Electronic modification of NaCrO₂ via 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 NaCr_0.95Ni_0.05O₂ 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 NaCr_0.95Ni_0.05O₂ 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.

Keywords

Sodium-ion battery / electronic structure / charge compensation / rate performance

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