First-Principles Investigations of the Working Mechanism of 2D h-BN as an Interfacial Layer for the Anode of Lithium Metal Batteries.

An issue with the use of metallic lithium as an anode material for lithium-based batteries is dendrite growth, causing a periodic breaking and repair of the solid electrolyte interphase (SEI) layer. Adding 2D atomic crystals, such as h-BN, as an interfacial layer between the lithium metal anode and liquid electrolyte has been demonstrated to be effective to mitigate dendrite growth, thereby enhancing the Columbic efficiency of lithium metal batteries. But the underlying mechanism leading to the reduced dendrite growth remains unknown. In this work, with the aid of first-principle calculations, we find that the interaction between the h-BN and lithium metal layers is a weak van der Waals force, and two atomic layers of h-BN are thick enough to block the electron tunneling from lithium metal to electrolyte, thus prohibiting the decomposition of electrolyte. The interlayer spacing between the h-BN and lithium metal layers can provide larger adsorption energies toward lithium atoms than that provided by bare lithium or h-BN, making lithium atoms prefer to intercalate under the cover of h-BN during the plating process. The combined high stiffness of h-BN and the low diffusion energy barriers of lithium at the Li/h-BN interfaces induce a uniform distribution of lithium under h-BN, therefore effectively suppressing dendrite growth.