Slight Multielement Doping-Induced Structural Order-Disorder Transition for High-Performance Layered Na-Ion Oxide Cathodes

Abstract

To realize concurrently the high-energy density and excellent cycling stability, maximum utilization of redox couple, minimization of detrimental phase transition, and structural degradation of O3-type layered oxide cathodes are critical for developing Na-ion batteries. Ni²⁺/Ni⁴⁺ redox couple showing multielectron reaction and higher redox potential is favorable to increase the energy density. However, the Jahn-Teller distortion of Ni³⁺ generated upon (dis)charging results in a strong anisotropy in the local crystal structure that causes irreversible interlayer bending and chemo-mechanical cracks of the cathode particles, compromising the electrochemical properties eventually. In this work, we show a slight multielement doping strategy that enlarges the amount of active redox components while minimizing the inactive contents. The results show that the uniform distribution of multiple components can help increase the disorder degree of atom arrangement and alleviate the structural changes and detrimental anisotropy cracks. As a proof of concept, a multielement-doped O3-type Na_0.9Ni_0.25Cu_0.05Mg_0.05Zn_0.05Fe_0.05Al_0.05Mn_0.40Ti_0.05Sn_0.05O₂ oxide is rationally prepared that presents better chemo-mechanical stability and delayed O3-P3 phase transition behavior. Compared to the high Ni-content Na_0.9Ni_0.35Fe_0.2Mn_0.45O₂ cathode, this as-prepared multielement material delivers a reversible capacity of about 120 mAh/g in the voltage range of 2-4.0 V, superior cycling stability with 90% of capacity retention after 500 cycles, and excellent rate capability (more than 70% of initial capacity at 5.0 C). This work indicates that the multielement doping method is highly suitable for the development of advanced Na-ion layered oxide cathodes.