The effect of ionic defect interactions on the hydration of yttrium-doped barium zirconate

Hydrated acceptor-doped barium zirconate is a well-investigated proton conductor. In the analysis of most experimental studies, an ideal defect model is applied to fit the measured hydration data and obtain corresponding enthalpies and entropies. However, the data show a distinct deviation from ideal behaviour and thus defect interactions cannot be neglected. In the present contribution, the thermodynamics of water uptake into the yttrium-doped bulk material are investigated on the microscopic level with regards to ionic defect interactions. Metropolis Monte Carlo simulations using interaction models from first-principles energy calculations are applied to obtain an estimation of the free energy of interaction. The present results indicate that the ionic defect interactions are the primary reason for the non-ideality observed in experiments with varying yttrium fraction, proton fraction, and temperature. The activity coefficient quotients for the mass action law are obtained, which connect the ideal and real model and are of relevance to data evaluation and theoretical calculations.

Automated summary

This study investigates the thermodynamics of water uptake into yttrium-doped barium zirconate on a microscopic level, focusing on ionic defect interactions. Monte Carlo simulations based on first-principles energy calculations reveal that ionic defect interactions are the primary reason for non-ideality observed in experiments under varying conditions. Activity coefficient quotients obtained from mass action law provide a link between ideal and real models for data evaluation and theoretical calculations.