Na3V2(PO4)3 (NVP) encounters significant obstacles, including limited intrinsic electronic and ionic conductivities, which hinder its potential for commercial feasibility. Currently, the substitution of V3+ with Mn2+ is proposed to introduce favorable carriers, enhancing the electronic conductivity of the NVP system while providing structural support and stabilizing the NASICON framework. This substitution also widens the Na+ migration pathways, accelerating ion transport. Furthermore, to bolster stability, Al2O3 coating is applied to suppress the dissolution of transition metal Mn in the electrolyte. Notably, the Al2O3 coating serves a triple role in reducing HClO4 concentration in the electrolyte, inhibiting Mn dissolution, and functioning as the ion-conducting phase. Likewise, carbon nanotubes (CNTs) effectively hinder the agglomeration of active particles during high-temperature sintering, thereby optimizing the conductivity of NVP system. In addition, the excellent structural stability is investigated by in situ XRD measurement, effectively improving the volume collapse during Na+ de-embedding. Moreover, the Na3V5.92/3Mn0.04(PO4)3/C@CNTs@1wt.%Al2O3 (NVMP@CNTs@1wt.%Al2O3) possesses unique porous structure, promoting rapid Na+ transport and increasing the interface area between the electrolyte and the cathode material. Comprehensively, the NVMP@CNTs@1wt.%Al2O3 sample demonstrates a remarkable reversible specific capacity of 122.6 mAh/g at 0.1 C. Moreover, it maintains a capacity of 115.9 mAh/g at 1 C with a capacity retention of 90.2 mAh/g after 1000 cycles. Even at 30 C, it achieves a capacity of 87.9 mAh/g, with a capacity retention rate of 84.87 % after 6000 cycles. Moreover, the NVMP@CNTs@1wt.%Al2O3//CHC full cell can deliver a high reversible capacity of 205.5 mAh/g at 0.1 C, further indicating the superior application potential in commercial utilization.

Surface modification is one of the impressive and widely used technique to improve the electrochemical performance of sodium-ion batteries by modifying the electrode-electrolyte interface. Herein, we used the atomic layer deposition (ALD) to modify the surface of P2-Na0.5Mn0.5Co0.5O2 by sub-monolayer Al2O3 coating on the prefabricated electrodes. Phase purity is confirmed using various structural and morphological studies. The pristine electrode delivered an initial discharge capacity of 154 mAh g-1 at 0.5C, and inferior rate performance of 23 mAh g-1 at 40C rate. On the other hand, the interfacial modified cathode with 5 cycles of ALD coating delivers a high capacity of 174 and 45 mAh g-1 at 0.5C and 40C rate, respectively. The Co2+/3+ redox couple is utilized for the faradaic process with high reversibility along with suppressed P2-O2 phase transition. The presence of the Al2O3 layer acts as an artificial cathode electrolyte interface by suppressing the electrolyte oxidation at higher cutoff potentials. This is clearly validated by the reduced charge transfer resistance of surface modified electrodes after cycling at various current rates. Even at an elevated temperature condition (50 °C), interfacial layer significantly improves the safety of the cell and ensures the stability of the cathode.