Na4FexP4O12+x/C钠离子电池正极材料的结构演变及其电化学性能

doi:10.15541/jim20240490

无机材料学报 ›› 2025, Vol. 40 ›› Issue (5): 497-503.DOI: 10.15541/jim20240490

Na₄Fe_xP₄O₁₂₊_x/C钠离子电池正极材料的结构演变及其电化学性能

万俊池(), 杜路路(), 张永上, 李琳, 刘建德, 张林森()

郑州轻工业大学新能源学院, 郑州 450001

收稿日期:2024-11-20 修回日期:2025-01-13 出版日期:2025-05-20 网络出版日期:2025-02-13
通讯作者: 杜路路, 讲师. E-mail: 2024007@zzuli.edu.cn;
张林森, 教授. E-mail: hnzhanglinsen@163.com
作者简介:万俊池(1995-), 男, 硕士研究生. E-mail: 875801788@qq.com
基金资助:
河南省重点研发专项(241111240300);郑州轻工业大学博士科研基金(2024BSJJ021);河南省杰出外籍科学家工作室(GZS2024016);中原学者工作站项目(234400510015);郑州市科技惠民计划项目(2023KJHM0028)

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

WAN Junchi(), DU Lulu(), ZHANG Yongshang, LI Lin, LIU Jiande, ZHANG Linsen()

School of New Energy, Zhengzhou University of Light Industry, Zhengzhou 450001, China

Received:2024-11-20 Revised:2025-01-13 Published:2025-05-20 Online:2025-02-13
Contact: DU Lulu, lecturer. E-mail: 2024007@zzuli.edu.cn;
ZHANG Linsen, professor. E-mail: hnzhanglinsen@163.com
About author:WAN Junchi (1995-), male, Master candidate. E-mail: 875801788@qq.com
Supported by:
Key Program of Henan Province for Science and Technology(241111240300);Doctoral Science Research Foundation of Zhengzhou University of Light Industry(2024BSJJ021);Henan Outstanding Foreign Scientists Studio(GZS2024016);Zhongyuan Scholar Workstation Funded Project(234400510015);Zhengzhou Science and Technology for People Project(2023KJHM0028)

摘要/Abstract

摘要：

开发低成本和长寿命的钠离子电池(SIBs)正极材料是实现大规模储能的关键。铁基磷酸盐正极材料具有高理论容量、良好的结构稳定性和丰富的储量, 近年来备受关注。本研究通过溶胶凝胶技术以及热处理过程, 制备了一系列Na₄Fe_xP₄O₁₂₊_x/C(x=2.6~3.3)电极材料, 探究了Na₄Fe_xP₄O₁₂₊_x/C电极材料的相结构对电化学性能的影响。研究发现Na₄Fe_xP₄O₁₂₊_x/C电极材料主要存在Na₂FeP₂O₇(NFPO)相、Na₄Fe₃(PO₄)₂P₂O₇(NFPP)相以及NaFePO₄(NFP)相。Na₄Fe_3.1P₄O_15.1/C电极材料中NFPP相的含量最高, 具有电子和钠离子传导快的特点, 表现出最佳的电化学性能。以Na₄Fe_3.1P₄O_15.1/C为正极的SIB表现出较高的可逆容量, 在0.1C(1C=129 mAh·g^-1)电流密度下放电比容量达到102.8 mAh·g^-1, 过700圈循环后容量保持率为88.7%。同时, 该电池具有出色的倍率性能, 在5C电流密度下放电比容量为61.5 mAh·g^-1。

关键词: 钠离子电池, 铁基磷酸盐, 相转变, 电化学性能

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

中图分类号:

TQ152

万俊池, 杜路路, 张永上, 李琳, 刘建德, 张林森. Na₄Fe_xP₄O₁₂₊_x/C钠离子电池正极材料的结构演变及其电化学性能[J]. 无机材料学报, 2025, 40(5): 497-503.

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.

