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Diffusion Process in LixW3O9F(1≤x≤3)

  • Michel Menetrier (a1), Soon-Ho Chang (a1), Kyung-Soo Suh (a1), Jean Senegas (a1), Jean-Pierre Chaminade (a1) and Claude Delmas (a1)...


The structure of LiW3O9F is built up of a peculiar stacking of hexagonal tungsten bronze-type layers. Li can be reversibly intercalated in this material, electrochemically or chemically up to the Li3W3O9F composition.

Diffusion coefficients are determined by the Honders method using Li/LiClO4-PC/Lix W3O9F cells which are discharged galvanostatically for given periods of time. This method does not require the knowledge of the Darken factor nor of the material/electrolyte contact area, which are both rather delicate to determine precisely in pratice.

The evolution of D with the intercalation amount exhibits a drastic increase (by three orders of magnitude) from x = 1 to x = 1.15 and a constant and rather high value afterwards. Different sites for the preexisting lithim (x ≤ 1) and the intercalated ones are therefore expected.

7Li NMR spectra have been recorded for various intercalation amounts. For x = 1, two first order quadrupolar signals are observed, corresponding to the sites of the immobile lithium ion. When lithium is intercalated (x = 1.1), another signal is observed, as well as a modification of that of the first lithium, due to intra site mobility. A more important change is observed between x = 1.1 and x = 1.2, which suggests an exchange process. For larger values of x, a single signal is observed, corresponding to mobile Li+ ions.

The sites in which lithium may be intercalated and the diffusion pathways are discussed on the basis of these results.



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1. Moutou, J.M., Vlasse, M., Cervera-Marzal, M., Chaminade, J.P. and Pouchard, M., J. Sol. State Chem., 51, 190 (1984).
2. Chaminade, J.P., Moutou, J.M., Villeneuve, G., Couzi, M., Pouchard, M. and Hagenmuller, P., J. Sol. State Chem., 65, 27 (1986).
3. Gérand, B., Nowogroki, G. and Figlarz, M., J. Sol. State Chem., 38, 212 (1981).
4. Magneli, A., Acta Scand., 7, 315 (1953).
5. Chang, S.H., Delmas, C., Chaminade, J.P. and Hagenmuller, P., Solid State Ionics, 39, 305 (1990).
6. Mendiboure, A. and Delmas, C., Computers and Chemistry, 11(3), 153 (1987).
7. Honders, A., Joung, E.W.A., Heeren, A.H. Van, Wit, J.H.W. de and Broers, G.H.J., Solid State Ionics, 9–10, 375 (1983).
8. Honders, A. and Broers, G.H.J., Solid State Ionics,.1, 173 (1985).
9. Honders, A., Kinderen, J.M. der, Heeren, A.H. Van, Wit, J.H.W. de and Broers, G.H.J., Solid State Ionics,.15, 265 (1985).
10. Honders, A., Young, E.W.A., Hintzen, A.J.H., Wit, J.H.W. de and Broers, G.H.J., Solid State lonics,.15, 277 (1985).


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