Theoretical study of the synthesis,characterization and hydrogen storage properties of a high-density hydrogen storage material: (CH3NH3)BH4

Inspired by both alkaline metal borohydrides and organic-inorganic hybrid perovskite, we predict a pair of complex structures of (CH₃NH₃)BH₄ with tremendous high hydrogen capacity (21.27 wt.%). Through comparison and analysis of the electronic structures of alkali metal atoms, CH₃NH₃, NH₄, and NH₃BH₃ molecule, it is concluded that similar spatial and electronic structures show the feasibility of synthesizing (CH₃NH₃)BH₄ by a substitution reaction. Firstly, theoretical structures (S₁ and S₂ in P₁) with stable configurations have been reconstructed by cation substitution followed by a series of restrictive structural optimizations, and both the lattice parameters and the position coordinate information of (CH₃NH₃)BH₄ are obtained. Ignoring the relatively mobile hydrogen, the structural symmetries of S₁ and S₂ are I4mm and P4/nmm, respectively. X-ray diffraction characterizations of S₁ and S₂ are consistent with the experimental results. Secondly, the calculated elastic constants of (CH₃NH₃)BH₄ (S₁ and S₂) with P₁ symmetry indicate that angles α, β and γ oscillate at right angles due to the influence of the cation orientation. The calculated spatial dependence of bulk (B), Young's (E), and shear (G) modulus obviously show that the two P₁ phases all have strong elastic anisotropy. Thirdly, the calculated electronic properties show that the protonic amine-H, hydridic borane-H, and neutral methane-H are widely distributed in (CH₃NH₃)BH₄, which allow for weaving in a planar dihydrogen bonding network, which in turn influences the dehydrogenation reaction. Last and most important, we propose the following dehydrogenation process of (CH₃NH₃)BH₄ via the intermediate compounds: 2(CH₃NH₃)BH₄ → CH₃NH₂BH₂NHCH₃BH₃+3H₂. For each dehydrogenation step, the free energy change is negative, which means (CH₃NH₃)BH₄ can decompose spontaneously, similar to ammonium borohydride, which is strongly related to the planar dihydrogen bonding network.