基于分子动力学模拟的 Bruce–Vincent 迁移数
Bruce-Vincent transference numbers from molecular dynamics simulations
AI总结：
本文利用 Onsager 系数推导浓电解质的 Bruce–Vincent 迁移数，并以 PEO-LiTFSI 为例说明可借此校准 MD 模拟并预测真实迁移数。
摘要：
迁移数是电化学储能系统中电解质材料的一项关键设计参数。然而，通过实验测定真实迁移数相当困难。另一方面，Bruce–Vincent 方法在实验室中被广泛用于近似测量聚合物电解质的迁移数，该方法在无限稀释极限下才变得精确。因此，显然需要能够在同等基础上处理 Bruce–Vincent 迁移数与真实迁移数的理论表述。在此，我们展示如何依据 Onsager 系数推导浓电解质溶液的 Bruce–Vincent 迁移数，而无需引入任何超热力学假设。通过以 PEO-LiTFSI 体系为例进行论证，这项工作为以下方向打开了大门：通过复现 Bruce–Vincent 迁移数来校准分子动力学（MD）模拟，并将 MD 模拟用作确定真实迁移数的预测工具。
英文摘要：
Transference number is a key design parameter for electrolyte materials used in electrochemical energy storage systems. However, the determination of the true transference number from experiments is rather demanding. On the other hand, the Bruce-Vincent method is widely used in the lab to measure transference numbers of polymer electrolytes approximately, which becomes exact in the limit of infinite dilution. Therefore, theoretical formulations to treat the Bruce-Vincent transference number and the true transference number on an equal footing are clearly needed. Here we show how the Bruce-Vincent transference number for concentrated electrolyte solutions can be derived in terms of the Onsager coefficients, without involving any extrathermodynamic assumptions. By demonstrating it for the case of PEO-LiTFSI system, this work opens the door to calibrating molecular dynamics (MD) simulations via reproducing the Bruce-Vincent transference number and using MD simulations as a predictive tool for determining the true transference number.
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