Elucidating the Effect of the Dopant Ionic Radius on the Structure and Electrochemical Performance of Ni-Rich Layered Oxides for Lithium-Ion Batteries

The merits of Ni-rich layered oxide cathodes in specific capacity and material cost accelerate their practical applications in electric vehicles and grid energy storage. However, detrimental structural deterioration occurs inevitably during long-term cycling, leading to potential instability and capacity decay of the cathodes. In this work, we investigate the effect of the doped cation radius on the electrochemical performance and structural stability of Ni-rich cathode materials by doping with Mg and Ca ions in LiNi_0.8Co_0.1Mn_0.1O₂. The results reveal that an increase in the doping ion radius can enlarge the interlayer spacing but lead to the collapse of the layered structure if the ion radius is too large, which undermines the cycling stability of the cathode material. Compared with the Ca-doped sample and the pristine material, Mg-doped LiNi_0.8Co_0.1Mn_0.1O₂ presents improved structural stability and superior thermal stability due to the pillar and glue roles of medium-sized Mg ions in the lithium layer. The results of this study suggest that a suitable ionic radius of the dopant is critical for stabilizing the structure and improving the electrochemical properties of Ni-rich layered oxide cathode materials.