In situ Lithiated ALD Niobium Oxide for Improved Long Term Cycling of Layered Oxide 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, within 3D cathode composites it is difficult to isolate the effect of the coating because of the additives and non-ideal interfaces. In this study we investigate niobium oxide (NbO_x) as cathode coating in a thin-film model system, which provides simple access to the cathode-coating-electrolyte interface. The conformal NbO_x coating was applied by atomic layer deposition (ALD) onto thin-film LiCoO₂ cathodes. The cathode/coating stacks were annealed to lithiate the NbO_x and ensure sufficient ionic conductivity. A range of different coating thicknesses were investigated to improve the electrochemical cycling with respect to the uncoated cathode. At a NbO_x 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 film. At the same thickness, the coating also showed a positive impact on the rate performance of the cathode: 47% of the initial capacity was accessible even at ultrahigh charge-discharge rates of 100 C. Using impedance spectroscopy measurements, we found 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_x coating. These results show that in situ lithiated ALD NbO_x can significantly improve the performance of layered oxide cathodes by enhancing interfacial charge transfer and inhibiting surface degradation of the cathode, resulting in better rate performance and cycle life.