Enhanced cycling stability of LiNiO2 cathodes through a Mg/W dual-cation modification strategy

LiNiO₂ cathodes for lithium-ion batteries offer the prospect of high specific capacities; however a plethora of structural and surface instabilities occur during cycling can limit their lifetime and impinge on their safety. Structural and surface modification strategies such as cation-doping have been shown to stabilise cycling performance and prolong cathode lifetimes yet often tackle either surface or bulk driven degradation processes. Here, we present a dual-cation substitution approach for the LiNiO₂ cathode which produces a coat-doped cathode in a single step. Judicious selection of cation substituents enables the targeted stabilisation of both bulk- and surface-originated instabilities, in this case magnesium and tungsten respectively. While the addition of tungsten as a sole-substituent promotes a rock-salt surface layer which typically reduces the observable capacity, we demonstrate that the incorporation of Mg into W-containing compositions can mitigate these structural transformations. These coat-doped Mg/W-LiNiO₂ cathodes exhibit superior cycling stabilities compared to unmodified LiNiO₂ and singly-substituted Mg- or W-LiNiO₂. X-ray diffraction computed tomography methods complement these findings, providing spatially resolved structural information on the location and heterogeneity of the coat-doped cathodes, guiding synthetic pathways to optimised materials that outperform undoped LiNiO₂ even in high-mass loading cell environments.