Insight into lithium distribution in lithium-stuffed garnet oxides through neutron diffraction and atomistic simulation: Li7-xLa 3Zr2-xTaxO12 (x = 0-2) series

Yuxing Wang, Ashfia Huq, Wei Lai

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Abstract

Lithium-stuffed garnet oxides are promising candidates of lithium ion electrolyte materials due to their high ionic conductivities and good chemical stability. In this study, time-of-flight (TOF) neutron diffraction experiments and the Rietveld refinement were performed on four garnet compounds in the Li7-xLa3Zr2-xTaxO12 (x = 0-2) series to study their average structures. Different structural models (split-site and anisotropic displacement) for lithium disorder at tetrahedral (Td) and octahedral (Oh) sites were compared and results suggested possible lithium disorder around both ideal Oh and ideal Td sites. To study the local lithium distribution, atomistic simulations based on static energy minimization with interatomic potentials were carried out on a large number of configurations of eight compositions. We demonstrated that energy probability distribution plots were helpful in understanding the lithium disorder/order in these materials. Nuclear density maps provided a visual presentation of structural disorder at both Td and Oh lithium sites. Our simulation results suggested that Td lithium occupancy is generally lower than that obtained from the average structure (Rietveld refinement) and the exclusion principle (no nearest-neighbor Td-Oh-Td lithium triplets). In addition, the nearest-neighbor Td-Oh lithium pairs and (Oh,□)-Td-(Oh,□) lithium clusters appear to be the characteristic local features contributing to the structure and conduction of these lithium-stuffed garnet oxides.

LanguageEnglish (US)
Pages39-49
Number of pages11
JournalSolid State Ionics
Volume255
DOIs
StatePublished - Feb 1 2014

Profile

Garnets
Neutron diffraction
Lithium
garnets
Oxides
neutron diffraction
lithium
oxides
simulation
disorders
Rietveld refinement
Order disorder transitions
Chemical stability
Ionic conductivity
exclusion
Probability distributions
ion currents
Electrolytes
plots
electrolytes

Keywords

  • Atomistic simulation
  • Disorder
  • Lithium-stuffed garnet oxides
  • Neutron diffraction
  • Solid-state ionic conductors

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Chemistry(all)

Cite this

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title = "Insight into lithium distribution in lithium-stuffed garnet oxides through neutron diffraction and atomistic simulation: Li7-xLa 3Zr2-xTaxO12 (x = 0-2) series",
abstract = "Lithium-stuffed garnet oxides are promising candidates of lithium ion electrolyte materials due to their high ionic conductivities and good chemical stability. In this study, time-of-flight (TOF) neutron diffraction experiments and the Rietveld refinement were performed on four garnet compounds in the Li7-xLa3Zr2-xTaxO12 (x = 0-2) series to study their average structures. Different structural models (split-site and anisotropic displacement) for lithium disorder at tetrahedral (Td) and octahedral (Oh) sites were compared and results suggested possible lithium disorder around both ideal Oh and ideal Td sites. To study the local lithium distribution, atomistic simulations based on static energy minimization with interatomic potentials were carried out on a large number of configurations of eight compositions. We demonstrated that energy probability distribution plots were helpful in understanding the lithium disorder/order in these materials. Nuclear density maps provided a visual presentation of structural disorder at both Td and Oh lithium sites. Our simulation results suggested that Td lithium occupancy is generally lower than that obtained from the average structure (Rietveld refinement) and the exclusion principle (no nearest-neighbor Td-Oh-Td lithium triplets). In addition, the nearest-neighbor Td-Oh lithium pairs and (Oh,□)-Td-(Oh,□) lithium clusters appear to be the characteristic local features contributing to the structure and conduction of these lithium-stuffed garnet oxides.",
keywords = "Atomistic simulation, Disorder, Lithium-stuffed garnet oxides, Neutron diffraction, Solid-state ionic conductors",
author = "Yuxing Wang and Ashfia Huq and Wei Lai",
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T2 - Solid State Ionics

AU - Wang,Yuxing

AU - Huq,Ashfia

AU - Lai,Wei

PY - 2014/2/1

Y1 - 2014/2/1

N2 - Lithium-stuffed garnet oxides are promising candidates of lithium ion electrolyte materials due to their high ionic conductivities and good chemical stability. In this study, time-of-flight (TOF) neutron diffraction experiments and the Rietveld refinement were performed on four garnet compounds in the Li7-xLa3Zr2-xTaxO12 (x = 0-2) series to study their average structures. Different structural models (split-site and anisotropic displacement) for lithium disorder at tetrahedral (Td) and octahedral (Oh) sites were compared and results suggested possible lithium disorder around both ideal Oh and ideal Td sites. To study the local lithium distribution, atomistic simulations based on static energy minimization with interatomic potentials were carried out on a large number of configurations of eight compositions. We demonstrated that energy probability distribution plots were helpful in understanding the lithium disorder/order in these materials. Nuclear density maps provided a visual presentation of structural disorder at both Td and Oh lithium sites. Our simulation results suggested that Td lithium occupancy is generally lower than that obtained from the average structure (Rietveld refinement) and the exclusion principle (no nearest-neighbor Td-Oh-Td lithium triplets). In addition, the nearest-neighbor Td-Oh lithium pairs and (Oh,□)-Td-(Oh,□) lithium clusters appear to be the characteristic local features contributing to the structure and conduction of these lithium-stuffed garnet oxides.

AB - Lithium-stuffed garnet oxides are promising candidates of lithium ion electrolyte materials due to their high ionic conductivities and good chemical stability. In this study, time-of-flight (TOF) neutron diffraction experiments and the Rietveld refinement were performed on four garnet compounds in the Li7-xLa3Zr2-xTaxO12 (x = 0-2) series to study their average structures. Different structural models (split-site and anisotropic displacement) for lithium disorder at tetrahedral (Td) and octahedral (Oh) sites were compared and results suggested possible lithium disorder around both ideal Oh and ideal Td sites. To study the local lithium distribution, atomistic simulations based on static energy minimization with interatomic potentials were carried out on a large number of configurations of eight compositions. We demonstrated that energy probability distribution plots were helpful in understanding the lithium disorder/order in these materials. Nuclear density maps provided a visual presentation of structural disorder at both Td and Oh lithium sites. Our simulation results suggested that Td lithium occupancy is generally lower than that obtained from the average structure (Rietveld refinement) and the exclusion principle (no nearest-neighbor Td-Oh-Td lithium triplets). In addition, the nearest-neighbor Td-Oh lithium pairs and (Oh,□)-Td-(Oh,□) lithium clusters appear to be the characteristic local features contributing to the structure and conduction of these lithium-stuffed garnet oxides.

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