Investigation of the thermochemical transformations in the LiAlH4-LiNH2 system

The thermal transformations in the lithium alanate-amide system consisting of lithium aluminum hydride (LiAlH₄) and lithium amide (LiNH₂), mixed in a 1:1 M ratio, were investigated using the pressure-composition-temperature analysis, solid-state nuclear magnetic resonance, X-ray powder diffraction, and residual gas analysis. Below 250 °C, the alanate decomposes into Al, LiH and H₂, through the formation of Li₃AlH₆, whereas the amide remains largely intact. The release of gaseous hydrogen corresponds to approximately 5 wt%. Above 250 °C, additional ∼4 wt% of hydrogen is produced through solid-state reactions among LiNH₂, LiH and metallic Al, through the formation of intermetallic Li-Al binary alloy and an unidentified intermediate. The overall reaction of the thermochemical transformation of the LiAlH₄-LiNH₂ mixture results in the production of Li₃AlN₂, metallic Al, LiH and the release of 9 wt% of gaseous hydrogen. The reaction mechanism of the thermal decomposition is different from one identified earlier during mechanical treatment of the same system. Rehydrogenation of the thermally-decomposed products of LiAlH₄-LiNH₂ mixture using high hydrogen pressure (180 bar) and heating (275 °C) yields LiNH₂ and amorphous aluminum nitride (AlN).