Li-Substituted Layered Spinel Cathode Material for Sodium Ion Batteries

The O3-type layered Na(NixFeyMnz)O2 (0 < x, y, z < 1) cathode materials have attracted great interest in sodium ion batteries due to the abundance and cost of raw materials and their high specific capacities. However, the cycling stability and rate capability at high voltages (> 4.0 V) of these materials remain an issue. In this work, we successfully synthesized a Li-substituted layered-tunneled (O3-spinel) intergrowth cathode (LS-NFM) to address these issues. The remarkable structural compatibility and connectivity of the two phases were confirmed by X-ray diffraction (XRD), selected area electron diffraction (SAED), and high-resolution transmission electron microscopy (HRTEM). The LS-NFM electrode reached a discharge capacity of 96 mAh g–1 with a capacity retention of 86% after 100 cycles at a current rate of 100 mA g–1 in a voltage window of 2.0–4.2 V. Moreover, the LS-NFM cathode exhibited an enhanced rate capability in comparison to the undoped single-phased layered cathode (NFM). The enhanced rate capability of LS-NFM can be explained by the significantly increased effective Na+ diffusivity measured by the galvanostatic intermittent titration technique (GITT) compared to the undoped control NFM cathode, which can be ascribed to the improved charge transport kinetics through shortened diffusion path by direct connection between the 3D channels in the spinel phase and 2D channels in the layered phase. The results from ex situ hard/soft X-ray adsorption spectroscopy (XAS) suggest that the capacity of the LS-NFM cathode is mainly associated with the Ni2+/Ni4+ redox couple and slightly from the Fe3+/Fe4+ redox couple. The voltage profile of the LS-NFM cathode exhibits a reversible plateau above 4.0 V, indicating great stability at high voltages and structural stabilization by the spinel phase. In addition to the substitution of various transition metals, or the modification of the stoichiometry of each transition metal, this study provides a new strategy to improve electrochemical performance of layered cathode materials for sodium ion batteries.