The influence of size on phase morphology and Li-ion mobility in nanosized lithiated anatase TiO2
until further notice
SourceChemistry : a European Journal, 13, 7, (2007), pp. 2023-2028
Article / Letter to editor
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Solid State NMR
Physical Chemistry/Solid State NMR
Chemistry : a European Journal
SubjectSolid State NMR
Sustainable energy storage in the form of Li-ion batteries requires new and advanced materials in particular with a higher power density. Nanostructuring appears to be a promising strategy, in which the higher power density in nanosized materials is related to the dramatically shortened Li-ion diffusion paths. However, nanosizing materials also changes intrinsic material properties, which influence both ionic and electronic conductivity. In this work neutron diffraction is used to show that in addition to these two aspects, nanostructuring changes the phase behavior and morphology. Lithiated 40-nm TiO2 anatase crystallites become single phase, either having the Li-poor original anatase phase, or the Li-rich Li-titanate phase, in contrast to microsized crystallites where these two phases coexist in equilibrium within one crystal particle. In addition, LixTiO2 compositions occur with stoichiometries that are not stable in micron-sized crystallites, indicating enhanced solid solution behavior. Reduced conduction electron densities at the sites of the Li ions are observed by NMR spectroscopy. This is accompanied by reduced spontaneous Li-ion mobility, suggesting a correlation between the electron density at the Li-ion site and the Li-ion mobility. The present results show that in the case of lithiated anatase TiO2, significant effects on phase composition, morphology, and electronic configurations are induced, as well as slower intracrystallite Li diffusion.
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