Effect of Mg substitution on crystal structure and oxide-ion conductivity of apatite-type lanthanum silicates

Two types of apatite-type lanthanum silicates, La(9.93)(Si(5.11) Mg(0.89))O(26) (space group P6(3)/m) and (La(8.48) Mg(1.28))Si(6)O(26) (space group P6(3)), were successfully synthesized. They were, together with La(9.33)Si(6)O(26) (space group P6(3)/m), examined by optical microscopy, impedance spectroscopy and X-ray powder diffraction. The crystal structures of the former two compounds were refined by single-crystal X-ray diffraction. The oxide-ion conductivity at 773 K was the highest for La(9.93)(Si(5.11) Mg(0.89))O(26). followed by La(9.33)Si(6)O(26) and (La(8.48) Mg(1.28))Si(6)O(26) in this order. The systematic change in conductivity was well accounted for by the atom arrangements of hexagonal channels, consisting of alternately stacking equilateral triangles of La and O along the c-axis. With La(9.93)(Si(5.11) Mg(0.89))O(25), the La triangle appreciably expanded as compared with that of La(9.33)Si(6)O(26), while the size of O triangle was kept almost constant. When the La sites were partially occupied by Mg atoms, the space group changed from P6(3)/m to P6(3), leading to the transformation of equivalent O triangles into the larger and smaller ones. On the assumption that conduction takes place inside the hexagonal channels through the migration of channel oxide-ions, they necessarily pass through the channel triangles. The smaller O triangle would act as a bottleneck hindering the migration of channel oxide ions. The expansion of La triangle would effectively enhance the conductivity. (C) 2010 Elsevier B.V. All rights reserved.