单个离子自扩散系数计算的假设最大电导率之间的相对差异。尽管定义明确，但参数Δ是一个解释力有限的全局量。类似的情况也适用于阳离子迁移数tcat*，它依赖于通常通过核磁共振或放射性示踪剂方法测量的相同离子扩散系数。特别是在中性离子对主导高阶聚集体的情况下，可以从用于计算Δ和tcat* 的相同实验数据体中提取更具体的信息。该信息涉及对阳离子和阴离子的扩散系数的贡献。此外，可以推导出真正的阳离子迁移数的基础上的带电物种。我们提出了基本的理论框架和一些有关的例子处理离子配对的聚合物电解质。
The degree of ion association in polymer electrolytes is often characterized by the Nernst–Einstein deviation parameter Δ, which quantifies the relative difference between the true ionic conductivity directly measured by electrical methods and the hypothetical maximum conductivity calculated from the individual ionic self-diffusion coefficients. Despite its unambiguous definition, the parameter Δ is a global quantity with limited explanatory power. Similar is true for the cation transport number tcat*, which relies on the same ionic diffusion coefficients usually measured by nuclear magnetic resonance or radiotracer methods. Particularly in cases when neutral ion pairs dominate over higher-order aggregates, more specific information can be extracted from the same body of experimental data that is used for the calculation of Δ and tcat*. This information concerns the pair contributions to the diffusion coefficient of cations and anions. Also the true cation transference number based on charged species only can be deduced. We present the basic theoretical framework and some pertinent examples dealing with ion pairing in polymer electrolytes.
DOI：
10.1021/jp2111956
发表时间：
2012-02
期刊：
The journal of physical chemistry. B
影响因子：
--
作者：
N. Stolwijk;M. Wiencierz;Christian Heddier;J. Kösters
通讯作者：
N. Stolwijk;M. Wiencierz;Christian Heddier;J. Kösters