First principles study of hydrogen storage material NaBH4 and LiAlH4 compounds: electronic structure and optical properties

Abstract

A comprehensive study of structure, phase stability, optical and electronic properties of LiAlH4 and NaBH4 light-metal hydrides is presented. The calculations are carried out within density functional theory using the full potential linear augmented plane wave method. The exchange-correlation potential is treated within the local density approximation and the generalized gradient approximation (GGA) to calculate the total energy. Furthermore, the Engel–Vosko GGA approach is employed to compute electronic and optical properties such as reflectivity spectra. The phases α, β and γ of LiAlH4 and NaBH4 hydrides are investigated, the phase transition from the β to the high-pressure γ phase is determined for NaBH4 and is accompanied by a 1% volume decrease. For LiAlH4, no phase transition is detected. The materials under consideration are classified as wide band gap compounds. From the analysis of the structures at different phases, it is deduced that the hydrides show strong covalent interaction between B (Al) and H in the [BH4]− ([AlH4]−) anions and ionic bonding character between [BH4]− and Na+ for NaBH4, and [AlH4]− and Li+ for LiAlH4. The complex dielectric function, absorption coefficient and the reflectivity spectra are also computed and analyzed in different phases.