Abstract
This work presents the correlation between structural stability and electrochemical impedance (EIS) performance of NaNi1-x(VO)xPO4 (x = 0.1, 0.3 and 0.5 mol %) mixed polyanion glass and glass–ceramic cathodes. XRD results confirm the presence of Na4Ni3(PO4)2(P2O7) (ICSD 82713), NaNi4(PO4)3 (ICSD 60964) and NaV2O5 (ICSD 1898) crystalline phases indexed with orthorhombic/Pna21 and orthorhombic/Cmcm and orthorhombic/Pmn21 structures, respectively. The inversion correlation between Rct and σb witnessed the lowest charge-transfer resistance (Rct = 7.2x103Ω) for the highest conducting NaNi0.7(VO)0.3PO4 glass–ceramic sample σb = 1.38x10-03 S/cm) using a half-cell. The best reduction potential of the Ni+4/Ni+2 ratio (2.29x10-14) by XPS for the optimally-conducting NaNi0.7(VO)0.3PO4 glass–ceramic network confirms that the present mixed polyanion glass–ceramic network exhibits relatively flexible active centres, along with its superior stability, which is responsible for achieving the excellent electrochemical performance.
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