图/表 11

图1 Na4FexP4O12+x/C材料的XRD图谱

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

图2 Na4Fe3.1P4O15.1/C材料的(a) FT-IR谱图、(b) Raman光谱图、(c) TG曲线和(d) Fe2p XPS谱图

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

图3 Na4Fe3.1P4O15.1/C材料的(a~c) SEM照片、(d~f) TEM照片和(g) EDS元素分布图

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

图4 Na4FexP4O12+x/C材料的CV曲线

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

图5 Na4FexP4O12+x/C作为正极材料的SIBs的电化学性能

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

图6 Na4Fe3.1P4O15.1/C作为正极材料的SIBs的性能

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

图7 Na4Fe3.1P4O15.1/C作为正极材料的SIBs的电化学性能

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

图S1 Na4FexP4O12+x/C材料的Raman光谱图

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

图S2 Na4FexP4O12+x/C材料的TG曲线

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

图S3 Na4FexP4O12+x/C材料的SEM照片

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

表S1 本工作与文献报道的聚阴离子类钠离子电池正极材料的循环性能对比[S1-S6]

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]

参考文献 34

[1]	DUNN B, KAMATH H, TARASCON J M. Electrical energy storage for the grid: a battery of choices. Science, 2011, 334(6058): 928.
[2]	ARMAND M, TARASCON J M. Building better batteries. Nature, 2008, 451(7179): 652.
[3]	YANG Z, ZHANG J, KINTNER-MEYER M C W, et al. Electrochemical energy storage for green grid. Chemical Reviews, 2011, 111(5): 3577.
[4]	CRABTREE G. Perspective: the energy-storage revolution. Nature, 2015, 526(7575): S92.
[5]	ABAS N, KALAIR A, KHAN N. Review of fossil fuels and future energy technologies. Futures, 2015, 69: 31.
[6]	ZU C X, LI H. Thermodynamic analysis on energy densities of batteries. Energy & Environmental Science, 2011, 4(8): 2614.
[7]	DE LA LLAVE E, BORGEL V, PARK K J, et al. Comparison between Na-ion and Li-ion cells: understanding the critical role of the cathodes stability and the anodes pretreatment on the cells behavior. ACS Applied Materials & Interfaces, 2016, 8(3): 1867.
[8]	HU M F, HUANG L P, LI H, et al. Research progress on hard carbon anode for Li/Na-ion batteries. Journal of Inorganic Materials, 2024, 39(1): 32.
[9]	HWANG J Y, MYUNG S T, SUN Y K. Sodium-ion batteries: present and future. Chemical Society Reviews, 2017, 46(12): 3529.
[10]	GUO Y J, JIN R X, FAN M, et al. Sodium layered oxide cathodes: properties, practicality and prospects. Chemical Society Reviews, 2024, 53(15): 7828.
[11]	SU H, JAFFER S, YU H. Transition metal oxides for sodium-ion batteries. Energy Storage Materials, 2016, 5: 116.
[12]	LAN Y, YAO W, HE X, et al. Mixed polyanionic compounds as positive electrodes for low-cost electrochemical energy storage. Angewandte Chemie International Edition, 2020, 59(24): 9255.
[13]	KOSOVA N V, SHINDROV A A. Mixed polyoxyanion cathode materials. Energy Storage Materials, 2021, 42: 570.
[14]	BARPANDA P. Pursuit of sustainable iron-based sodium battery cathodes: two case studies. Chemistry of Materials, 2016, 28(4): 1006.
[15]	NI Q, BAI Y, WU F, et al. Polyanion-type electrode materials for sodium-ion batteries. Advanced Science, 2017, 4(3): 1600275.
[16]	FERGUS J W. Recent developments in cathode materials for lithium ion batteries. Journal of Power Sources, 2010, 195(4): 939.
[17]	HE L, LI H, GE X, et al. Iron-phosphate-based cathode materials for cost-effective sodium-ion batteries: development, challenges, and prospects. Advanced Materials Interfaces, 2022, 9(20): 2200515.
