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Al/Ga-doped Li7La3Zr2O12 garnets as li-ion solid-state battery electrolytes : atomistic insights into local coordination environments and their influence on 17O, 27Al, and 71Ga NMR spectra
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Karasulu, Bora, Emge, Steffen P., Groh, Matthias F., Grey, Clare P. and Morris, Andrew J. (2020) Al/Ga-doped Li7La3Zr2O12 garnets as li-ion solid-state battery electrolytes : atomistic insights into local coordination environments and their influence on 17O, 27Al, and 71Ga NMR spectra. Journal of the American Chemical Society, 142 (6). pp. 3132-3148. doi:10.1021/jacs.9b12685 ISSN 0002-7863.
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Official URL: http://dx.doi.org/10.1021/jacs.9b12685
Abstract
Li7La3Zr2O12 (LLZO) garnets are among the most promising solid electrolytes for next-generation all-solid-state Li-ion battery applications due to their high stabilities and ionic conductivities. To help determine the influence of different supervalent dopants on the crystal structure and site preferences, we combine solid-state 17O, 27Al, and 71Ga magic angle spinning (MAS) NMR spectroscopy and density-functional theory (DFT) calculations. DFT-based defect configuration analysis for the undoped and Al and/or Ga-doped LLZO variants uncovers an interplay between the local network of atoms and the observed NMR signals. Specifically, the two characteristic features observed in both 27Al and 71Ga NMR spectra result from both the deviations in the polyhedral coordination/site-symmetry within the 4-fold coordinated Li1/24d sites (rather than the doping of the other Li2/96h or La sites) and with the number of occupied adjacent Li2 sites that share oxygen atoms with these dopant sites. The sharp 27Al and 71Ga resonances arise from dopants located at a highly symmetric tetrahedral 24d site with four corner-sharing LiO4 neighbors, whereas the broader features originate from highly distorted dopant sites with fewer or no immediate LiO4 neighbors. A correlation between the size of the 27Al/71Ga quadrupolar coupling and the distortion of the doping sites (viz. XO4/XO5/XO6 with X = {Al/Ga}) is established. 17O MAS NMR spectra for these systems provide insights into the oxygen connectivity network: 17O signals originating from the dopant-coordinating oxygens are resolved and used for further characterization of the microenvironments at the dopant and other sites.
| Item Type: | Journal Article | ||||||||||||||||||
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| Subjects: | Q Science > QD Chemistry T Technology > TK Electrical engineering. Electronics Nuclear engineering |
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| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||||||||
| Library of Congress Subject Headings (LCSH): | Electrolytes, Electrolytes -- Conductivity, Solid state batteries , Lithium ion batteries , Nuclear magnetic resonance spectroscopy , Density functionals | ||||||||||||||||||
| Journal or Publication Title: | Journal of the American Chemical Society | ||||||||||||||||||
| Publisher: | American Chemical Society | ||||||||||||||||||
| ISSN: | 0002-7863 | ||||||||||||||||||
| Official Date: | 12 February 2020 | ||||||||||||||||||
| Dates: |
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| Volume: | 142 | ||||||||||||||||||
| Number: | 6 | ||||||||||||||||||
| Page Range: | pp. 3132-3148 | ||||||||||||||||||
| DOI: | 10.1021/jacs.9b12685 | ||||||||||||||||||
| Status: | Peer Reviewed | ||||||||||||||||||
| Publication Status: | Published | ||||||||||||||||||
| Access rights to Published version: | Open Access (Creative Commons) | ||||||||||||||||||
| Date of first compliant deposit: | 15 June 2021 | ||||||||||||||||||
| Date of first compliant Open Access: | 16 June 2021 | ||||||||||||||||||
| RIOXX Funder/Project Grant: |
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| Is Part Of: | 1 |
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