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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

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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
Subjects: Q Science > QD Chemistry
T Technology > TK Electrical engineering. Electronics Nuclear engineering
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:
DateEvent
12 February 2020Published
17 January 2020Available
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:
Project/Grant IDRIOXX Funder NameFunder ID
EP/P003532/1[EPSRC] Engineering and Physical Sciences Research Councilhttp://dx.doi.org/10.13039/501100000266
GR 5342/1-1[DFG] Deutsche Forschungsgemeinschafthttp://dx.doi.org/10.13039/501100001659
iCASE 1834544[EPSRC] Engineering and Physical Sciences Research Councilhttp://dx.doi.org/10.13039/501100000266
RP\R1\180147Royal Societyhttp://dx.doi.org/10.13039/501100000288
EP/P020259/1[EPSRC] Engineering and Physical Sciences Research Councilhttp://dx.doi.org/10.13039/501100000266
Is Part Of: 1

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