Designing Optimal Perovskite Structure for High Ionic Conduction.

Gao, Ran; Jain, Abhinav C P; Pandya, Shishir; Dong, Yongqi; Yuan, Yakun; Zhou, Hua; Dedon, Liv R; Thoréton, Vincent et al. · Adv Mater · 2020

basic_science · Level V

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Abstract

Solid-oxide fuel/electrolyzer cells are limited by a dearth of electrolyte materials with low ohmic loss and an incomplete understanding of the structure-property relationships that would enable the rational design of better materials. Here, using epitaxial thin-film growth, synchrotron radiation, impedance spectroscopy, and density-functional theory, the impact of structural parameters (i.e., unit-cell volume and octahedral rotations) on ionic conductivity is delineated in La<sub>0.9</sub> Sr<sub>0.1</sub> Ga<sub>0.95</sub> Mg<sub>0.05</sub> O<sub>3-</sub> <sub>δ</sub> . As compared to the zero-strain state, compressive strain reduces the unit-cell volume while maintaining large octahedral rotations, resulting in a strong reduction of ionic conductivity, while tensile strain increases the unit-cell volume while quenching octahedral rotations, resulting in a negligible effect on the ionic conductivity. Calculations reveal that larger unit-cell volumes and octahedral rotations decrease migration barriers and create low-energy migration pathways, respectively. The desired combination of large unit-cell volume and octahedral rotations is normally contraindicated, but through the creation of superlattice structures both expanded unit-cell volume and large octahedral rotations are experimentally realized, which result in an enhancement of the ionic conductivity. All told, the potential to tune ionic conductivity with structure alone by a factor of ≈2.5 at around 600 °C is observed, which sheds new light on the rational design of ion-conducting perovskite electrolytes.