In Situ Lithiated ALD Niobium Oxide for Improved Long Term Cycling of LiCoO2 Cathodes: A Thin-Film Model Study
Protective coatings applied to cathodes help to overcome interface stability issues and extend the cycle life of Li-ion batteries. However, it is difficult to isolate the effect of the coating because of the additives and non-ideal interfaces within 3D cathode composites. In this study we investigate niobium oxide (NbO<sub>x</sub>) as cathode coating in a thin-film model system, which allows assessing the cathode-coating-electrolyte interfaces. The conformal NbO<sub>x</sub> coating was applied by atomic layer deposition (ALD) onto thin-film LiCoO<sub>2</sub> cathodes. The cathode/coating stacks were annealed to lithiate and ensure sufficient ionic conductivity. A range of different coating thicknesses were investigated to improve the electrochemical cycling as compared to the uncoated cathodes. At a NbO<sub>x</sub> thickness of 30 nm, the cells retained 80% of the initial capacity after 493 cycles at 10 C, more than doubling the cycle life of the uncoated cathode. At the same thickness, a residual initial capacitance of 47% remained even at very high charge-discharge rates of 100 C. Using impedance spectroscopy measurements, we find that the enhanced performance is due to suppressed interfacial resistance growth during cycling. Elemental analysis using TOF-SIMS and XPS further revealed a bulk and surface contribution of the NbO<sub>x</sub> coating. These results show that lithiated ALD NbO<sub>x</sub> can significantly improve the performance of layered oxide cathodes by inhibiting the cathode degradation, resulting in prolonged cycle life.<br>