Strong Proton‐Phonon Coupling Drives Fast Ion Transport in Perovskites

TL;DR

This paper explains how proton transport in perovskite materials is enhanced by strong coupling between protons and phonons, particularly through yttrium substitution.

Contribution

The study identifies an imaginary phonon mode formed by yttrium substitution that lowers proton transport barriers.

Findings

Yttrium substitution creates an imaginary phonon mode that enhances proton conduction.

The oxygen sub-lattice transfers momentum to protons, governed by the ratio of ionic radii.

Phonon-phonon interactions extend transition state theory for proton transport.

Abstract

Conduction of protons in solids is a cooperative process propelled by phonons, with molecular details obscured by the irregular movements in the thermal bath. It is shown that substitution with Y forms an imaginary phonon mode, instrumental for the function as proton conductor and effectively lowering the activation barrier for proton transport. To untangle the interplay in the exemplary proton conductor BaSn0.9Y0.1O3, its crystallographic structure is determined with high resolution neutron diffractometry and its phonon density of states with density functional theory calculations, experimentally validated by element specific nuclear resonant vibration spectroscopy. Based on phonon analysis, a quantitative transport model is present, which predicts the activation energy and performance by the ratio of ionic radii. Rather than individual vibrational modes, it is the oxygen sub‐lattice which exerts its momentum on the protons. The extent of this momentum transfer is governed by the ratio of ionic radii. This model extends the transition state theory by the phonon‐phonon interaction and complements the previously proposed idea that lattice dynamics is decisive for proton transport and specifies which properties of the material exactly define the vibration properties.

Experimental and computational phonon analysis of ABO3‐type proton conductor BaSnO3 shows that substitution on the B‐site with yttrium forms an imaginary phonon mode which is instrumental for the function as proton conductor. This overcompensates the adverse proton trapping effect of the yttrium.

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