Ohba, Nobuko Miwa, Kazutoshi Aoki, Masakazu Noritake, Tatsuo Towata, Shin-ichi Nakamori, Yuko Orimo, Shin-ichi Züttel, Andreas 2006-08-25 We report the results of the first-principles calculation on the intermediate compounds of LiBH₄. The stability of LiB₃H₈ and Li₂B_<i>n</i>H_<i>n</i> (<i>n</i>=5–12) has been examined with the ultrasoft pseudopotential method based on the density-functional theory. Theoretical prediction has suggested that monoclinic Li₂B₁₂H₁₂ is the most stable among the candidate materials. We propose the following hydriding (dehydriding) process of LiBH₄ via this intermediate compound: LiBH₄ <-> 1/2Li₂B₁₂H₁₂+5/6LiH+13/12H₂ <-> LiH+B+3/2H₂. The hydrogen content and enthalpy of the first reaction are estimated to be 10 mass % and 56 kJ/mol H₂, respectively, and those of the second reaction are 4 mass % and 125 kJ/mol H₂. They are in good agreement with experimental results of the thermal desorption spectra of LiBH₄. Our calculation has predicted that the bending modes for the Γ-phonon frequencies of monoclinic Li₂B₁₂H₁₂ are lower than that of LiBH₄, while stretching modes are higher. These results are very useful for the experimental search and identification of possible intermediate compounds. application/pdf https://folia.unifr.ch/global/documents/300168 https://folia.unifr.ch/documents/300168/files/zuettel_fps.pdf eng info:eu-repo/semantics/altIdentifier/doi/10.1103/PhysRevB.74.075110 info:eu-repo/semantics/openAccess License undefined Physical Review B. - 2006, vol. 74, p. 075110 info:eu-repo/classification/udc/53 First-principles study on the stability of intermediate compounds of LiBH₄ http://purl.org/coar/resource_type/c_6501