Mitigating the High-Charge Detrimental Phase Transformation in LiNiO2 Using Doping Engineering

Cobalt-free layered LiNiO2 has gained increased interest due to the scarcity and high cost of cobalt. However, LiNiO2 suffers from poor cycling stability, which is mainly due to oxygen loss and structural instability, especially when operating at high voltages. Herein, we present a doping strategy to mitigate the detrimental O3-to-O1 phase transformation in LiNiO2 from first-principles calculations. Temperature-composition phase diagrams of pristine and doped Li1-xNiO2 are obtained using a cluster-expansion and Monte Carlo simulation approach. We investigate the effects of dopant oxidation states, sizes, and concentrations on the dopant distribution in LiNi(1-y)MyO(2) (M = Sb, Ti, Si, Al, and Mg) as well as the phase transitions during delithiation. We find that introducing high-valence dopants with ionic radii similar to that of Ni3+ into LiNiO2 stabilizes the O3-phase cathode bulk structure at high charge. Our results provide a general guidance on using doping engineering to realize Ni-rich, Co-free cathodes for lithium-ion batteries.

Automated summary

We propose a doping strategy to mitigate the O3-to-O1 phase transformation in LiNiO2, improving its cycling stability. The introduction of high-valence dopants with similar ionic radii to Ni3+ stabilizes the bulk structure of LiNiO2 at high charge. This study provides general guidance for the development of Ni-rich, Co-free cathodes for lithium-ion batteries.