Structural Toughness of Fluorinated–Nitrided Interphase Passivation Layers for Lithium-Ion Batteries: A Reactive Molecular Dynamics Study

Abstract

The performance of lithium-ion batteries largely depends on the stability of the solid electrolyte interphase (SEI) layer formed on the anode surface. Strategies to improve SEI robustness often rely on optimizing its composition through electrolytic additives. Recently, the amalgamation of fluorinated cosolvents with nitride sources as additives has been shown to enable the construction of sustainable fluorinated−nitrided SEI layers (FN-SEI). Furthermore, the presence of lithiophilic nitrides embedded in lithium fluoride (LiF) was found to contribute toward stability of a beneficial amorphous phase for interfacial passivation. However, there is a lack of understanding on how key indicators of mechanical longevity, like plasticity and fracture resistance, may evolve in such multiphase SEI building blocks. Herein, in conjunction with first-principles calculations, a reactive force field (ReaxFF) has been developed for deriving new mechanistic insights into the intriguing FN-SEI. Our studies demonstrate that owing to a significant elasticity mismatch, the hard nitride phases have a propensity to affect the native deformation modes when embedded in a soft amorphous LiF-rich matrix. Impact of the volume fraction and distribution of the nitride (Li 3 N) phases are discussed from the perspective of how they interfere with the propagation of shear bands. Interestingly, brittle−ductile−brittle regimes are recognized along the nitride infusion window, providing a glimpse into the effect of phase distribution on the structural toughness of the LiF−Li 3 N-enhanced SEI.