Details
| Original language | English |
|---|---|
| Pages (from-to) | 1569-1576 |
| Number of pages | 8 |
| Journal | Chemistry of materials |
| Volume | 18 |
| Issue number | 6 |
| Publication status | Published - 21 Mar 2006 |
Abstract
The intercalation reaction of Li into the complex ternary selenide Cr 4TiSe8 was investigated as function of time and temperature. The treatment of the host compound with a solution of butyl lithium in n-hexane (BuLi) leads to Li insertion up to the composition Li 2.8Cr4TiSe8. The intercalation reaction is accompanied by a structural phase transition of the host material. The monoclinic symmetry of pristine Cr4TiSe8 is changed to trigonal when x in LixCr4TiSe8 exceeds approximately 0.4. With increasing Li content the axes of the new trigonal unit cell are significantly enlarged. The structural phase transition was characterized by Rietveld refinement of X-ray (XRD) powder patterns for different values of x. The phase transition is electronically driven rather than being due to geometric reasons. Immediately after removal of the excess BuLi of partially intercalated phases, the product is not in equilibrium and undergoes a structural relaxation. When the lithiated products are treated with water, the intercalated Li is removed while the symmetry does not switch back from trigonal to monoclinic. The final composition of the deintercalated samples was always Li≈0.4Cr4TiSe8. The strain of the samples introduced by the Li insertion and the phase transition was investigated with line profile analysis (LPA) of the XRD patterns. The intercalation reaction is accompanied by a strong increase of the strain. Static 7Li NMR measurements of the fully intercalated sample Li 2.8Cr4TiSe8 show a broad line due to the strong interaction of the Li nuclei with the Cr ions. 7Li magic angle spinning (MAS) NMR studies reveal the presence of two nonequivalent Li sites.
ASJC Scopus subject areas
- Chemistry(all)
- General Chemistry
- Chemical Engineering(all)
- General Chemical Engineering
- Materials Science(all)
- Materials Chemistry
Cite this
- Standard
- Harvard
- Apa
- Vancouver
- BibTeX
- RIS
In: Chemistry of materials, Vol. 18, No. 6, 21.03.2006, p. 1569-1576.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Lithium intercalation into monoclinic Cr4TiSe8
T2 - Synthesis, structural phase transition, and properties of LixCr 4TiSe8 (x = 0.1-2.8)
AU - Behrens, Malte
AU - Riemenschneider, Oliver
AU - Bensch, Wolfgang
AU - Indris, Sylvio
AU - Wilkening, Martin
AU - Heitjans, Paul
PY - 2006/3/21
Y1 - 2006/3/21
N2 - The intercalation reaction of Li into the complex ternary selenide Cr 4TiSe8 was investigated as function of time and temperature. The treatment of the host compound with a solution of butyl lithium in n-hexane (BuLi) leads to Li insertion up to the composition Li 2.8Cr4TiSe8. The intercalation reaction is accompanied by a structural phase transition of the host material. The monoclinic symmetry of pristine Cr4TiSe8 is changed to trigonal when x in LixCr4TiSe8 exceeds approximately 0.4. With increasing Li content the axes of the new trigonal unit cell are significantly enlarged. The structural phase transition was characterized by Rietveld refinement of X-ray (XRD) powder patterns for different values of x. The phase transition is electronically driven rather than being due to geometric reasons. Immediately after removal of the excess BuLi of partially intercalated phases, the product is not in equilibrium and undergoes a structural relaxation. When the lithiated products are treated with water, the intercalated Li is removed while the symmetry does not switch back from trigonal to monoclinic. The final composition of the deintercalated samples was always Li≈0.4Cr4TiSe8. The strain of the samples introduced by the Li insertion and the phase transition was investigated with line profile analysis (LPA) of the XRD patterns. The intercalation reaction is accompanied by a strong increase of the strain. Static 7Li NMR measurements of the fully intercalated sample Li 2.8Cr4TiSe8 show a broad line due to the strong interaction of the Li nuclei with the Cr ions. 7Li magic angle spinning (MAS) NMR studies reveal the presence of two nonequivalent Li sites.
AB - The intercalation reaction of Li into the complex ternary selenide Cr 4TiSe8 was investigated as function of time and temperature. The treatment of the host compound with a solution of butyl lithium in n-hexane (BuLi) leads to Li insertion up to the composition Li 2.8Cr4TiSe8. The intercalation reaction is accompanied by a structural phase transition of the host material. The monoclinic symmetry of pristine Cr4TiSe8 is changed to trigonal when x in LixCr4TiSe8 exceeds approximately 0.4. With increasing Li content the axes of the new trigonal unit cell are significantly enlarged. The structural phase transition was characterized by Rietveld refinement of X-ray (XRD) powder patterns for different values of x. The phase transition is electronically driven rather than being due to geometric reasons. Immediately after removal of the excess BuLi of partially intercalated phases, the product is not in equilibrium and undergoes a structural relaxation. When the lithiated products are treated with water, the intercalated Li is removed while the symmetry does not switch back from trigonal to monoclinic. The final composition of the deintercalated samples was always Li≈0.4Cr4TiSe8. The strain of the samples introduced by the Li insertion and the phase transition was investigated with line profile analysis (LPA) of the XRD patterns. The intercalation reaction is accompanied by a strong increase of the strain. Static 7Li NMR measurements of the fully intercalated sample Li 2.8Cr4TiSe8 show a broad line due to the strong interaction of the Li nuclei with the Cr ions. 7Li magic angle spinning (MAS) NMR studies reveal the presence of two nonequivalent Li sites.
UR - http://www.scopus.com/inward/record.url?scp=33645499719&partnerID=8YFLogxK
U2 - 10.1021/cm0518628
DO - 10.1021/cm0518628
M3 - Article
AN - SCOPUS:33645499719
VL - 18
SP - 1569
EP - 1576
JO - Chemistry of materials
JF - Chemistry of materials
SN - 0897-4756
IS - 6
ER -