Interfacial Effects on Solid Electrolyte Interphase in Lithium-ion Batteries.

The existence of passivating layers at the interfaces in batteries is a major factor enabling modern lithium-ion (Li-ion) batteries and determines cycle life and performance. A special case is the solid electrolyte interphase (SEI), a heterogeneous multi-component film formed due to the instability and subsequent decomposition of the electrolyte at the surface of the anode. The SEI acts as a passivating layer that hinders further electrolyte disintegration, which could lead to insufficient Coulombic efficiency. In this work, we investigate, using first-principles simulations, the kinetic and electronic properties of the interface between lithium fluoride (LiF) and lithium carbonate (Li$_2$CO$_3$), two common SEI components present in Li-ion batteries with organic liquid electrolytes. We find that despite being thermodynamically favorable, there exists a substantial barrier for the migration of Li ions from LiF to Li$_2$CO$_3$, forming interstitials in Li$_2$CO$_3$ responsible for ion transport. Once formed, we find that the activation energy of Li hopping is reduced from $0.3$ eV in bulk Li$_2$CO$_3$ to $0.16$ eV in the interfacial structure considered, demonstrating the favorable role of the interface. We further perform Car-Parrinello molecular dynamics simulations to explore Li ion conduction in our interfacial structure, which reveal an enhanced Li ion diffusion in the vicinity of the interface. Understanding interfacial properties of SEI components represents an important frontier to enable next-generation batteries.