The role of oxygen vacancies on the vibrational motions of hydride ions in the oxyhydride of barium titanate
Artikel i vetenskaplig tidskrift, 2020

Perovskite-type oxyhydrides, BaTiO3-xHx, represent a novel class of hydride ion conducting materials of interest for several electrochemical applications, but fundamental questions surrounding the defect chemistry and hydride ion transport mechanism remain unclear. Here we report results from powder X-ray diffraction, thermal gravimetric analysis, nuclear magnetic resonance spectroscopy, inelastic neutron scattering (INS), and density functional theory (DFT) simulations on three metal hydride reduced BaTiO3 samples characterized by the simultaneous presence of hydride ions and oxygen vacancies. The INS spectra are characterized by two predominating bands at around 114 (ω⊥) and 128 (ω∥) meV, assigned as fundamental Ti-H vibrational modes perpendicular and parallel to the Ti-H-Ti bond direction, respectively, and four additional, weaker, bands at around 99 (ω1), 110 (ω2), 137 (ω3) and 145 (ω4) meV that originate from a range of different local structures associated with different configurations of the hydride ions and oxygen vacancies in the materials. Crucially, the combined analyses of INS and DFT data confirm the presence of both nearest and next-nearest neighbouring oxygen vacancies to the hydride ions. This supports previous findings from quasielastic neutron scattering experiments, that the hydride ion transport is governed by jump diffusion dynamics between neighbouring and next-nearest neighbouring hydride ion-oxygen vacancy local structures. Furthermore, the investigation of the momentum transfer dependence of the INS spectrum is used to derive the mean square displacement of the hydride ions, which is shown to be in excellent agreement with the calculations. Analysis of the mean square displacement confirms that the hydrogen vibrational motions are localized in nature and only very weakly affected by the dynamics of the surrounding perovskite structure. This insight motivates efforts to identify alternative host lattices that allow for a less localization of the hydride ions as a route to higher hydride ion conductivities.

Författare

[Person a4757e15-a517-4068-a0c1-25e84be97175 not found]

Chalmers, Kemi och kemiteknik, Energi och material, Oorganisk miljökemi 2

[Person 6b530805-7d33-457e-8b42-5200a199056a not found]

Chalmers, Kemi och kemiteknik, Energi och material, Oorganisk miljökemi 2

[Person a7883578-30ab-4db5-8169-fa30c0a5f9bb not found]

Chalmers, Fysik, Material- och ytteori

[Person e0691d19-811f-4f05-a549-9e058a05797d not found]

Chalmers, Fysik, Kondenserad materie- och materialteori

[Person cccdc9c9-5eb7-41bc-b690-abd74d68cdae not found]

Stockholms universitet

[Person b4790a2f-8382-489f-8f22-25904454aca4 not found]

Stockholms universitet

[Person d1d14e47-b164-4f89-92f6-ab8afbf09cd5 not found]

Stockholms universitet

[Person 264ba6d8-c6dc-4777-8e15-d746b68ef202 not found]

Stockholms universitet

[Person 4ddb7f7f-09c5-4b5c-8853-e2ca2b49a688 not found]

Rutherford Appleton Laboratory

[Person f728c8c6-0b5e-4c45-9a87-a114c06b4b0e not found]

Oak Ridge National Laboratory

[Person 5f03008f-6848-4003-99ca-6d7beb8433fe not found]

Chalmers, Fysik, Materialfysik

[Person ca85ed47-f855-42bc-b446-a6435c030365 not found]

Chalmers, Kemi och kemiteknik, Energi och material, Oorganisk miljökemi 2

Journal of Materials Chemistry A

20507488 (ISSN) 20507496 (eISSN)

Vol. 8 13 6360-6371

Protonledning och nanojonik

Energimyndigheten, 2013-01-01 -- 2016-12-31.

Proton- och hydridjon-ledning i perovskiter

Energimyndigheten, 2018-01-01 -- 2021-12-31.

Utforskning av vätedynamik i nya perovskitoxyhydridmaterial med neutronspridningstekniker

Vetenskapsrådet (VR), 2015-01-01 -- 2018-12-31.

Ämneskategorier

Den kondenserade materiens fysik

DOI

10.1039/c9ta11912d

Mer information

Senast uppdaterat

2021-01-21