The Fine Line between a Two‐Phase and Solid‐Solution Phase Transformation and Highly Mobile Phase Interfaces in Spinel Li4+xTi5O12

Phase transitions play a crucial role in Li‐ion battery electrodes being decisive for both the power density and cycle life. The kinetic properties of phase transitions are relatively unexplored and the nature of the phase transition in defective spinel Li_4+xTi₅O₁₂ introduces a controversy as the very constant (dis)charge potential, associated with a first‐order phase transition, appears to contradict the exceptionally high rate performance associated with a solid–solution reaction. With the present density functional theory study, a microscopic mechanism is put forward that provides deeper insight in this intriguing and technologically relevant material. The local substitution of Ti with Li in the spinel Li_4+xTi₅O₁₂ lattice stabilizes the phase boundaries that are introduced upon Li‐ion insertion. This facilitates a subnanometer phase coexistence in equilibrium, which although very similar to a solid solution should be considered a true first‐order phase transition. The resulting interfaces are predicted to be very mobile due to the high mobility of the Li ions located at the interfaces. This highly mobile, almost liquid‐like, subnanometer phase morphology is able to respond very fast to nonequilibrium conditions during battery operation, explaining the excellent rate performance in combination with a first‐order phase transition.