Abstract
Li3Ni2NbO6has a partially ordered rock salt superstructure in which Nb occupies fully one set of octahedral sites and Li/Ni are distributed nonrandomly over three other sets of octahedral sites (Matheret al.,J. Mater. Chem.5, 1177 (1995)). Over the temperature range 25–1100°C the Li/Ni site occupancy distribution is largely unchanged. Above 1100°C, Nb increasingly occupies the Li/Ni sites until, above 1300°C, the cations are completely disordered. The transition appears to be fully continuous, with no evidence of a transition enthalpy by DTA. Cr3+ions are able to substitute partially into both ordered and disordered structures by a range of mechanisms. The temperature range of the order–disorder transition decreases with Cr content, as shown in the phase diagram of the vacancy solid solutions, Li3−xNi2−xCrxNbO6(0 <x< 0.18). The materials are modest semiconductors.
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