• Vinayan, B. P.
• Behm, R. J.
• Cambaz, M. A.
• Fichtner, M.
• Diemant, T.
• Geßwein, H.
• Schiele, A.
• Brezesinski, Torsten
• Mazilkin, A.
• Ehrenberg, H.
• Sarapuolva, A.

Abstract

Li-rich disordered rock-salt oxides such as Li$_{1.2}$Ni$_{1/3}$Ti$_{1/3}$Mo$_{2/15}$O$_{2}$ are receiving increasing attention as high-capacity cathodes due to their potential as high-energy materials with variable elemental composition. However, the first-cycle oxygen release lowers the cycling performance due to cation densification and structural reconstruction on the surface region. This work explores the influence of lithium excess on the charge compensation mechanism and the effect of surface modification with LiNbO$_{3}$ on the cycling performance. Moving from a stoichiometric LiNi$_{0.5}$Ti$_{0.5}$O$_{2}$ composition toward Li-rich Li$_{1.2}$Ni$_{1/3}$Ti$_{1/3}$Mo$_{2/15}$O$_{2}$, oxygen redox is accompanied by oxygen release. Thereby, cationic charge compensation is governed by the Ni$^{2+/3+}$ and Mo$^{3+/6+}$ redox reaction. Contrary to the bulk oxidation state of Mo$^{6+}$ in the charged state, a mixed Mo valence on the surface is found by XPS. Furthermore, it is observed that smaller particle sizes result in higher specific capacities. Tailoring the surface properties of Li$_{1.2}$Ni$_{1.3}$Ti$_{1/3}$Mo$_{2/15}$O$_{2}$ with a solid electrolyte layer of LiNbO$_{3}$ altered the voltage profile, resulting in a higher average discharge voltage as compared to the unmodified material. The results hint at the interdiffusion of cations from the metal oxide surface coating into the electrode material, leading to bulk composition changes (doping) and a segregated Nb-rich surface. The main finding of this work is the enhanced cycling stability and lower impedance of the surface-modified compound. We argue that surface densification is mitigated by the Nb doping/surface modification.

Topics

• impedance spectroscopy
• surface
• compound
• x-ray photoelectron spectroscopy
• Oxygen
• Lithium
• densification
• interdiffusion