Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li3AlP2 and Li3GaP2

The lithium phosphidoaluminate Li9AlP4 represents a promising new compound with a high lithium ion mobility. This triggered the search for new members in the family of lithium phosphidotrielates, and the novel compounds Li3AlP2 and Li3GaP2, obtained directly from the elements via ball milling and subsequent annealing, are reported here. It was unexpectedly found through band structure calculations that Li3AlP2 and Li3GaP2 are direct band gap semiconductors with band gaps of 3.1 and 2.8 eV, respectively. Rietveld analyses reveal that both compounds crystallize isotypically in the orthorhombic space group Cmce (no. 64) with lattice parameters of a=11.5138(2), b=11.7634(2) and c=5.8202(1) Å for Li3AlP2, and a=11.5839(2), b=11.7809(2) and c=5.8129(2) Å for Li3GaP2. The crystal structures feature TrP4 (Tr=Al, Ga) corner‐ and edge‐sharing tetrahedra, forming two‐dimensional ∞2TrP23- layers. The lithium atoms are located between and inside these layers. The crystal structures were confirmed by MAS‐NMR spectroscopy. Layer structure in phosphidoaluminates and ‐gallates: The two new isotopic structures of Li3AlP2 and Li3GaP2 exhibit layers of corner‐ and edge‐sharing AlP4/GaP4 tetrahedra. The compounds are easily accessible through ball milling of the elements and are both semiconductors with a direct band gap of 3.1 and 2.8 eV, respectively.