Solid State Ionics, Vol.217, 40-45, 2012
Anisotropy of oxide-ion conduction in apatite-type lanthanum silicate
The anisotropy of oxide-ion conduction was clarified for the apatite-type La9.33+2x(SiO4)(6)O2+3x (0.01 <= x <= 0.13). We synthesized the polycrystalline materials of apatite by the isothermal heating of the sandwich-type La2Si2O7/La2SiO5/La2Si2O7 diffusion couples at 1873 K for 100 h. The resulting polycrystals were subsequently characterized using optical microscopy, X-ray diffractometry and impedance spectroscopy. The individual c-axes of the crystallites were appreciably aligned along the diffusion direction, while their a-axes were, around the common c-axis direction, oriented randomly. We obtained the impedance spectroscopy data of the polycrystalline electrolyte, the planar electrodes of which were parallel to the common c-axis. Thus, the obtained bulk conductivity ((sigma) over bar (bulk) perpendicular to c) corresponds to the average value of those perpendicular to the c-axis, which steadily increased from 1.6x10(-5) to 3.8x10(-4) S/cm with increasing temperature from 623 to 848 K. The bulk conductivity parallel to the c-axis (sigma(bulk) parallel to c) that was determined in a previous study was, when compared at the same temperature, necessarily higher than the corresponding (sigma) over bar (bulk) perpendicular to c value; the magnitude of anisotropy (sigma(bulk) parallel to c / (sigma) over bar (bulk) perpendicular to c) steadily decreased with increasing temperature from 2.1 x 10(2) at 623 K to 4.5x10(1) at 823 K. The activation energy of (sigma) over bar (bulk) perpendicular to c was 0.71 eV, which is almost twice that of sigma(bulk) parallel to c (0.35 eV). (C) 2012 Elsevier B.V. All rights reserved.
Keywords:lanthanum silicate;oxide-ion conductor;apatite-type structure;anisotropy of oxide-ion conduction