标题： 预测锂插层石墨边缘平面界面电化学过程的电压依赖性 显示英文标题

标题： Predicting the Voltage Dependence of Interfacial Electrochemical Processes at Lithium-Intercalated Graphite Edge Planes

摘要： 施加的电位控制锂离子电池中的锂插层和电极钝化反应，但在凝聚相DFT计算中校准具有挑战性。 在本工作中，使用从头算分子动力学（AIMD）、之前引入的Li+转移自由能方法以及实验测得的Li+/Li(s)值作为参考，计算了电中性锂插层石墨（LiC(6)）在氧化边缘平面处的“阳极电位”随锂含量n(Li)的变化情况。 通过来自氟代乙烯碳酸酯自由基阴离子标记物的显式电子转移，验证了电压分配。 显示PF6-在我们电压校准技术所施加的低电位下会发生电化学分解（即，不仅仅是热分解）。 我们证明过量电子存在于有机碳酸酯液态区域的带隙内局部态中，这与文献中普遍假设的半导体型（带态型）不同。 显示英文摘要

摘要： The applied potential governs lithium-intercalation and electrode passivation reactions in lithium ion batteries, but are challenging to calibrate in condensed phase DFT calculations. In this work, the "anode potential" of charge-neutral lithium-intercalated graphite (LiC(6)) with oxidized edge planes is computed as a function of Li-content n(Li)) at edge planes, using ab initio molecular dynamics (AIMD), a previously introduced Li+ transfer free energy method, and the experimental Li+/Li(s) value as reference. The voltage assignments are corroborated using explicit electron transfer from fluoroethylene carbonate radical anion markers. PF6- is shown to decompose electrochemically (i.e., not just thermally) at low potentials imposed by our voltage calibration technique. We demonstrate that excess electrons reside in localized states-in-the-gap in the organic carbonate liquid region, which is not semiconductor-like (band-state-like) as widely assumed in the literature.