Abstract
In this work, the - and -site cation migration pathways involving defect complexes in bulk (LSM) at are investigated based on density-functional-theory modeling for solid-oxide fuel-cell (SOFC) cathode applications. We propose a dominant -site cation migration mechanism which involves an -site cation (e.g., ) hop into a of a cluster, where , , and, are , -site vacancy, and -site vacancy in bulk LSM, respectively, and is the first nearest-neighbor and pair. This hop exhibits an approximately 1.6-eV migration barrier as compared to approximately 2.9 eV of the hop into a . This decrease in the cation migration barrier is attributed to the presence of the relieving the electrostatic repulsion and steric constraints to the migrating -site cations in the transition-state image configurations. The interaction energy is predicted to be weakly repulsive (0.2–0.3 eV) in bulk LSM, which enables the cluster to readily form. The predicted apparent activation energy of in (LMO) for the -site migration pathway is about 1.4 eV, in good agreement with the experimental -site cation impurity diffusivity measurements. By examining the -site cation migration barriers among different metal cations (, , ) relevant for SOFC applications, it is demonstrated that migration barriers of the cation impurity in bulk LSM correlate with the ionic charge and ionic radius at a given formal cationic charge. The -site cation migration barrier takes place by an analogous mechanism that involves a ( on the site) hop into a via the path with the same cation transport carrier of . This diffusion pathway is found to have a barrier of approximately 1.6 eV, similar to the analogous -site hop. However, hopping of the antisite defect ( on the site) to a nearest-neighbor [ () mechanism] has a barrier of only 0.5 eV. Such a low () migration barrier opens the possibility to activate Mn transport in bulk LSM through the diffusion of the antisite () pathway on the -site lattice, particularly when the concentration of the Mn antisite defect can be altered upon varying the ratio and the activity of . The increase in doping concentration in bulk () is found to influence primarily the formation energies of cation transport carriers (cation vacancies), whereas the cation migration barriers exhibit only a weak dependence on the concentration.
4 More- Received 11 March 2017
DOI:https://doi.org/10.1103/PhysRevApplied.8.044001
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