Regulating local chemical environment in O3-type layered sodium oxides by dual-site Mg2+/B3+ substitution achieves durable and high-rate cathode

Abstract

The O3-Na0.85Ni0.2Fe0.4Mn0.4O2 layered oxide cathode material possesses the advantages of high specific capacity, low cost, and simple synthesis. However, sluggish kinetics and complicated phase transition caused by the large size difference between Na+ and tetrahedral gaps lead to poor rate and cycling performance. Therefore, a scalable and feasible strategy was proposed to modulate local chemical environment by introducing Mg2+ and B3+ into O3-Na0.85Ni0.2Fe0.4Mn0.4O2, which can distinctly improve kinetic transport rate as well as electrochemical performance. The capacity retention of O3-(Na0.82Mg0.04)(Ni0.2Fe0.4Mn0.4)B0.02O2 (NFMB) increases from 43.3% and 12.4% to 89.5% and 89.0% at 1 C and 3 C after 200 cycles, respectively. Moreover, the electrode still delivers high rate capacity of 93.9 mAh/g when current density increases to 10 C. Mg2+ ions riveted on Na layer act as a “pillar” to stabilize crystal structure and inhibit structural change during the desodiumization process. B3+ ions entering tetrahedral interstice of the TM layer strengthen the TM-O bond, lower Na+ diffusion energy barrier and inhibits the slip of TM layer. Furthermore, the assembled full batteries with the modified cathode material deliver a high energy density of 278.2 Wh/kg with commercial hard carbon as anode. This work provides a strategy for the modification of high-performance SIB layered oxide materials to develop the next-generation cost-effective energy storage grid systems.