Preparation and property evaluation of Nb-doped Na3V2O2 （PO4 ） 2F hollow microspheres as cathode materials for sodium-ion batteries

doi:10.19799/j.cnki.2095-4239.2023.0177

Abstract

Abstract:

Na₃V₂O₂(PO₄)₂F(NVOPF) is a cathode material with potential application prospects in sodium-ion batteries. This is due to its suitably stable polyanion structure, high operating voltage, and high theoretical specific capacity. However, the intrinsic conductivity of the material is low, and it is prone to irregular agglomeration during the synthesis process, resulting in low actual specific capacity and unsatisfactory rate and cycling performances. Ion doping and micro/nanostructured materials have been found to benefit the intrinsic conductivity and stability of the material. This work, for the first time, reports the synthesis of Nb⁵⁺-doped NVOPF(NVNOPF, Na₃V_2-_x Nb _x O₂(PO₄)₂F (0≤x≤0.15)) material with a hollow microspheric structure by the polyol-assisted hydrothermal method. The as-prepared NVOPF and NVNOPF materials were microspheres with sizes of 0.7-1.0 μm with hollow structures. The microspheres were found to be composed of nanoparticles of with sizes <100 nm. Nanoparticles shortened the diffusion distance between sodium ions, buffered the volume change caused by the intercalation/extraction of sodium ions, and improved the material cycling stability. Meanwhile, doping Nb⁵⁺ increased the lattice parameters of NVNOPF and enlarged the Na⁺ diffusion pathway. The solid-phase diffusion coefficient of Na⁺ in the material increased from 6.46×10^-16 for Na₃V₂O₂(PO₄)₂F to 3.52×10^-15 cm²/s for Na₃V_1.90Nb_0.10O₂(PO₄)₂F. The discharge specific capacity of Na₃V_1.90Nb_0.10O₂(PO₄)₂F was 126.4 mAh/g (0.1 C rate) and 98.1 mAh/g (10 C rate). After 500 cycles of charge and discharge at the 10 C rate, the capacity retention was 95.2%, which is better than that of the undoped material (66.8%). The results showed that Nb-doped and hollow spherical micro-/nanostructures could effectively improve the electrochemical performance and cyclic stability of NVOPF.

Key words: cathode material for sodium ion battery, Na₃V₂O₂(PO₄)₂F, polyol assisted hydrothermal method, hollow microspheres, niobium doping

CLC Number:

TM 911.1

Zinan ZHANG, Jian CHEN. Preparation and property evaluation of Nb-doped Na₃V₂O₂ （PO₄ ） ₂F hollow microspheres as cathode materials for sodium-ion batteries[J]. Energy Storage Science and Technology, 2023, 12(8): 2370-2381.

Figures/Tables 18

Fig. 1

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Fig. 3

Table 1

Fig. 4

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Table 2

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Table 3

EIS fitting results of the NVOPF and NVNOPF cathodes and diffusion coefficient of Na+"

样品	R_s/Ω	R_ct/Ω	D $N a +$ /(cm²/s)
NVOPF	10.1	751.9	6.46×10^-16
NVNOPF-0.05	6.2	421.6	2.21×10^-15
NVNOPF-0.10	5.2	223.6	3.52×10^-15
NVNOPF-0.15	7.6	584.1	1.06×10^-15

Table 3

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样品	a=b/Å	c/Å	V/Å³	Occ.(Na 1)	Occ.(Na 2)	Occ.(V)	Occ.(Nb)
NVOPF	6.36958	10.60727	430.353	0.380	0.190	1.000	0
NVNOPF-0.05	6.37247	10.61682	431.132	0.380	0.190	0.975	0.025
NVNOPF-0.10	6.38463	10.62043	432.926	0.380	0.190	0.950	0.050
NVNOPF-0.15	6.38841	10.62859	433.772	0.380	0.190	0.925	0.075

样品	设计摩尔含量Na∶V∶Nb	实际摩尔含量Na∶V∶Nb
NVNOPF-0.05	3.00∶1.95∶0.05	2.998∶1.952∶0.048
NVNOPF-0.10	3.00∶1.90∶0.10	3.000∶1.906∶0.094
NVNOPF-0.15	3.00∶1.85∶0.15	2.999∶1.853∶0.147

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Preparation and property evaluation of Nb-doped Na₃V₂O₂ （PO₄ ） ₂F hollow microspheres as cathode materials for sodium-ion batteries

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