Kinetic pathways of ionic transport in fast-charging lithium titanate

Fast-charging batteries typically use electrodes capable of accommodating lithium continuously by means of solid-solution transformation because they have few kinetic barriers apart from ionic diffusion. One exception is lithium titanate (Li₄Ti₅O₁₂), an anode exhibiting extraordinary rate capability apparently inconsistent with its two-phase reaction and slow Li diffusion in both phases. Through real-time tracking of Li⁺ migration using operando electron energy-loss spectroscopy, we reveal that facile transport in Li₄₊ x Ti₅O₁₂ is enabled by kinetic pathways comprising distorted Li polyhedra in metastable intermediates along two-phase boundaries. Our work demonstrates that high-rate capability may be enabled by accessing the energy landscape above the ground state, which may have fundamentally different kinetic mechanisms from the ground-state macroscopic phases. This insight should present new opportunities in searching for high-rate electrode materials.