Titanium migration driven by Li vacancies in Li1−xTi2O4 spinelElectronic supplementary information (ESI) available: Cif file for the combined PXRD and PND refinement of Li0.33Ti2O4. See DOI: 10.1039/c5cc02800k

Gentle oxidation of lithium titanate spinel (LiTi 2 O 4 ) with water at room temperature gives Li-deficient Li 0.33 Ti 2 O 4 . Combined X-ray and neutron Rietveld analysis shows that 28% of the Ti cations are displaced to alternative octahedral sites, in keeping with a proposed model based on Ti-migration limited by Li-vacancy concentration. Gentle oxidation of lithium titanate by water gives Li 0.33 Ti 2 O 4 with many Ti cations displaced to alternative octahedral sites (marked 'X').