Mabrouk Y, Safaei N, Hanke F, Carlsson J M, Diddens D, Heuer A
Forschungszentrum Jülich GmbH, Helmholtz-Institute Münster (IEK-12), Corrensstraße 46, 48149, Münster, Germany.
Dassault Systémes Deutschland GmbH, Am Kabellager 11-13, 51063, Cologne, Germany.
Sci Rep. 2024 May 4;14(1):10281. doi: 10.1038/s41598-024-60063-0.
The development of reliable computational methods for novel battery materials has become essential due to the recently intensified research efforts on more sustainable energy storage materials. Here, we use a recently developed framework allowing to consistently incorporate quantum-mechanical activation barriers to classical molecular dynamics simulations to study the reductive solvent decomposition and formation of the solid electrolyte interphase for a graphite/carbonate electrolyte interface. We focus on deriving condensed-phase effective rates based on the elementary gas-phase reduction and decomposition energy barriers. After a short initial transient limited by the elementary barriers, we observe that the effective rate shows a transition to a kinetically slow regime influenced by the changing coordination environment and the ionic fluxes between the bulk electrolyte and the interface. We also discuss the impact of the decomposition on the ionic mobility. Thus, our work shows how elementary first-principles properties can be mechanistically leveraged to provide fundamental insights into electrochemical stability of battery electrolytes.
由于最近对更可持续的储能材料的研究力度加大，开发用于新型电池材料的可靠计算方法变得至关重要。在此，我们使用一种最近开发的框架，该框架允许将量子力学活化能垒一致地纳入经典分子动力学模拟，以研究石墨/碳酸盐电解质界面处的还原溶剂分解和固体电解质界面的形成。我们专注于基于基本气相还原和分解能垒推导凝聚相有效速率。在受基本能垒限制的短暂初始瞬态之后，我们观察到有效速率显示出向动力学缓慢区域的转变，该区域受不断变化的配位环境以及本体电解质与界面之间的离子通量影响。我们还讨论了分解对离子迁移率的影响。因此，我们的工作展示了如何从机理上利用基本的第一性原理性质来深入了解电池电解质的电化学稳定性。
