One-Dimensional Oxygen Diffusion Mechanism in Sr2ScGaO5 Electrolyte Explored by Neutron and Synchrotron Diffraction, 17O NMR, and Density Functional Theory Calculations
| Autor: | Serena Corallini, Hellmut Eckert, Andrea Piovano, Josef Stern, Noriya Ichikawa, Jinjun Ren, Werner Paulus, Shubra Singh, Gilles Silly, K. Conder, Yuichi Shimakawa, Monica Ceretti, Clemens Ritter, Wei-Tin Chen, Fangcheng Chou |
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| Přispěvatelé: | Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Institut Laue-Langevin (ILL), ILL, Institut für Physikalische Chemie [Münster], Westfälische Wilhelms-Universität Münster (WWU), Insituto die Fisica, Univesidade de Sao Paulo, Paul Scherrer Institute (PSI), Center for Condensed Matter Sciences, National Taiwan University, Taiwan Consortium of Emergent Crystalline Materials, Institute for Chemical Research, Kyoto University, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR), Westfälische Wilhelms-Universität Münster = University of Münster (WWU), Instituto de Fisica da Universidade de São Paulo (IFUSP), Universidade de São Paulo = University of São Paulo (USP) |
| Rok vydání: | 2015 |
| Předmět: |
Phase transition
chemistry.chemical_element 02 engineering and technology engineering.material 010402 general chemistry 01 natural sciences Oxygen RESSONÂNCIA MAGNÉTICA NUCLEAR Brownmillerite Neutron Physical and Theoretical Chemistry Solid oxygen [CHIM.MATE]Chemical Sciences/Material chemistry 021001 nanoscience & nanotechnology 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials Crystallography General Energy chemistry Chemical physics engineering Orthorhombic crystal system Density functional theory 0210 nano-technology Electric field gradient |
| Zdroj: | Repositório Institucional da USP (Biblioteca Digital da Produção Intelectual) Universidade de São Paulo (USP) instacron:USP Journal of Physical Chemistry C Journal of Physical Chemistry C, American Chemical Society, 2015, pp.11447. ⟨10.1021/acs.jpcc.5b02173⟩ Journal of Physical Chemistry C, 2015, pp.11447. ⟨10.1021/acs.jpcc.5b02173⟩ |
| ISSN: | 1932-7455 1932-7447 |
| Popis: | We investigated moderate-temperature oxygen diffusion mechanisms in Sr2ScGaO5 with Brownmillerite structure type. From oxygen isotope 18O−16O exchange experiments we determined that oxygen mobility sets in above 550 °C. Temperature-dependent neutron and X-ray (synchrotron) diffraction experiments allowed us to correlate the oxygen mobility with a subtle phase transition of the orthorhombic room-temperature structure with I2mb space group toward Imma, going along with a disorder of the (GaO4)∞-tetrahedral chains. From lattice dynamical simulations we could clearly evidence that dynamic switching of the (GaO4)∞-tetrahedral chains from its R to L configuration sets in at 600 °C, thus correlating oxygen diffusion with the dynamic disorder. Oxygen ion diffusion pathways are thus constrained along the onedimensional oxygen vacancy channels, which is a different diffusion mechanism compared to that of the isostructural CaFeO2.5, where diffusion of the apical oxygen atoms into the vacant lattice sites are equally involved in the diffusion pathway. The proposed ordered room-temperature structure in I2mb is strongly supported by 17O, 45Sc, and 71Ga NMR measurements, which indicate the presence of crystallographically unique sites and the absence of local disordering effects below the phase transition. The electric field gradient tensor components measured at the nuclear sites are found to be in excellent agreement with calculated values using the WIEN2k program. The oxygen site assignment has been independently confirmed by 17O{45Sc} transfer of adiabatic populations double-resonance experiments. |
| Databáze: | OpenAIRE |
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