Tellurium Surface Doping to Enhance the Structural Stability and Electrochemical Performance of Layered Ni-Rich...

The Ni-rich layered oxides are considered as a candidate of next-generation cathode materials for high energy density lithium-ion batteries; however, the finite cyclic life and poor thermostability impede their practical applications. There is often a tradeoff between structure stability and high capacity because the intrinsical instability of oxygen framework will lead to the structural transformation of Ni-rich materials. Because of the strong binding energy between the Te atom and O atom, herein a new technology of surface tellurium (Te) doping in the Ni-rich layered oxide (LiNi_0.88Co_0.09Al_0.03O₂) is proposed to settle the above predicament. Based on density function theory calculations and experiment analysis, it has been confirmed that the doped Te⁶⁺ ions are positioned in the TM layer near the oxide surface, which can constrain the TM-O slabs by strong Te-O bonds and prevent oxygen release from the surface, thus enhancing the stability of the lattice framework in deep delithium (>4.3 V). Especially, 1 wt % Te doping (Te 1%-NCA) shows the superiority in performance improvement. Furthermore, the reversibility of H2-H3 phase transition is also improved to relieve effectively the capacity decline and the structural transformations at extended cycling, which can facilitate the fast Li⁺ diffusion kinetic. Consequently, Te 1%-NCA cathode exhibits the improved cycling stability even at high voltages (4.5 and 4.7 V), good rate capability (159.2 mA h g^-1 at 10 C), and high thermal stability (the peak temperature of 258 °C). Therefore, the appropriate Te surface doping provides a significant exploration for industrial development of the high-performance Ni-rich cathode materials with high capacity and structural stability.