Structure determination of LixTiS2 by neutron diffraction

Dahn, J. R.; McKinnon, W. R.; Haering, R. R.; Buyers, W. J. L.; Powell, B. M.

doi:10.1139/p80-033

Cited by 106 publications

(74 citation statements)

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“…As has been reported before for the 1T phase [7], lithium was also only found in the octahedral voids at 0, 0, 1 / 2 in 3R-Li x TiS 2 . Spurious negative scatteringlength density occurred in tetrahedral voids, but did not significantly exceed the noise level.…”

Section: Crystal Structure Of the 3r Phasessupporting

confidence: 82%

“…As expected, the difference between = 0.7 and 0.9 in is small, whereas it is considerable in (being larger for the more lithium-rich compounds) [5,7,32].…”

Section: Evolution Of Lattice Parameterssupporting

confidence: 77%

“…Their crystal structure with respect to the lithium-ion positions has been unambiguously elucidated by neutron powder diffractometry for = 0.12, 0.33, 0.67, and 1. A formerly discussed occupation of tetrahedral voids has been ruled out [7]. Also, the influence of on the lattice parameters has been extensively and comparatively studied with materials of different origins [8].…”

Section: Introductionmentioning

confidence: 99%

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The High-Temperature Transformation from 1T- to 3R-Li_xTiS₂ (x = 0.7, 0.9) as Observed in situ with Neutron Powder Diffraction

Wiedemann

Nakhal

Senyshyn

et al. 2015

Zeitschrift Für Physikalische Chemie

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Layered titanium disulfide is used as lithium-ion intercalating electrode material in batteries. The room-temperature stable trigonal 1T polymorphs of the intercalates Li x TiS 2 ( ≤ 1) are widely-investigated. However, the rombohedral 3R polymorphs, being stable at higher temperatures for large , are less well known.In this study, we report on the synthesis of phase-pure 1T-Li x TiS 2 ( = 0.7, 0.9) and its transformation to the 3R phase between 673 and 873 K as monitored using high-temperature neutron powder diffractometry. For the 3R polymorph, full Rietveld refinements show lithium ions to be statistically distributed over octahedral voids at the fractional coordinates 0, 0, 1 / 2 , exclusively. The comparison of Madelung energies with results of periodic quantum-chemical calculations reveals that the evolution of lattice parameters and the room-temperature stability of the 1T phase are not governed by electrostatics, but by correlation and polarization. The insights gained do not only elucidate the structure of 3R-Li x TiS 2 , but also help to understand and control polymorphism in layered transition-metal sulfides.

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Section: Crystal Structure Of the 3r Phasessupporting

confidence: 82%

“…As expected, the difference between = 0.7 and 0.9 in is small, whereas it is considerable in (being larger for the more lithium-rich compounds) [5,7,32].…”

Section: Evolution Of Lattice Parameterssupporting

confidence: 77%

Section: Introductionmentioning

confidence: 99%

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The High-Temperature Transformation from 1T- to 3R-Li_xTiS₂ (x = 0.7, 0.9) as Observed in situ with Neutron Powder Diffraction

Wiedemann

Nakhal

Senyshyn

et al. 2015

Zeitschrift Für Physikalische Chemie

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“…4 . Li + ions in h-Li x TiS 2 reside preferentially in octahedral sites between the TiS 2 layers 36 ͑see Fig. 1͒.…”

Section: Lithium Titanium Disulfidementioning

confidence: 99%

Li jump process inh−Li0.7TiS2studied by two-time
Wilkening
¹
,
Heitjans
²

2008
Phys. Rev. B
98
8
158
1
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7 Li spin-alignment NMR is used to trace ultraslow diffusion of Li + in the layered Li conductor Li x TiS 2 ͑x = 0.7͒. Two-time correlation functions were recorded for fixed evolution times as a function of mixing time at temperatures within the 7 Li rigid-lattice regime. The corresponding decay rates were identified as Li jump rates −1 ranging from 10 −1 to 10 3 s −1 between temperatures T = 148 K and 213 K. The jump rates obtained directly from spin-alignment echo NMR and those from diffusion induced maxima of spin-lattice relaxation peaks, monitored in the laboratory as well as in the rotating frame, are consistent with each other and follow an Arrhenius law with an activation energy of 0.41͑1͒ eV and a preexponential factor of 6.3͑1͒ ϫ 10 12 s −1 . Altogether, a solitary Li diffusion process was found between 148 and 510 K. Li diffusion was investigated in a dynamic range of about 10 orders of magnitude, i.e., 0.1ഛ −1 ഛ 7.8ϫ 10 8 s −1 . Additionally, the analysis of final-state echo amplitudes of the two-time correlation functions revealed information about the Li diffusion pathway in Li 0.7 TiS 2 . Obviously, a two-site jump process is present, i.e., besides the regularly occupied octahedral sites also the vacant tetrahedral ones within the van der Waals gap are involved in the overall two-dimensional diffusion process.

