Ultrathin Titanium Dioxide Coating Enables High-Rate and Long-Life Lithium Cobalt Oxide

Lithium cobalt oxide (LCO) has been widely used as a leading cathode material for lithium-ion batteries in consumer electronics. However, unstable cathode electrolyte interphase (CEI) and undesired phase transitions during fast Li⁺ diffusivity always incur an inferior stability of the high-voltage LCO (HV-LCO). Here, an ultra-thin amorphous titanium dioxide (TiO₂) coating layer engineered on LCO by an atomic layer deposition (ALD) strategy is demonstrated to improve the high-rate and long-cycling properties of the HV-LCO cathode. Benefitting from the uniform TiO₂ protective layer, the Li⁺ storage properties of the modified LCO obtained after 50 ALD cycles (LCO-ALD50) are significantly improved. The results show that the average Li⁺ diffusion coefficient is nearly tripled with a high-rate capability of 125 mAh g^-1 at 5C. An improved cycling stability with a high-capacity retention (86.7%) after 300 cycles at 1C is also achieved, far outperforming the bare LCO (37.9%). The in situ XRD and ex situ XPS results demonstrate that the dense and stable CEI induced by the surface TiO₂ coating layer buffers heterogenous lithium flux insertion during cycling and prevents electrolyte, which contributes to the excellent cycling stability of LCO-ALD50. This work reveals the mechanism of surface protection by transition metal oxides coating and facilitates the development of long-life HV-LCO electrodes.