Highly Stable Two-Dimensional Iron Monocarbide with Planar Hypercoordinate Moiety and Superior Li-Ion Storage Performance

Stable planar hypercoordinate motifs have been recently demonstrated in two-dimensional (2D) confinement systems, while perfectly planar hypercoordinate motifs in 2D carbon–transition metal systems are rarely reported. Here, by using comprehensive ab initio computations, we discover two new iron monocarbide (FeC) binary sheets stabilized at 2D confined space, labeled as tetragonal-FeC (t-FeC) and orthorhombic-FeC (o-FeC), which are energetically more favorable compared with the previously reported square and honeycomb lattices. The proposed t-FeC is the global minimum configuration in the 2D space, and each carbon atom is four-coordinated with four ambient iron atoms, considered as the quasi-planar tetragonal lattice. Strikingly, the o-FeC monolayer is an orthorhombic phase with a perfectly planar pentacoordinate carbon moiety and a planar seven-coordinate iron moiety. These monolayers are the first example of a simultaneously pentacoordinate carbon and planar seven-coordinate Fe-containing material. State-of-the-art theoretical calculations confirm that all these monolayers have significantly dynamic, mechanical, and thermal stabilities. Among these two monolayers, the t-FeC monolayer shows a higher theoretical capacity (395 mAh g–1) and can stably adsorb Li up to t-FeCLi4 (1579 mAh g–1). The low migration energy barrier is predicted as small as 0.26 eV for Li, which results in the fast diffusion of Li atoms on this monolayer, making it a promising candidate for lithium-ion battery material.