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“…Furthermore, instead of two anions of different sizes, voids of partial occupancy are present. Nevertheless we can calculate a formal approximate "∆ r" value for Li x TiS 2 from the S-S distances in TiS 2 (3.48Å [21]) and in LiTiS 2 (3.81Å [22]) which can be seen as a difference between the "void radius" and the Li radius. The corresponding value of 0.16Å seems rather low with respect to the large ∆t 0.5 value.…”

Section: Attempt To Explain the Observed Strong Deviation From Vegardmentioning

confidence: 99%

A Strong Deviation from Vegard’s Rule: X-Ray Powder Investigations of the Three Quasi-Binary Phase Systems BiOX–BiOY (X, Y = Cl, Br, I)

Keller

Krämer

2005

Zeitschrift Für Naturforschung B

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The three quasi-binary phase systems BiOX-BiOY (X, Y = Cl, Br, I) have been investigated by X-ray powder methods. No quaternary phases were found in the three systems. BiOCl-BiOBr and BiOBr-BiOI form systems of unlimited mutual solubility. BiOCl-BiOI is a system of limited solubility at the iodine-rich side. In the BiOBr-BiOI system a strong deviation from Vegard's rule is observed with respect to one of the lattice parameters. A few methods to quantify such a deviation are briefly discussed and a possible explanation for the strong deviation in the BiOBr-BiOI system is proposed. Error calculations have been performed to estimate uncertainties in the concentration parameter x of the investigated mixtures. The crystal structure of BiOI has been re-determined by single crystal structure analysis.

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Structure determination of Li_xTiS₂ by neutron diffraction

Cited by 106 publications

References 0 publications

The High-Temperature Transformation from 1T- to 3R-Li_xTiS₂ (x = 0.7, 0.9) as Observed in situ with Neutron Powder Diffraction

The High-Temperature Transformation from 1T- to 3R-Li_xTiS₂ (x = 0.7, 0.9) as Observed in situ with Neutron Powder Diffraction

Li jump process inh−Li0.7TiS2studied by two-time
Wilkening
¹
,
Heitjans
²

2008
Phys. Rev. B
98
8
158
1
View full text Add to dashboard Cite

A Strong Deviation from Vegard’s Rule: X-Ray Powder Investigations of the Three Quasi-Binary Phase Systems BiOX–BiOY (X, Y = Cl, Br, I)

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Structure determination of LixTiS2 by neutron diffraction

Cited by 106 publications

References 0 publications

The High-Temperature Transformation from 1T- to 3R-Li x TiS2 (x = 0.7, 0.9) as Observed in situ with Neutron Powder Diffraction

The High-Temperature Transformation from 1T- to 3R-Li x TiS2 (x = 0.7, 0.9) as Observed in situ with Neutron Powder Diffraction

Li jump process inh−Li0.7TiS2studied by two-timeWilkening1, Heitjans2 2008Phys. Rev. B9881581View full textAdd to dashboardCite

A Strong Deviation from Vegard’s Rule: X-Ray Powder Investigations of the Three Quasi-Binary Phase Systems BiOX–BiOY (X, Y = Cl, Br, I)

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Structure determination of Li_xTiS₂ by neutron diffraction

The High-Temperature Transformation from 1T- to 3R-Li_xTiS₂ (x = 0.7, 0.9) as Observed in situ with Neutron Powder Diffraction

The High-Temperature Transformation from 1T- to 3R-Li_xTiS₂ (x = 0.7, 0.9) as Observed in situ with Neutron Powder Diffraction

Li jump process inh−Li0.7TiS2studied by two-time
Wilkening
¹
,
Heitjans
²

2008
Phys. Rev. B
98
8
158
1
View full text Add to dashboard Cite