<p>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<sub>x</sub>) as cathode coating in a thin-film model system, which provides
simple access to the cathode-coating-electrolyte interface. 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 the NbO<sub>x</sub>
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<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 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<sub>x</sub> coating. These results show that in situ
lithiated ALD NbO<sub>x</sub> 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.</p>