Etude de l'insertion de lithium dans In16Sn4S32 par RMN (7Li) et spectrométrie Mössbauer (119Sn)

Elidrissi-Moubtassim, M. L.; Olivier‐Fourcade, J.; Jumas, Jean‐Claude; Senegas, J.

doi:10.1016/0022-4596(90)90057-5

Cited by 12 publications

(7 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Asymmetric 7 Li NMR line shapes have been reported previously for lithium-inserted indium tin spinels. − The single 7 Li NMR resonances acquired under static conditions were decomposed in a narrow component and a broad component. The narrow component was assigned to lithium in octahedral vacant sites, and the broad component to lithium in tetrahedral sites that provide less space for lithium motion.…”

Section: Resultssupporting

confidence: 64%

Structure and Dynamics of Lithium-Intercalated SnS₂. ^6,7Li and ¹¹⁹Sn Solid State NMR

Pietraß¹,

Taulèlle²,

Lavela³

et al. 1997

J. Phys. Chem. B

Self Cite

View full text Add to dashboard Cite

Lithium-intercalated SnS2 compounds have been studied with 6,7Li and 119Sn solid state NMR spectroscopy addressing the location of the insertion sites of the lithium. The central transition in the 7Li NMR spectra can be decomposed into two components giving rise to different quadrupole coupling constants and may be assigned to lithium in octahedral and tetrahedral lattice sites. 1H and 7Li decoupling experiments with 6Li NMR detection as well as the narrowing effect of magic angle spinning on the 7Li NMR line width indicate the presence of dipolar interactions. Temperature dependent 7Li NMR spin−lattice relaxation times reveal a decrease in activation energy for lithium motion at higher lithium contents. 119Sn spectra revealed additional peaks shifted downfield from the Sn(IV) resonance. 119Sn spin−lattice relaxation times and the total number of observable tin nuclei indicate that with increasing lithium content interactions with delocalized electrons may be present. In summary, the NMR results show that the lithium is preferentially inserted in the interlayer space. A mechanism describing the lithium insertion process is derived.

show abstract

Section: Resultssupporting

confidence: 64%

Structure and Dynamics of Lithium-Intercalated SnS₂. ^6,7Li and ¹¹⁹Sn Solid State NMR

Pietraß¹,

Taulèlle²,

Lavela³

et al. 1997

J. Phys. Chem. B

Self Cite

View full text Add to dashboard Cite

show abstract

“…In this system, a solid-state region has been defined where mixed valence X sulfides are based on the spinel form of In 2 S 3 . , These spinel sulfides are three-dimensional and characterized by the presence of vacancies and the possibility for X atoms to adopt two oxidation states (Sn II-IV , Fe II-III , or Cu I-II ) which correspond to different electronic configurations. Up to now, the lithium insertion has been analyzed in the spinel tin indium sulfides with the help of various experimental techniques. , As deduced from X-ray diffraction spectroscopy, the reaction occurs without structural change. Atomic emission spectroscopy has been used to measure the inserted lithium quantity and has shown that the insertion is nearly reversible.…”

mentioning

confidence: 99%

Lithium Insertion in Three-Dimensional Tin Sulfides

and¹,

Lannoo²,

Moubtassim³

et al. 1997

Chem. Mater.

View full text Add to dashboard Cite

The tin reduction during lithium insertion in spinel sulfide compounds is investigated. Mössbauer and RMN spectroscopy are combined with tight binding calculations to analyze the reduction mechanism. It is shown that the formal reaction SnIV + 2e- → SnII is involved without an intermediate Sn oxidation state. The following mechanism is proposed: lithium ions create shallow and deep-defect donor states; the trapping of two electrons on the deep one, which exhibits a negative U behavior, induces the reduction of the corresponding tin atom.

show abstract

“…However, Lamb−Mossbauer factors are needed to convert relative spectral areas of the two components of the 119 Sn Mossbauer spectrum into tin abundances. 98 It is well-known that, at RT, these factors have largely different values for Sn 2+ and Sn 4+ . 99 This explains that, at 300 K, the area fraction of the absorption peak related to Sn 4+ contribution is much more important than that of Sn 2+ (Figure 5 and Table 2), conversely to the expected Sn 2+ /Sn 4+ ratio in Cr 2 Sn 3 S 7 .…”

Section: ■ Resultsmentioning

confidence: 99%

Is the Presence of Sn²⁺ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Guiot,

Prestipino,

Guilmeau

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

Comprehending the relationship between crystal structures and transport properties is crucial to develop materials with improved electrical and thermal properties for thermoelectric applications. In this article, we report on the complex crystal structure and physical properties of Cr 2 Sn 3 S 7 , a n-type magnetic semiconductor with a low energy band gap and low thermal conductivity. Importantly, we demonstrate that the high level of structural complexity is related to the coexistence of two sublattices: a host lattice, [Cr 4 Sn 2 S 11 ] 2− , characterized by a mixed Sn 4+ /Cr 3+ occupancy of its cationic sites, and a guest lattice characterized by [Sn 4 S 3 ] 2+ chains, containing Sn 2+ cations only, closely related to the ones encountered in the orthorhombic SnS compound. By combining experiments including X-ray diffraction with ab initio calculations of electrons and phonons, we succeeded to elucidate the origin of the low thermal conductivity in Cr 2 Sn 3 S 7. We demonstrate that the low dimensionality of the [Sn 4 S 3 ] 2+ chains, which generates weak Sn•••S interactions with the 3D host lattice, is induced by the lone pair stereochemical activity of Sn 2+ . This lattice softening favors strong anisotropic vibrations at low frequencies, highlighting the primordial role played by Sn 2+ cations in both crystal structure dimensionality and low thermal conductivity in tin-based sulfides. 2 =, where S, σ, κ, and T represent the Seebeck coefficient or thermopower, electrical conductivity, total thermal conductivity, and operating absolute temperature, respectively). This anisotropy in the

show abstract

Etude de l'insertion de lithium dans In16Sn4S32 par RMN (7Li) et spectrométrie Mössbauer (119Sn)

Cited by 12 publications

References 14 publications

Structure and Dynamics of Lithium-Intercalated SnS₂. ^6,7Li and ¹¹⁹Sn Solid State NMR

Structure and Dynamics of Lithium-Intercalated SnS₂. ^6,7Li and ¹¹⁹Sn Solid State NMR

Lithium Insertion in Three-Dimensional Tin Sulfides

Is the Presence of Sn²⁺ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Contact Info

Product

Resources

About

Etude de l'insertion de lithium dans In16Sn4S32 par RMN (7Li) et spectrométrie Mössbauer (119Sn)

Cited by 12 publications

References 14 publications

Structure and Dynamics of Lithium-Intercalated SnS2. 6,7Li and 119Sn Solid State NMR

Structure and Dynamics of Lithium-Intercalated SnS2. 6,7Li and 119Sn Solid State NMR

Lithium Insertion in Three-Dimensional Tin Sulfides

Is the Presence of Sn2+ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?

Contact Info

Product

Resources

About

Structure and Dynamics of Lithium-Intercalated SnS₂. ^6,7Li and ¹¹⁹Sn Solid State NMR

Structure and Dynamics of Lithium-Intercalated SnS₂. ^6,7Li and ¹¹⁹Sn Solid State NMR

Is the Presence of Sn²⁺ a Crucial Factor for the Generation of Low Thermal Conductivity in Tin-Based Sulfides?