Improving Chemo-Mechanical Stability of Proton-Conducting Perovskites

Abstract

The superior ionic conductivity of selected proton-conducting perovskites enables development of intermediate temperature electrochemical devices, such as solid oxide fuel/electrolysis cells, gas separation membranes, and electrochemical reactors. The lower operating temperature, compared to those of most oxide ion-conductors, can benefit the durability of the devices, as most degradation mechanisms are thermally activated. On the other hand, the chemical strains associated with hydration/dehydration during processing or operation can be considerably larger than those seen in their oxide ion-conducting counterparts during oxygen loss/gain. There is therefore a significant need to develop proton conductors with lower coefficients of chemical expansion (CCE), which is the chemical strain normalized to the change in defect (proton) concentration. Since design principles for engineering CCEs are not well developed, we have previously been investigating the role of various structural and chemical features, such as size of the oxygen vacancy and charge localization.In this presentation, I will focus on our more recent work investigating the role of octahedral distortions and deviations away from the perfect cubic perovskite structure. By substituting differently sized isovalent cations on the A- and B-site of perovskites, it is possible to engineer the tolerance factor to vary the symmetry and distortions. We have therefore synthesized a series of (Ba,Sr)(Zr,Ce)0.9Y0.1O3-x perovskites with gradually varying tolerance factor. To measure hydration strains, isothermal in situ X-ray diffraction and dilatometry were performed at temperature points in the range ~360-680 °C, in varying humidities. To evaluate the corresponding changes in proton concentration, isothermal thermogravimetric analysis was applied under identical conditions; an intermediate, constant oxygen partial pressure was chosen to avoid the possibility of any simultaneous redox reactions contributing significantly to mass changes and strains. The combined results show that by diminishing the perovskite tolerance factor in this family of zirconate/cerate proton conductors, the coefficient of chemical expansion can be lowered by 500%. Further in situ X-ray diffraction analysis of powder vs. bulk samples, and density functional theory simulations of single crystals, have revealed that there are both crystal chemical and microstructural contributions to the trend seen. The results show that inducing octahedral rotations and lowering symmetry, by altering the cation radius ratio, is an effective route to increase chemo-mechanical stability by lowering CCEs.