Role of site–specific doping in stabilizing high–nickel cathodes for high-performance lithium- ion -batteries

Abstract

The growing demand for high-capacity and energy-dense lithium-ion batteries has driven the increase of nickel content in commercially available cathodes. However, during deep charging (delithiation), these Ni-rich cathodes experience a detrimental phase transformation and a sudden, significant decrease in lattice volume. This lattice collapse is considered the primary culprit behind the limitations in the cathode's electrochemical performance. Notably, the exact cause-and-effect relationship between the phase change and the collapse remains unclear. In the present study, the effect of the site of substitution on the performance of the LiNiO2 cathode has been investigated by adopting tungsten as a dopant. To gain deeper insights into this connection within Ni-rich LiNiO2, the contraction of the c-axis and the change in the a-axis during the delithiation have been investigated using ab initio density functional theory. Findings reveal that the free energy difference between the suspected phases in Ni-rich LiNiO2 is minimal at room temperature, facilitating the transition from the H2 to the H3 phase. This transition appears to be driven by the movement (gliding) of the NiO2 layer towards the adjacent Li layer. The findings of the present study indicate that among two different configurations due to different sites of substitution, the WLNO-2 configuration suppresses H2 –H3 phase conversion to a greater extent by hindering the gliding of the NiO2 layer toward the Li layer. Furthermore, a reduction in the collapse of the c-axis lattice during deep de-lithiation for the WLNO-2 configuration has been observed. This reduced collapse is primarily attributed to the altered charge distribution within oxygen atoms and the weakened screening effect from lithium ions.