Capacity Fade Mechanism of Li4Ti5O12 Nanosheet Anode

Zero-strain and long-term stability of nanoscale lithium titanate (LTO) anode materials make possible the fabrication of exceptionally stable lithium ion batteries. But one issue must be considered that of nanostructure-induced relaxation in 2D LTO nanosheets which profoundly modifies their Li storage properties and structural stability. Excessively intercalated Li ions at both 8a and 16c sites trigger nucleation of the relaxed LTO structure in the nearsurface region, which impedes Li-ion diffusion and causes the increasing polarization of LTO nanosheet electrodes. Nuclei of relaxed LTO then undergo isotropic growth along the 3D Li-ion pathways in LTO to completely convert near-surface regions into relaxed LTO. With increasing population of trapped Li ions, the enhanced conductivity due to Ti4+/Ti3+ reduction gradually eliminates the raised polarization. In the meantime, spontaneous electrolyte/LTO reduction to form the solid electrolyte interphase starts playing a major role in capacity loss once the transformation of near-surface region into relaxed LTO becomes saturated. Elucidation of these fundamental intercalation-induced surface structure transformations contribute greatly into the design of highly performing 2D nanoscaled LTO and other electrode materials.