The temperature dependent conductivity of yttria stabilized zirconia (YSZ) exhibits a bending in Arrhenius' plots which is frequently discussed in terms of free and associated oxygen vacancies. However, the very high doping concentration in YSZ leads to such a strong defect interaction that the concept of free vacancies becomes highly questionable. Therefore, the temperature dependent conductivity of YSZ is reconsidered. The conductivity of YSZ with different doping concentration was measured in a broad temperature range. The data are analyzed in terms of two different barrier heights that have to be passed along an average path of an oxygen vacancy in YSZ (two barrier model). For 8-10 mol% yttria, the two barriers are in the range of 0.6 eV and 1.1-1.2 eV, respectively. The conductivity and thus the barrier heights also depend on the cooling rate after a high temperature pre-treatment. This indicates that different frozen-in distributions of dopants affect the vacancy motion by different energy landscapes. Temporarily existing defect configurations, possibly with a strong effect of repulsive oxygen vacancy interaction, are suggested as the reason of high barriers. Future dynamic ab-initio calculations may reveal whether this modified model of the YSZ conductivity is mechanistically meaningful. Yttria stabilized zirconia (YSZ) is among the most important ion conducting solids and acts as a kind of model material representing fast oxide ion conductors. Owing to this model character of YSZ, but also due to its application in solid oxide fuel cells (SOFCs), solid oxide electrolysis cells (SOECs) and oxygen sensors, a vast amount of papers can be found dealing with its oxide ion conduction. The ionic conductivity is based on the motion of oxygen vacancies, introduced by Y 3+ ions replacing Zr 4+ . For concentrations above ca. 8 mol%, yttria doping also stabilizes the cubic structure down to room temperature. A detailed review of the science of YSZ and related materials is far beyond the scope of this paper but a few important facts regarding the ionic conductivity of zirconia-based solid electrolytes can be briefly summarized as follows:1-9 i) Doping concentrations above ca. 8 mol% Y 2 O 3 lead to a decrease of the conductivity, despite increasing oxygen vacancy concentration. ii) The conductivity not only depends on the vacancy concentration but also on the kind of dopant. For example, Sc-doped zirconia shows significantly higher conductivity than YSZ. iii) The temperature dependence of the conductivity cannot be described by a single activation energy (E act ) but shows higher E act values at lower temperatures.Numerous theoretical studies were performed in order to understand these experimental observations and to get a deeper insight into defect thermodynamics and kinetics of doped zirconia and of the closely related ceria-based ion conductors, see e.g. Refs. 10-29. Those model studies employed different simulation approaches such as molecular dynamics (MD), density functional theory (DFT) and kinetic Monte Carl...
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