Na-Ni-H Phase Formation at High Pressures and High Temperatures: Hydrido Complexes [NiH₅]^3- Versus the Perovskite NaNiH₃

The Na-Ni-H system was investigated by in situ synchrotron diffraction studies of reaction mixtures NaH-Ni-H₂ at around 5, 10, and 12 GPa. The existence of ternary hydrogen-rich hydrides with compositions Na₃NiH₅ and NaNiH₃, where Ni attains the oxidation state II, is demonstrated. Upon heating at ∼5 GPa, face-centered cubic (fcc) Na₃NiH₅ forms above 430 °C. Upon cooling, it undergoes a rapid and reversible phase transition at 330 °C to an orthorhombic (Cmcm) form. Upon pressure release, Na₃NiH₅ further transforms into its recoverable Pnma form whose structure was elucidated from synchrotron powder diffraction data, aided by first-principles density functional theory (DFT) calculations. Na₃NiH₅ features previously unknown square pyramidal 18-electron complexes NiH₅ ^3-. In the high temperature fcc form, metal atoms are arranged as in the Heusler structure, and ab initio molecular dynamics simulations suggest that the complexes are dynamically disordered. The Heusler-type metal partial structure is essentially maintained in the low temperature Cmcm form, in which NiH₅ ^3- complexes are ordered. It is considerably rearranged in the low pressure Pnma form. Experiments at 10 GPa showed an initial formation of fcc Na₃NiH₅ followed by the addition of the perovskite hydride NaNiH₃, in which Ni(II) attains an octahedral environment by H atoms. NaNiH₃ is recoverable at ambient pressures and represents the sole product of 12 GPa experiments. DFT calculations show that the decomposition of Na₃NiH₅ = NaNiH₃ + 2 NaH is enthalpically favored at all pressures, suggesting that Na₃NiH₅ is metastable and its formation is kinetically favored. Ni-H bonding in metallic NaNiH₃ is considered covalent, as in electron precise Na₃NiH₅, but delocalized in the polyanion [NiH₃]^-.