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Floating zone crystal growth, structure, and properties of a cubic Li5.5La3Nb1.5Zr0.5O12 garnet-type lithium-ion conductor

Journal Article · · Journal of Materials Chemistry. A
DOI:https://doi.org/10.1039/d3ta04606k· OSTI ID:2203417
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [1];  [7];  [5];  [8];  [5];  [1]
  1. Univ. of Utah, Salt Lake City, UT (United States)
  2. Johns Hopkins Univ., Baltimore, MD (United States)
  3. Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW (Australia); Univ. of Sydney, NSW (Australia)
  4. Los Alamos National Laboratory (LANL), Los Alamos, NM (United States). National High Magnetic Field Lab. (MagLab)
  5. Platform for the Accelerated Realization, Analysis and Discovery of Interface Materials (PARADIM)
  6. Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  7. Cornell Univ., Ithaca, NY (United States). Cornell High Energy Synchrotron Source (CHESS)
  8. National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
+ Show Author Affiliations
As a promising candidate for solid-state electrolytes in Li-ion batteries, the garnet-type Li-ion conductor series Li5+xLa3Nb2-xZrxO12 (LLNZO) (0 ≤ x ≤ 2) exhibits high ionic conductivity at room temperature. However, no previous single-crystal growth or characterization has been reported for LLNZO compositions 0 ≤ x ≤ 1. To obtain a complete understanding of the trend in the structure–property relationship in this class of materials, we used the floating zone (FZ) method to grow a single crystal of Li5.5La3Nb1.5Zr0.5O12 that was 4 mm in diameter and 10 mm in length. Using Laue neutron single-crystal diffraction, two distinct Li sites were observed: tetrahedral 24d and octahedral 96h sites. The maximum entropy method (MEM) based on neutron single-crystal diffraction data was used to map Li nuclear density and estimate that the bottleneck of Li transport exists between neighboring tetrahedral and octahedral sites, and that Li is delocalized between split octahedral sites. Room-temperature Li-ion conductivity in Li5.5La3Nb1.5Zr0.5O12 measured with electrochemical impedance spectroscopy (EIS) was 1.37 × 10-4 S cm-1. The Li migration activation energy was estimated to be 0.50 eV from EIS and 0.47 eV from dielectric relaxation measurements. The Li-ion jump attempt rate was estimated to be 1.47 × 1012 Hz while the time scale of successful migration is 10-7 to 10-6 s.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE; NSF
Grant/Contract Number:
89233218CNA000001
OSTI ID:
2203417
Report Number(s):
LA-UR--23-30252
Journal Information:
Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 40 Vol. 11; ISSN 2050-7488
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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