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LiCoO2 (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 operando 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/gLCO (~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. Operando 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. |
