Novel NASICON‐Type Na‐V‐Mn‐Ni‐Containing Cathodes for High‐Rate and Long‐Life SIBs

Abstract Partial substitution of V by other transition metals in Na 3 V 2 (PO 4 ) 3 (NVP) can improve the electrochemical performance of NVP as a cathode for sodium–ion batteries (SIBs). Herein, phosphate Na–V–Mn–Ni–containing composites based on NASICON (Natrium Super Ionic Conductor)–type structure have been fabricated by sol–gel method. The synchrotron–based X–ray study, X–ray diffraction (XRD), and X–ray photoelectron spectroscopy (XPS) studies show that manganese/nickel combinations successfully substitute the vanadium in its site within certain limits. Among the received samples, composite based on Na 3.83 V 1.17 Mn 0.58 Ni 0.25 (PO 4 ) 3 (VMN–0.5, 108.1 mAh g −1 at 0.2 C) shows the highest electrochemical ability. The cyclic voltammetry, galvanostatic intermittent titration technique, in situ XRD, ex situ XPS, and bond valence site energy calculations exhibit the kinetic properties and the sodium storage mechanism of VMN–0.5. Moreover, VMN–0.5 electrode also exhibits excellent electrochemical performance in quasi–solid–state sodium metal batteries with PVDF–HFP quasi‐solid electrolyte membranes. The presented work analyzes the advantages of VMN–0.5 and the nature of the substituted metal in relation to the electrochemical properties of the NASICON–type structure, which will facilitate further commercialization of SIBs.