Effect of Sodium Phosphate Coating on Cu and Mg-Substituted P2-Na_0.67Ni_0.33Mn_0.67O₂ for Improving the Cycling Performance of Sodium-Ion Capacitors

Sodium-ion capacitors (SICs) bridge the performance gaps between batteries and supercapacitors by providing a high energy and power density in a single configuration. As battery-type active materials, sodium preintercalated layered metal oxides are desirable owing to their unique crystal structure, simple synthesis process, and high working voltage. However, their poor cyclic stability and low kinetics limit their application. Herein, we report increased rate capability and cycle stability achieved by introducing transition metal substitution and surface coating strategies. By substituting a portion of Ni and Mn with Cu and Mg (the sample name was denoted as NMCM), the P2-O2 transition which occurs at high voltages was alleviated. Additionally, a thin and uniform sodium phosphate coating layer suppressed surface side reactions occurring during charge-discharge processes, as observed through ex-situ X-ray photoelectron spectroscopy and ex-situ transmission electron microscopy. Compared to the pristine sample, the capacity improved by 48% at a high current density of 4 A g(-1). After 100 cycles, the sodium-phosphate-coated sample (NMCM@P) retained about 90% of its capacity, whereas NMCM had a capacity retention of 63%. When evaluating the longer stability of SIC full cells, NMCM@P exhibited an outstanding stability of 71% after 5000 cycles. This was higher than that of NMCM, which retained only 17% of its initial capacity.