LiCoO<sub>2</sub> (LCO) is one of the most-widely used cathode active materials for Li-ion batteries. Even though the material undergoes an electronic two-phase transition upon Li-ion cell charging, LCO exhibits competitive performance in terms of rate capability. Herein the insulator-metal transition of LCO is investigated by <i>operando</i> Raman spectroscopy complemented with DFT calculations and a newly-developed sampling volume model. We confirm the presence of a Mott insulator α-phase at dilute Li-vacancy concentrations (x > 0.87) that transforms into a metallic β-phase at x < 0.75. In addition, we find that the charge-discharge intensity trends of LCO Raman-active bands exhibit a characteristic hysteresis, which, unexpectedly, narrows at higher cycling rates. When comparing these trends to a newly-developed numerical model of laser penetration into a spatially-heterogeneous particle we provide compelling evidence that the insulator-metal transition of LCO follows a two-phase route at very low cycling rates, which is suppressed in favor of a solid-solution route at rates above 10 mA/g<sub>LCO</sub> (~C/10). The observations explain why LCO exhibits competitive rate capabilities despite being observed to undergo an intuitively slow two-phase transition route: a kinetically faster solid-solution transition route becomes available when the active material is cycled at rates >C/10. <i>Operando</i> Raman spectroscopy combined with sample volume modelling and DFT calculations is shown to provide unique insights into fundamental processes governing the performance of state-of-the-art cathode materials for Li-ion batteries.
Charge and Discharge Behaviour of Li-Ion Batteries at Various Temperatures Containing LiCoO2 Nanostructured Cathode Produced by CCSO