论文标题
基于音量的不可压缩液体电解质中的传输及其在离子液体中的应用
A Volume-based Description of Transport in Incompressible Liquid Electrolytes and its Application to Ionic Liquids
论文作者
论文摘要
转移数对于理解电解质的动态和评估其在电池中的性能是重要的作用。不幸的是,这些传输参数在高度浓缩的液体电解质(例如离子液体)中很难测量。同样,对它们的迹象和幅度的解释引发了文献中持续的辩论,这种辩论因使用不同语言而变得更加复杂。在这项工作中,我们强调了参考框架使用我们的新型热力学一致理论来解释传输参数的作用,用于高度相关的电解质。我们认为,局部体积保护是不可压缩液体电解质的关键原理,并使用基于体积的漂移速度作为参考。我们将一般框架应用于电泳NMR实验。对于离子液体基电解质,我们发现可以使用此基于卷的描述最好地描述ENMR测量结果。这突出了广泛使用的质量参考框架的局限性,例如,它构成了分子动力学模拟的基础 - 传输参数的理论计算的标准工具。它表明,在宏观量表上那些系统中,局部动量保护的假设是不正确的。
Transference numbers play an important role for understanding the dynamics of electrolytes and assessing their performance in batteries. Unfortunately, these transport parameters are difficult to measure in highly concentrated, liquid electrolytes such as ionic liquids. Also, the interpretation of their sign and magnitude has provoked an ongoing debate in the literature further complicated by the use of different language. In this work, we highlight the role of the reference frame for the interpretation of transport parameters using our novel thermodynamically consistent theory for highly correlated electrolytes. We argue that local volume conservation is a key principle in incompressible liquid electrolytes and use the volume-based drift velocity as reference. We apply our general framework to electrophoretic NMR experiments. For ionic liquid based electrolytes, we find that the results of the eNMR measurements can be best described using this volume-based description. This highlights the limitations of the widely used center-of-mass reference frame which for example forms the basis for molecular dynamics simulations - a standard tool for the theoretical calculation of transport parameters. It shows that the assumption of local momentum conservation is incorrect in those systems on the macroscopic scale.