Re-investigating the structure-property relationship of the solid electrolytes Li 3- x In 1- x Zr x Cl 6 and the impact of In-Zr(iv) substitution.

Autor: van der Maas E; Department of Radiation Science and Technology, Delft University of Technology Delft Netherlands s.ganapathy@tudelft.nl m.wagemaker@tudelft.nl., Famprikis T; Department of Radiation Science and Technology, Delft University of Technology Delft Netherlands s.ganapathy@tudelft.nl m.wagemaker@tudelft.nl., Pieters S; Magnetic Resonance Research Center, Radboud University Nijmegen Netherlands erhve@nmr.ru.nl., Dijkstra JP; Magnetic Resonance Research Center, Radboud University Nijmegen Netherlands erhve@nmr.ru.nl., Li Z; Department of Radiation Science and Technology, Delft University of Technology Delft Netherlands s.ganapathy@tudelft.nl m.wagemaker@tudelft.nl., Parnell SR; Department of Radiation Science and Technology, Delft University of Technology Delft Netherlands s.ganapathy@tudelft.nl m.wagemaker@tudelft.nl., Smith RI; ISIS Facility, Rutherford Appleton Laboratory Chilton Didcot Oxfordshire UK OX11 0QX., van Eck ERH; Magnetic Resonance Research Center, Radboud University Nijmegen Netherlands erhve@nmr.ru.nl., Ganapathy S; Department of Radiation Science and Technology, Delft University of Technology Delft Netherlands s.ganapathy@tudelft.nl m.wagemaker@tudelft.nl., Wagemaker M; Department of Radiation Science and Technology, Delft University of Technology Delft Netherlands s.ganapathy@tudelft.nl m.wagemaker@tudelft.nl.
Jazyk: angličtina
Zdroj: Journal of materials chemistry. A [J Mater Chem A Mater] 2023 Jan 25; Vol. 11 (9), pp. 4559-4571. Date of Electronic Publication: 2023 Jan 25 (Print Publication: 2023).
DOI: 10.1039/d2ta08433c
Abstrakt: Chloride-based solid electrolytes are considered interesting candidates for catholytes in all-solid-state batteries due to their high electrochemical stability, which allows the use of high-voltage cathodes without protective coatings. Aliovalent Zr(iv) substitution is a widely applicable strategy to increase the ionic conductivity of Li 3 M(iii)Cl 6 solid electrolytes. In this study, we investigate how Zr(iv) substitution affects the structure and ion conduction in Li 3- x In 1- x Zr x Cl 6 (0 ≤ x ≤ 0.5). Rietveld refinement using both X-ray and neutron diffraction is used to make a structural model based on two sets of scattering contrasts. AC-impedance measurements and solid-state NMR relaxometry measurements at multiple Larmor frequencies are used to study the Li-ion dynamics. In this manner the diffusion mechanism and its correlation with the structure are explored and compared to previous studies, advancing the understanding of these complex and difficult to characterize materials. It is found that the diffusion in Li 3 InCl 6 is most likely anisotropic considering the crystal structure and two distinct jump processes found by solid-state NMR. Zr-substitution improves ionic conductivity by tuning the charge carrier concentration, accompanied by small changes in the crystal structure which affect ion transport on short timescales, likely reducing the anisotropy.
Competing Interests: The authors declare no competing interests.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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