Structural Evolution and Electrochemical Performance of Na4FexP4O12+x/C Cathode Materials for Sodium-ion Batteries

doi:10.15541/jim20240490

Abstract

Abstract:

The development of low-cost and long-lifespan sodium-ion battery (SIB) cathode materials is crucial for large-scale energy storage. Iron-based phosphate cathode materials have attracted significant attention in recent years for their high theoretical capacity, excellent structural stability and rich resources. Here, a series of Na₄Fe_xP₄O₁₂₊_x/C (x=2.6-3.3) electrode materials are prepared using Sol-Gel technique and thermal treatment process. Effect of the phase structure on electrochemical performance of Na₄Fe_xP₄O₁₂₊_x/C electrode materials is investigated. It is found that three phases, including Na₂FeP₂O₇ (NFPO), Na₄Fe₃(PO₄)₂P₂O₇ (NFPP) and NaFePO₄(NFP), mainly exist in the Na₄Fe_xP₄O₁₂₊_x/C system. Among Na₄Fe_xP₄O₁₂₊_x/C electrode materials, Na₄Fe_3.1P₄O_15.1/C electrode material with the highest content of NFPP phase possesses rapid electronic and sodium-ion conduction characteristics, thereby exhibiting the optimal electrochemical performance. As a result, the SIB equipped with Na₄Fe_3.1P₄O_15.1/C electrode material shows high reversible capacity, with a discharge specific capacity of 102.8 mAh·g^-1 at a current density of 0.1C (1C=129 mAh·g^-1), as well as capacity retention of 88.7% after 700 cycles. Furthermore, the as-assembled battery exhibits excellent rate performance with a discharge specific capacity of 61.5 mAh·g^-1 at a current density of 5C.

Key words: sodium-ion battery, iron-based phosphate, phase transition, electrochemical performance

CLC Number:

TQ152

WAN Junchi, DU Lulu, ZHANG Yongshang, LI Lin, LIU Jiande, ZHANG Linsen. Structural Evolution and Electrochemical Performance of Na₄Fe_xP₄O₁₂₊_x/C Cathode Materials for Sodium-ion Batteries[J]. Journal of Inorganic Materials, 2025, 40(5): 497-503.

Figures/Tables 11

Fig. 1 XRD patterns of Na4FexP4O12+x/C materials (a) 2θ=5°-60°; (b) 2θ=8°-18°; (c) 2θ=30°-40°

Fig. 2 (a) FT-IR spectrum, (b) Raman spectrum, (c) TG curve, and (d) Fe2p XPS spectrum of Na4Fe3.1P4O15.1/C material

Fig. 3 (a-c) SEM images, (d-f) TEM images and (g) EDS elemental mappings of Na4Fe3.1P4O15.1/C material

Fig. 4 CV curves of Na4FexP4O12+x/C materials (a) x=2.6-2.9; (b) x=3.0-3.3

Fig. 5 Electrochemical performance of SIBs with Na4FexP4O12+x/C as cathodes (a) Initial charge-discharge curves; (b) Initial specific discharge capacities and Coulombic efficiencies; (c) Cycling test at 0.1C. Colorful figures are available on website

Fig. 6 Performance of SIBs with Na4Fe3.1P4O15.1/C as cathodes (a) Rate performance; (b) Charge-discharge curves at different rates; (c) Cycling performance at different rates

Fig. 7 Electrochemical performance of Na4Fe3.1P4O15.1/C as cathodes of SIBs (a) EIS plots; (b) Charge-discharge curves with different cycles at 0.1C; (c) Long-term cycling performance at 0.1C; Colorful figures are available on website

Fig. 8 S1 Raman spectra of Na4FexP4O12+x/C materials (a) x=2.6; (b) x=2.7; (c) x=2.8; (d) x=2.9; (e) x=3.0; (f) x=3.1; (g) x=3.2; (h) x=3.3

Fig. 9 S2 TG curves of Na4FexP4O12+x/C materials (a) x=2.6; (b) x=2.7; (c) x=2.8; (d) x=2.9; (e) x=3.0; (f) x=3.1; (g) x=3.2; (h) x=3.3

Fig. 10 S3 SEM images of Na4FexP4O12+x/C materials (a) x=2.6; (b) x=2.7; (c) x=2.8; (d) x=2.9; (e) x=3.0; (f) x=3.1; (g) x=3.2; (h) x=3.3

Table S1 Cycle performance comparison of polyanionic cathode materials of sodium-ion batteries in this work and literature[S1-S6]

Material	Initial discharge capacity/ (mAh·g^-1)	(Reversible capacity/(mAh·g^-1))/ cycle number	Capacity retention	Ref.
Na₄Fe_3.1P₄O_15.1/C	102.8	101.2/200; 95.0/500	98.8%; 92.4%	This work
Na₄Fe_2.9Mn_0.14(PO₄)₂(P₂O₇)@C	94.5	92.1/100	97.4%	[S1]
Na₄Fe₃(PO₄)₂(P₂O₇)/C	95.3	90/100	94.7%	[S2]
NaNi_0.4Fe_0.2Mn_0.4O₂	100	70/100	70%	[S3]
Na₄Fe₃(PO₄)₂(P₂O₇)@C/Ti₃C₂Tx	93.4	91.1/200	97.5%	[S4]
Na₃V₂(PO₄)₃/C	102	94/500	92.1%	[S5]
Na_0.44MnO₂/C	114	74.1/1000	65%	[S6]

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Structural Evolution and Electrochemical Performance of Na₄Fe_xP₄O₁₂₊_x/C Cathode Materials for Sodium-ion Batteries

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