Observing different modes of mobility in lithium titanate spinel by nuclear magnetic resonance

Lithium titanate (LTO) is a spinel material that is able to reversibly intercalate Li ions with minimal changes of the unit cell dimensions ("zero-strain"), making it an attractive choice as anode material for Li ion batteries. However, the nature of the Li transport in this material is still not fully understood. Here, the Li mobility in Li 4+ x Ti 5 O 12 with x = 0 and x 1.6 is investigated. By regularized inversion of nuclear magnetic resonance (NMR) relaxation and spin alignment echo (SAE) data and supported by DFT simulations, solid-state NMR spectra were analyzed as a function of the respective relaxation times and correlation time constants. A clear correlation between mobility and NMR spectral features was observed, suggesting the presence of local domains with high Li ion mobility. The long-range mobility is limited by the much slower hopping between such domains and appears to be faster for either larger or less ordered local domains. For x 1.6, spectral features indicate the formation of separate stoichiometric and overlithiated phases rather than a solid solution, yet no segregation into a fast and a slow component was observed in the relaxation and in the SAE dimension, which points towards an entangling of the two phases on a microscopic scale. Using a newly developed analysis method for SAE NMR and ab initio calculations we show the formation of localized high-mobility domains in lithium titanate that influence its global ion mobility.