A New Solid Solution Series Linking LiTi2O4and Li2Ti3O7Ramsdellites: A Combined X-Ray and Neutron Study

Abstract

We report the discovery of a new solid solution linking the LiTi2O4and Li2Ti3O7ramsdellite phases. The solid solution system is Li1+xTi2−2xO4(0≤x≤0.143), where Li2Ti3O7can be written as Li1.143Ti1.714O4. Combined Rietveld refinement of X-ray and neutron diffraction data sets has been used to determine the structure of various members of this solid solution. Unit-cell dimensions were seen to decrease as the Li content increased, in accord with the expected decrease in ionic size of Ti on oxidation. The Li channel and framework occupancy was seen to follow a simple substitutional mechanism; for every two titanium atoms in the framework that are replaced by lithium atoms, one lithium is lost from the channel sites, introducing a channel vacancy site. The lithium temperature factors were seen to increase over a composition range fromx=0 tox=0.143. This is probably related to the increased number of channel vacancies. No evidence was observed for the splitting of the Li channel sites, even for thex=0.143 end member.