Modifying Crystal Symmetry and B-O Charge Distribution to Tailor Chemical Expansion in Mixed Conducting Perovskites

Abstract

The exchange of ions between a lattice and the gaseous phase makes mixed conducting oxides ideal for a range of electrochemical applications. Altering oxygen ion concentration is accompanied by a change to electronic species concentrations, and this influences electrical, chemical, kinetic, and mechanical properties. The stability of electrochemical devices like fuel cells and batteries can heavily rely on the mechanical response to changes in chemical defect concentrations. Under both dynamic and steady-state operation of these devices, large volume strains and strain mismatch at interfaces can result in fracture, warping, and delamination that can cause performance degradation and/or failure. Strains between different materials are compared using the coefficient of chemical expansion (CCE), which normalizes the isothermal chemical strain by the change in defect concentration. Here, we advance the understanding of chemo-mechanical coupling through the study of PrGa0.9Mg0.1O3-δ and BaPr0.9Y0.1O3-δ by demonstrating CCEs 2-5x lower than any previously reported perovskite oxide1.Isothermal CCEs were evaluated with in situ, high temperature, and variable atmosphere x-ray diffraction and dilatometry for chemical strains, and with thermogravimetric analysis for stoichiometry changes. The experimental results show chemical strains to be significantly lower than predictions from simple empirical models that assume pseudo-cubic structures and full charge localization on multivalent cations, like Pr. To evaluate actual charge distribution, in situ impedance spectroscopy and density functional theory calculations were performed. The collaboration of experimental and computational work combines accurate and reliable material characterization with insights into atomic and electronic structures that are difficult to probe experimentally.Our results for the studied compositions indicate 2 primary factors that can be used to modify CCEs: 1) Altering the crystal structure away from the isotropic, cubic phase encourages anistropic expansion and lower CCEs in polycrystalline materials, and 2) Varying the distribution of charge along B-O bonds is shown to dramatically alter the CCE. While the first factor provides rather clear guidance to tailor expansion, we elaborate on the second by suggesting band structure design principles for near-zero redox-strain perovskites, and the benefit of locating holes partially or fully on oxygen is highlighted. These new findings add to the growing collection of crystal-chemical design rules for the rational tailoring of chemo-mechanical coupling in perovskite oxides.(1) Anderson, L. O.; Yong, A. X. Bin; Ertekin, E.; Perry, N. H. Toward Zero-Strain Mixed Conductors: Anomalously Low Redox Coefficients of Chemical Expansion in Praseodymium-Oxide Perovskites. Chem. Mater. 2021, 33 (21), 8378–8393. https://doi.org/10.1021/ACS.CHEMMATER.1C02739.