Polymorphism and crystal chemistry of Li2.5Ga0.5GeO4, an Li3PO4 analogue

The structures of γ- and β-Li2.5Ga0.5GeO4 have been determined using Rietveld refinement of X-ray powder diffraction data. They are stoichiometric derivatives of γ- and β-Li3PO4. The arrangements of GeO4/PO4 tetrahedra are the same in each case, but the Li sites, especially Li(2), contain a disordered mixture of Li and Ga in γ- and β-Li2.5Ga0.5GeO4. Such cation disorder is unusual in a stoichiometric phase. The γ phase may be regarded as entropy-stabilised since it exists under equilibrium conditions only at high temperatures, ca. 1200°C, just below melting: the size mismatch between Li+ and Ga3+ ions and the likely unfavourable enthalpy of mixing associated with Li/Ga disorder is offset by the large entropy contribution to the Gibbs energy at high temperatures. A discussion of possible mechanisms for the β ⇋ γ transition is given.