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Layered LixMoO2Phases with Different Composition for Electrochemical Application: Structural Considerations

Mikhailova, Daria and Bramnik, Natalia N. and Bramnik, Kirill G. and Reichel, P. and Oswald, S. and Senyshyn, A. and Trots, D. M. and Ehrenberg, Helmut (2011):
Layered LixMoO2Phases with Different Composition for Electrochemical Application: Structural Considerations.
In: Chemistry of Materials, pp. 3429-3441, 23, (15), ISSN 0897-4756, [Online-Edition: http://dx.doi.org/10.1021/cm2010715],
[Article]

Abstract

Different modifications of LixMoO2 (1) without metallic Mo–Mo bonds (R-3m, a = 2.858(2) Å, c = 15.701(13) Å), (2) with endless Mo chains with metallic bonds (C2/m, a = 10.614(3) Å, b = 2.878(1) Å, c = 4.955(2) Å, β = 99.37(3)°), and (3) with Mo4O16 clusters (C2/m, a = 9.905(6) Å, b = 5.739(3) Å, c = 5.472(4) Å, β = 107.43(7)°) were synthesized by high-temperature solid-state reaction. Increasing lithium content supports the formation of the rhombohedral form. In situ structural investigations during electrochemical Li extraction and insertion between 2.4–3.5 V on Li1.0MoO2 material containing rhombohedral and monoclinic modifications with endless molybdenum chains revealed the instability of the monoclinic Li0.9MoO2 form with decreasing Li content against transformation into two rhombohedral phases LixMoO2 and Lix≈0MoO2. In contrast, the rhombohedral Li1.0(Mo0.9Li0.1)O2 form showed a topotactical single-phase behavior during Li extraction and insertion. Further oxidation of LixMoO2 at voltages above 4.5 V led to insertion of large anions such as PF6– or BF4– into the crystal structure. The Li-free rhombohedral form is stable in Ar up to 570 K and transforms irreversibly at higher temperature into a rutile-like structure.

Item Type: Article
Erschienen: 2011
Creators: Mikhailova, Daria and Bramnik, Natalia N. and Bramnik, Kirill G. and Reichel, P. and Oswald, S. and Senyshyn, A. and Trots, D. M. and Ehrenberg, Helmut
Title: Layered LixMoO2Phases with Different Composition for Electrochemical Application: Structural Considerations
Language: English
Abstract:

Different modifications of LixMoO2 (1) without metallic Mo–Mo bonds (R-3m, a = 2.858(2) Å, c = 15.701(13) Å), (2) with endless Mo chains with metallic bonds (C2/m, a = 10.614(3) Å, b = 2.878(1) Å, c = 4.955(2) Å, β = 99.37(3)°), and (3) with Mo4O16 clusters (C2/m, a = 9.905(6) Å, b = 5.739(3) Å, c = 5.472(4) Å, β = 107.43(7)°) were synthesized by high-temperature solid-state reaction. Increasing lithium content supports the formation of the rhombohedral form. In situ structural investigations during electrochemical Li extraction and insertion between 2.4–3.5 V on Li1.0MoO2 material containing rhombohedral and monoclinic modifications with endless molybdenum chains revealed the instability of the monoclinic Li0.9MoO2 form with decreasing Li content against transformation into two rhombohedral phases LixMoO2 and Lix≈0MoO2. In contrast, the rhombohedral Li1.0(Mo0.9Li0.1)O2 form showed a topotactical single-phase behavior during Li extraction and insertion. Further oxidation of LixMoO2 at voltages above 4.5 V led to insertion of large anions such as PF6– or BF4– into the crystal structure. The Li-free rhombohedral form is stable in Ar up to 570 K and transforms irreversibly at higher temperature into a rutile-like structure.

Journal or Publication Title: Chemistry of Materials
Volume: 23
Number: 15
Uncontrolled Keywords: monoclinic LixMoO2; rhombohedral LixMoO2; Mo4O16-clusters; in situ structural characterization; lithium extraction/insertion; thermal stability
Divisions: DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > B - Characterisation > Subproject B4: In situ investigations of the degradation of intercalation batteries and their modelling
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > B - Characterisation
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue
Zentrale Einrichtungen
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres
DFG-Collaborative Research Centres (incl. Transregio)
Date Deposited: 15 Sep 2011 14:11
Official URL: http://dx.doi.org/10.1021/cm2010715
Additional Information:

SFB 595 B4

Identification Number: doi:10.1021/cm2010715
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