The NASICON-structured Na4VMn(PO4)3 (NVMP) cathode material, known for its three-dimensional
framework
and high theoretical capacity, faces limitations due to its poor electronic
conductivity. To enhance its practicality for sodium-ion battery (SIB)
applications, we employed strategies such as coating with a thin conducting
carbon layer and doping Zn2+ ions into the Mn2+ sites of NVMP. These modifications aimed to improve the intrinsic
properties and reduce Jahn–Teller distortion effects. Zn or
Zn-based oxides, typically anode materials for SIBs, serve as structural
support when doped into cathodes. We synthesized Na4VMn1–x
Zn
x
(PO4)3/C (Zn(x)-NVMP/C, where x = 0.00, 0.05, 0.10,
0.15, 0.20) via a citric acid-assisted sol–gel method, followed
by calcination at 750 °C under an Ar atmosphere. Characterizations
using XRD, XPS, HRTEM, and Raman spectroscopy confirmed the high purity
of these materials. Among them, Zn(0.15)-NVMP/C exhibited the best
performance, with lower internal resistance and enhanced diffusion
kinetics, achieving a stable capacity of 72 mAh g–1 at 10C with 83% retention after 3000 cycles, and high rate tolerance
up to 50C. Operando XRD studies revealed highly reversible two-phase
charge storage mechanisms, and ex situ XPS analysis
confirmed the charge storage mechanism of the cathode, while electrochemical
impedance spectroscopy (EIS) and cyclic voltammetry (CV) analyses
confirmed reduced polarization of the NVMP cathode after Zn doping.
These findings indicate that Zn(0.15)-NVMP/C is a promising cathode
material for SIB applications.