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La 3 Li 3 W2O 12 : Ionic Diffusion in a Perovskite with Lithium on Both A- and BSites

DOI: 10.1021/acs.chemmater.6b03220 DOI Help

Authors: Alma B. Santibáñez-mendieta (Department of Chemistry, University of Liverpool) , Christophe Didier (Department of Chemistry, University of Liverpool) , Kenneth K. Inglis (Department of Chemistry, University of Liverpool) , Alex J. Corkett (Department of Chemistry, University of Liverpool) , Michael Pitcher (Department of Chemistry, University of Liverpool) , Marco Zanella (Department of Chemistry, University of Liverpool) , J. Felix Shin (Department of Chemistry, University of Liverpool) , Luke Daniels (Department of Chemistry, University of Liverpool) , Aydar Rakhmatullin (CEMHTI-CNRS UPR3079, Conditions Extrêmes et Matériaux: Haute Température et Irradiation) , Ming Li (Faculty of Engineering, University of Nottingham) , Matthew S. Dyer (Department of Chemistry, University of Liverpool) , John B. Claridge (University of Liverpool) , Frédéric Blanc (University of Liverpool) , Matthew J. Rosseinsky (University of Liverpool)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry Of Materials

State: Published (Approved)
Published: September 2016
Diamond Proposal Number(s): 12336

Abstract: The structure and Li+ ion dynamics of a new class of ABO3 perovskite with Li on both the A- and B-sites are described. La3Li3W2O12 is synthesised by solid state reaction at 900°C and shown by powder X-ray diffraction to adopt the structure of a monoclinic double perovskite (A2)BBꞌO6, (La1.5Li0.5)WLiO6, with rock salt order of W6+ and Li+ on the B-site. High resolution powder neutron diffraction locates A-site Li in a distorted tetrahedron displaced from the conventional perovskite A-site, which differs considerably from the sites occupied by Li in the well studied La2/3-xLi3xTiO3 family. This is confirmed by the observation of a lower coordinated Li+ ion in the 6Li magic angle spinning nuclear magnetic resonance (NMR) spectra, in addition to the B-site LiO6, and supported computationally by density functional theory (DFT), which also suggests local order of A-site La3+ and Li+. DFT shows that the vacancies necessary for transport can arise from Frenkel or La excess defects, with an energetic cost of ~0.4 eV/vacancy in both cases. Ab initio molecular dynamics establishes that the Li+ ion dynamics occur by a pathway involving a series of multiple localised Li hops between two neighbouring A-sites with an overall energy barrier of ~0.25 eV, with additional possible pathways involving Li exchange between the A- and B-sites. A similar activation energy for Li+ ion mobility (~0.3 eV) was obtained from variable temperature 6Li and 7Li line narrowing and relaxometry NMR experiments, suggesting that the barrier to Li hopping between sites in La3Li3W2O12 is comparable to the best oxide Li+ ion conductors. AC impedance-derived conductivities confirm that Li+ ions are mobile but that the long-range Li+ diffusion has a higher barrier (~0.5 eV) which may be associated with blocking of transport by A-site La3+ ions.

Subject Areas: Chemistry, Materials

Instruments: I11-High Resolution Powder Diffraction

Added On: 12/10/2016 13:31

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