Identifying the nature of interaction between LiBH4 and two-dimensional substrates: DFT study with van der Waals correction

•The interaction between LiBH4 and 2-dimensional substrates was examined using DFT.•Monomer LiBH4–2D interface interaction is governed by the dipole of LiBH4 monomer.•Bulk LiBH4–2D interface interaction is dominated by the dispersion forces.•Binding energy of bulk LiBH4–2D interface is comparable to LiBH4 surface energy. Addressing the nature of interaction at the LiBH4−carbon interface is the key to unveiling mechanism for the carbon-facilitated desorption of lithium borohydride (LiBH4). Density functional theory calculations, taking into account the long range dispersion forces, have been performed to explore the interaction between LiBH4, in the form of either a monomer unit or a crystalline bulk, and two-dimensional (2D) substrate, represented by graphene and hexagonal boron nitride. At the monomer−2D contact, the permanent dipole of LiBH4 induces polarization of the π electrons of the 2D, and the resultant permanent dipole–induced dipole attraction becomes the main source of binding. At the bulk−2D interface, van der Waals attraction dominates the interfacial binding rather than the dipole–dipole attraction. The absolute values of the calculated interface energy match closely with the surface energy of pristine (001) LiBH4, hinting that the energy released by the formation of the interface has enough magnitude to overcome the surface energy of LiBH4.