电极-电解质界面的Marcus-Hush-Chidsey动力学
Marcus-Hush-Chidsey Kinetics at Electrode-Electrolyte Interfaces
摘要：
电极-电解质界面处的电化学动力学限制了包括燃料电池和蓄电池的装置的性能。虽然已经认识到超越Butler-Volmer动力学并将电极的电子态密度的影响纳入其中的重要性，但仍然缺乏将这些方面直接纳入电化学性能模型的统一框架。在这项工作中，我们明确占DFT计算的状态密度数值计算电化学反应速率的各种电极-电解质界面。我们首先示出了这两种情况下的实用程序，与Li金属电沉积和剥离在Li表面和Cu表面（无阳极配置）。反应速率的偏差是轻微的情况下，与平坦的状态密度，如锂，但由于非色散的d-带产生大的变化是显着的铜。最后，我们考虑了由LiF和Li $_2$ CO $_3$组成的固体电解质中间相（SEI）的半导体情况，并注意到界面处的费米能级的重要性，由那里发生的氧化还原反应钉扎。我们确定的不对称性反应速率的函数放电/充电自然在这种方法。本工作中使用的分析代码在Github上是开源的。
英文摘要：
Electrochemical kinetics at electrode-electrolyte interfaces limit performance of devices including fuel cells and batteries. While the importance of moving beyond Butler-Volmer kinetics and incorporating the effect of electronic density of states of the electrode have been recognized, a unified framework that incorporates these aspects directly into electrochemical performance models is still lacking. In this work, we explicitly account for the DFT-calculated density of states numerically in calculating electrochemical reaction rates for a variety of electrode-electrolyte interfaces. We first show the utility of this for two cases related to Li metal electrodeposition and stripping on a Li surface and a Cu surface (anode-free configuration). The deviation in reaction rates is minor for cases with flat densities of states such as Li, but is significant for Cu due to nondispersive d-bands creating large variation. Finally, we consider a semiconducting case of a solid-electrolyte interphase (SEI) consisting of LiF and Li$_2$CO$_3$ and note the importance of the Fermi level at the interface, pinned by the redox reaction occuring there. We identify the asymmetry in reaction rates as a function of discharge/charge naturally within this approach. The analysis code used in this work is available open-source on Github.
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