Understanding the High Voltage Behavior of LiNiO₂ Through the Electrochemical Properties of the Surface Layer

Nickel-rich layered oxides are adopted as electrode materials for EV's. They suffer from a capacity loss when the cells are charged above 4.15 V versus Li/Li⁺ . Doping and coating can lead to significant improvement in cycling. However, the mechanisms involved at high voltage are not clear. This work is focused on LiNiO₂ to overcome the effect of M cations. Galvanostatic intermittent titration technique (GITT) and in situ X-ray diffraction (XRD) experiments are performed at very low rates in various voltage ranges (3.8-4.3 V,). On the "4.2-4.3 V" plateau the R2 phase is transformed simultaneously in R3, R3 with H4 stacking faults and H4. As the charge proceeds above 4.17 V cell polarization increases, hindering Li deintercalation. In discharge, such polarization decreases immediately. Upon cycling, the polarization increases at each charge above 4.17 V. In discharge, the capacity and dQ/dV features below 4.1 V remain constant and unaffected, suggesting that the bulk of the material do not undergo significant structural defect. This study shows that the change in polarization results from the electrochemical behavior of the grain surface having very low conductivity above 4.17 V and high conductivity below this threshold. This new approach can explain the behavior observed with dopants like tungsten.