Lithium insertion into Sn-doped TiO2 anatase was studied in order to clarify the mechanism responsible
for the first plateau observed at 1.75 V vs Li. One of the other aims of this study was to get deeper
insight into the process responsible for the appearance of a first domain observed at a small amount of
lithium (before the plateau) and a third domain between 1.7 and 1.2 V (after the plateau). Pure and
Sn-substituted anatase were synthesized by several synthetic methods with different precursors and solvents.
These materials are expected to have different electrochemical properties because crystallite size modifies
the Li-insertion process. Their electrochemical behavior is discussed in order to establish a relationship
between the materials properties and the electrochemical performances. Three processes have been
identified from both X-ray diffraction and 119Sn Mössbauer spectroscopy: (i) topotactic insertion into the
Li-poor compound Li
x
TiO2, with the x value depending on the particle size; (ii) a two-phase system
mechanism leading to the phase transition Li
x
TiO2 (Anatase, I41/a
md) → Li
y
TiO2 (orthorhombic distortion,
Imma); and (iii) another topotactic insertion into the Li-rich compound Li
y
TiO2. Crystallite size governs
the topotactic mechanism but does not improve the overall electrochemical capacity of the material.
Anatase. -Li insertion into Sn-doped TiO2 anatase is characterized by XRD and 119 Sn Moessbauer spectroscopy. Three processes are identified: (i) topotactic insertion into the Li-poor compound LixTiO2, (ii) a two-phase system mechanism leading to the phase transition from LixTiO2 (anatase type, I41/amd) to LiyTiO2 (orthorhombic distortion, Imma), and (iii) another topotactic insertion into the Li-rich compound Li y TiO 2 . Crystallite size governs the topotactic mechanism but does not improve the overall electrochemical capacity of the material. -(ALDON*, L.; KUBIAK, P.; PICARD, A.; JUMAS, J.-C.; OLIVIER-FOURCADE, J.; Chem.
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