论文标题
聚合物电解质中的转移编号：请注意参考框架间隙
Transference number in polymer electrolytes: mind the reference-frame gap
论文作者
论文摘要
电解质溶液的传输系数，尤其是转移数量，是电化学能源存储设备的重要设计参数。在某些条件下，最近观察到PEO-LITFSI中的负转移数量已经通过实验和理论手段引起了有关其分子起源的很多讨论。但是，这些努力的一个被忽视的因素是参考框架（RF）的重要性。在比较实验和模拟时，这会产生不可忽略的差距，因为在不同的RF中定义了传输系数的实验测量中的通量以及分子动力学模拟中使用的线性响应理论。在这项工作中，我们表明，通过应用适当的RF转换，可以实现实验和仿真结果之间的一致性。此外，据揭示了阴离子质量和阴离子 - 动物相关性而不是离子聚集体对报告的负转移数字起着至关重要的作用。
The transport coefficients, in particular the transference number, of electrolyte solutions are important design parameters for electrochemical energy storage devices. Recent observation of negative transference numbers in PEO-LiTFSI under certain conditions has generated much discussion about its molecular origins, by both experimental and theoretical means. However, one overlooked factor in these efforts is the importance of the reference frame (RF). This creates a non-negligible gap when comparing experiment and simulation, because the fluxes in the experimental measurements of transport coefficients and in the linear response theory used in the molecular dynamics simulation are defined in different RFs. In this work, we show that by applying a proper RF transformation, a much improved agreement between experimental and simulation results can be achieved. Moreover, it is revealed that the anion mass and the anion-anion correlation, rather than ion aggregates, play a crucial role for the reported negative transference numbers.
