Effective Incorporation of Cobalt Near Surface Region for Cobalt-Free Cathodes in Lithium-Ion Batteries

Cobalt-free cathode materials, particularly Ni-rich layered oxide cathode materials, are ideal for electric vehicle Li-ion batteries, offering high energy density and cost-effectiveness. However, high Ni content in high-temperature synthesis leads to issues like increased Li/Ni cation mixing and reduced rate capability, mainly due to the absence of Co. Therefore, this study investigated the utilization of a small amount of Co instead of completely removing it to enhance electrochemical performance. A simple pre-calcination process was used to induce Co substitution beneath the Ni-rich layered oxide cathode materials surface. A coating process was also performed for comparison. The Li/Ni cation mixing in the Co-substituted sample during high-temperature calcination was 2.43%, demonstrating a superior value compared to the Co-coating process. Rate capability tests showed superior performance for Co-substituted sample (164.2 mAh g-1) at 2 C compared to coated sample (151.0 mAh g-1). Moreover, Co substitution improved not only the cycle stability but also the high-temperature stability at an elevated state of charge. This study focuses on the surface modification of cobalt-free cathode, providing direct insight into the effects of Co substitution and typical Co coating and suggests an optimal process that uses small amounts of Co.