Cation composition effects on oxide conductivity in the Zr_2Y_2O_7-Y_3NbO_7 system

TL;DR

This study uses molecular dynamics simulations with first-principles potentials to explore how cation composition influences oxide ionic conductivity and lattice disorder in the Zr2Y2O7-Y3NbO7 system, revealing trends and limitations.

Contribution

It provides new insights into the effects of cation charge and size on vacancy ordering and conductivity, highlighting the role of cation disorder in this oxide system.

Findings

Conductivity decreases with increasing Nb5+ content.

Cation charge and size influence vacancy ordering.

Simulations overestimate conductivity in Y3NbO7.

Abstract

Realistic, first-principles-based interatomic potentials have been used in molecular dynamics simulations to study the effect of cation composition on the ionic conductivity in the Zr2Y2O7-Y3NbO7 system and to link the dynamical properties to the degree of lattice disorder. Across the composition range, this system retains a disordered fluorite crystal structure and the vacancy concentration is constant. The observed trends of decreasing conductivity and increasing disorder with increasing Nb5+ content were reproduced in simulations with the cations randomly assigned to positions on the cation sublattice. The trends were traced to the influences of the cation charges and relative sizes and their effect on vacancy ordering by carrying out additional calculations in which, for example, the charges of the cations were equalised. The simulations did not, however, reproduce all the observed properties, particularly for Y3NbO7. Its conductivity was significantly overestimated and prominent diffuse scattering features observed in small area electron diffraction studies were not always reproduced. Consideration of these deficiencies led to a preliminary attempt to characterise the consequence of partially ordering the cations on their lattice, which significantly affects the propensity for vacancy ordering. The extent and consequences of cation ordering seem to be much less pronounced on the Zr2Y2O7 side of the composition range.