LiBH4 which have attracted considerable attention from researchers due to the crystal structure characteristics is a metal hydride that can bind four hydrogen atoms. LiBH4 which has high gravimetric and volumetric hydrogen density shows phase transitions at high pressures. In this regard, we created and analyzed LiBH4 structure based on the first principles calculations, and then obtained the super-cell LiBH4 structure. We achieved the phase transitions up to 20 GPa pressure with 2 GPa regular intervals for the super-cell LiBH4 . We observed the Pnma to Pnma*, Pnma* to P2(1)/c, and P2(1)/c to C2/c phase transitions and calculated the volume contractions accompanying these phase transitions. According to the obtained volumetric values, one can conclude that LiBH4 can minimize the volumetric requirements of the hydrogen storage for systems that can be used at high pressures. Thus, the hydrogen storage capacity of LiBH4 may increase at particular phases.