Confinement Effects for Lithium Borohydride: Comparing Silica and Carbon Scaffolds.

LiBH is a promising material for hydrogen storage and as a solid-state electrolyte for Li ion batteries. Confining LiBH in porous scaffolds improves its hydrogen desorption kinetics, reversibility, and Li conductivity, but little is known about the influence of the chemical nature of the scaffold. Here, quasielastic neutron scattering and calorimetric measurements were used to study support effects for LiBH confined in nanoporous silica and carbon scaffolds. Pore radii were varied from 8 Å to 20 nm, with increasing confinement effects observed with decreasing pore size. For similar pore sizes, the confinement effects were more pronounced for silica than for carbon scaffolds. The shift in the solid-solid phase transition temperature is much larger in silica than in carbon scaffolds with similar pore sizes. A LiBH layer near the pore walls shows profoundly different phase behavior than crystalline LiBH. This layer thickness was 1.94 ± 0.13 nm for the silica and 1.41 ± 0.16 nm for the carbon scaffolds. Quasi-elastic neutron scattering confirmed that the fraction of LiBH with high hydrogen mobility is larger for the silica than for the carbon nanoscaffold. These results clearly show that in addition to the pore size the chemical nature of the scaffold also plays a significant role in determining the hydrogen mobility and interfacial layer thickness in nanoconfined metal hydrides.