Atomistic insights into the conversion reaction in iron fluoride: a dynamically adaptive force field approach.

Nanoscale metal fluorides are promising candidates for high capacity lithium ion batteries, in which a conversion reaction upon exposure to Li ions enables access to the multiple valence states of the metal cation. However, little is known about the molecular mechanisms and the reaction pathways in conversion that relate to the need for nanoscale starting materials. To address this reaction and the controversial role of intercalation in a promising conversion material, FeF(2), a dynamically adaptive force field that allows for a change in ion charge during reactions is applied in molecular dynamics simulations. Results provide the atomistic view of this conversion reaction that forms nanocrystals of LiF and Fe(0) and addresses the important controversy regarding intercalation. Simulations of Li(+) exposure on the low energy FeF(2) (001) and (110) surfaces show that the reaction initiates at the surface and iron clusters as well as crystalline LiF are formed, sometimes via an amorphous Li-F. Li intercalation is also observed as a function of surface orientation and rate of exposure to the Li, with different behavior on (001) and (110) surfaces. Intercalation along [001] rapid transport channels is accompanied by a slight reduction of charge density on multiple nearby Fe ions per Li ion until enough Li saturates a region and causes the nearby Fe to lose sufficient charge to become destabilized and form the nanocluster Fe(0). The resultant nanostructures are fully consistent with postconversion TEM observations, and the simulations provide the solution to the controversy regarding intercalation versus conversion and the atomistic rationale for the need for nanoscale metal fluoride starting particles in conversion cathodes.