Enhancing High-Voltage Performance of Ni-Rich Cathode by Surface Modification of Self-Assembled NASICON Fast Ionic Conductor LiZr2(PO4)3

Coating methodology is commonly employed in the enhancement of Ni-rich cathodes for Li-ion batteries as an efficient approach, while its strategy and effect are still great challenges to achieve success in surface modifications for comprehensive electrochemical properties. In this work, the surface of Ni-rich cathode LiNi_0.82Co_0.15Al_0.03O₂ (NCA) is modified by intimately coating NASICON-type solid electrolyte LiZr₂(PO₄)₃ (LZP) via a facile approach involving electrostatic attraction. With well-designed architecture and a uniform NASICON-type LZP nanolayer wrapping over the NCA microsphere, the entire electrode demonstrates exceptional Li⁺ diffusion and conductivity and suppresses the side reaction between electrolyte and electroactive NCA, stabilizing the phase interface with less Li⁺/Ni²⁺ cation mixing. As a result, the NCA@LZP can deliver a high reversible capacity of 182 mAh g^-1 at 1C in 2.7-4.3 V, maintaining the capacity retention of 84.6% after 100 cycles. More importantly, the structure stability of NCA is enhanced substantially by surface modification of LZP at high cutoff voltage. It achieves a reversible capacity of 204 mAh g^-1 and keeps 100.4 mAh g^-1 after 500 cycles at 1C in the potential range of 2.7-4.5 V. This effective strategy of using NASICON fast ionic conductor like LZP as a coating layer may provide a new insight to modify the surface of Ni-rich electrode, improving the rate capability and cyclic performance under high voltage.