Electronic modification of NaCrO₂ <i>via</i> Ni²⁺ substitution as efficient cathode for sodium-ion batteries

Abstract

The feature of high theoretical capacity, long thermal stability, and low-cost fabrication offers the layered transition metal oxide NaCrO2 as an excellent candidate for sodium-ion batteries. Here, we show an effective method for electronic modulation of NaCrO2 by partial substitution of Cr3+ with low-valent Ni2+ to produce NaCr0.95Ni0.05O2 as an efficient cathode for these batteries. We found that Ni2+ substitution plays a critical role in the ionic character of transition metal-oxygen bonds, which increases the interlayer separation and thus improves sodium-ion diffusion kinetics. Furthermore, Ni2+ substitution reduces the deterioration of NaCrO2 throughout charge-discharge processes and thus boosts the cycle performance of the materials. The resultant NaCr0.95Ni0.05O2 cathode displays a remarkable rate performance with specific capacities of 91.2 mAh g-1 at 50 C and a high retention (~80%) of the initial capacity after cycling for 1,000 cycles at 10 C.