First-principles study on the intermediate compounds of LiBH$_4$

TL;DR

This study uses first-principles calculations to identify stable intermediate compounds of LiBH4 and predicts their role in hydrogen release, aligning well with experimental data and aiding future experimental identification.

Contribution

The paper predicts the most stable intermediate compound of LiBH4 and details its role in hydrogen release, providing theoretical insights into the hydriding/dehydriding process.

Findings

Li2B12H12 is the most stable intermediate among candidates.

Predicted hydrogen content and enthalpy match experimental spectra.

Vibrational modes differ between LiBH4 and Li2B12H12, aiding experimental identification.

Abstract

We report the results of the first-principles calculation on the intermediate compounds of LiBH$_4$. The stability of LiB$_3$H$_8$ and Li$_2$B$_n$H$_n (n=5-12)$ has been examined with the ultrasoft pseudopotential method based on the density functional theory. Theoretical prediction has suggested that monoclinic Li$_2$B$_{12}$H$_{12}$ is the most stable among the candidate materials. We propose the following hydriding/dehydriding process of LiBH$_4$ via this intermediate compound : LiBH$_4 \leftrightarrow {1/12}$Li$_{2}$B$_{12}$H$_{12} + {5/6}$ LiH $+ {13/12}$H$_2 \leftrightarrow $LiH $+$ B $+ {3/2} $H$_2$. The hydrogen content and enthalpy of the first reaction are estimated to be 10 mass% and 56 kJ/mol H$_2$, respectively, and those of the second reaction are 4 mass% and 125 kJ/mol H$_2$. They are in good agreement with experimental results of the thermal desorption spectra of LiBH$_4$. Our calculation has predicted that the bending modes for the $\Gamma$-phonon frequencies of monoclinic Li$_2$B$_{12}$H$_{12}$ are lower than that of LiBH$_4$, while stretching modes are higher. These results are very useful for the experimental search and identification of possible intermediate compounds.