Title :

Lithium insertion mechanism in CoSb3 analysed by 121Sb Mössbauer spectrometry, X-ray: Absorption Spectroscopy and electronic structure calculations

Author(s) :

Devos, Isabelle [Auteur]
Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 [IEMN]
Womes, Manfred [Auteur]
Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM ICMMM]
Heilemann, Mike [Auteur]
Goethe University Frankfurt
Olivier-Fourcade, Josette [Auteur]
Laboratoire des Agrégats Moléculaires et Matériaux Inorganiques [LAMMI]
Jumas, Jean-Claude [Auteur]
Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM ICMMM]
Tirado, José Luis [Auteur]
Universidad de Córdoba = University of Córdoba [Córdoba]

Journal title :

Journal of Materials Chemistry

Pages :

1759-1767

Publisher :

Royal Society of Chemistry

Publication date :

2004

ISSN :

0959-9428

HAL domain(s) :

Chimie

English abstract : [en]

The lithium insertion mechanism into the skutterudite-type CoSb3 compound has been studied using X-ray Absorption Near Edge Structure (XANES), 121Sb Mössbauer spectrometry and electronic structure calculations based on the ...
Show more >The lithium insertion mechanism into the skutterudite-type CoSb3 compound has been studied using X-ray Absorption Near Edge Structure (XANES), 121Sb Mössbauer spectrometry and electronic structure calculations based on the Density Functional Theory (DFT) in the Linear Muffin Tin Orbital (LMTO) framework. 121Sb Mössbauer spectra are in agreement with a progressive restructuring which occurs during the second stage (voltage plateau at 0.6 V). The Mössbauer hyperfine parameters show the formation of Li3Sb and of a ternary intermediate phase LixCoSby whose variable composition depends on the insertion conditions. XANES spectra at Sb LI, III and Co K edges have been compared to calculated Projected Densities of States (PDOS) of reference compounds containing Co, Sb and Li. This analysis has allowed specification of the restructuring mechanism as a distortion of the CoSb6 octahedral units and confirms the formation of Li3Sb. The overall characterisations have been interpreted to suggest the first discharge mechanism of restructuring in accordance with the global reaction:CoSb3 + (y + z) Li → (LixCo1−mSby + m Co + Li3Sb) ↔ LizCo + y Li3SbShow less >

Language :

Anglais

Popular science :

Non

Collections :

• Institut d'Électronique, de Microélectronique et de Nanotechnologie (IEMN) - UMR 8520

Source :

Harvested from HAL