[18]	LI H, XU M, LONG H, et al. Stabilization of multicationic redox chemistry in polyanionic cathode by increasing entropy. Advanced Science, 2022, 9(25):2202082.
[19]	AHSAN Z, CAI Z, WANG S, et al. Recent development of phosphate based polyanion cathode materials for sodium-ion batteries. Advanced Energy Materials, 2024, 14(27): 2400373.
[20]	SHI Y, JIANG P, WANG S, et al. Slight compositional variation- induced structural disorder-to-order transition enables fast Na⁺ storage in layered transition metal oxides. Nature Communications, 2022, 13: 7888.
[21]	WANG J, ZENG W, ZHU J, et al. Fe-rich pyrophosphate with prolonged high-voltage-plateaus and suppressed voltage decay as sodium-ion battery cathode. Nano Energy, 2023, 116: 108822.
[22]	ZHAO A, LIU C, JI F, et al. Revealing the phase evolution in Na₄Fe_xP₄O₁₂₊_x (2≤x≤4) cathode materials. ACS Energy Letters, 2023, 8(1): 753.
[23]	REN W, QIN M, ZHOU Y, et al. Electrospun Na₄Fe₃(PO₄)₂(P₂O₇) nanofibers as free-standing cathodes for ultralong-life and high-rate sodium-ion batteries. Energy Storage Materials, 2023, 54: 776.
[24]	SONG H J, KIM K H, KIM J C, et al. Superior sodium storage performance of reduced graphene oxide-supported Na_3.12Fe_2.44(P₂O₇)₂/C nanocomposites. Chemical Communications, 2017, 53(67): 9316.
[25]	WANG J, XU S D, LU Z H, et al. Hollow-structured CoSe₂/C anode materials: preparation and sodium storage properties for sodium-ion batteries. Journal of Inorganic Materials, 2022, 37(12): 1344.
[26]	YOU S, ZHANG Q, LIU J, et al. Hard carbon with an opened pore structure for enhanced sodium storage performance. Energy & Environmental Science, 2024, 17(21): 8189.
[27]	LIU Y, ZHANG N, WANG F, et al. Approaching the downsizing limit of maricite NaFePO₄ toward high-performance cathode for sodium-ion batteries. Advanced Functional Materials, 2018, 28(30): 1801917.
[28]	ZHANG L M, HE X D, WANG S, et al. Hollow-sphere-structured Na₄Fe₃(PO₄)₂(P₂O₇)/C as a cathode material for sodium-ion batteries. ACS Applied Materials & Interfaces, 2021, 13(22): 25972.
[29]	WU X, ZHONG G, YANG Y. Sol-Gel synthesis of Na₄Fe₃(PO₄)₂(P₂O₇)/C nanocomposite for sodium ion batteries and new insights into microstructural evolution during sodium extraction. Journal of Power Sources, 2016, 327: 666.
[30]	KONG G Q, LENG M Z, ZHOU Z R, et al. Sb doped O3 type Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂ cathode material for Na-ion battery. Journal of Inorganic Materials, 2023, 38(6): 656.
[31]	YUAN T, WANG Y, ZHANG J, et al. 3D graphene decorated Na₄Fe₃(PO₄)₂(P₂O₇) microspheres as low-cost and high-performance cathode materials for sodium-ion batteries. Nano Energy, 2019, 56: 160.
[32]	PENG B, WAN G, AHMAD N, et al. Recent progress in the emerging modification strategies for layered oxide cathodes toward practicable sodium ion batteries. Advanced Energy Materials, 2023, 13(27): 2300334.
[33]	WANG C, LIU L, ZHAO S, et al. Tuning local chemistry of P2 layered-oxide cathode for high energy and long cycles of sodium- ion battery. Nature Communications, 2021, 12: 2256.
[34]	LI M, QIU X, YIN Y, et al. O3-type Ni-Rich NaNi_2/3Mn_1/6Fe_1/6O₂: a high-performance cathode material for sodium-ion batteries. Journal of Alloys and Compounds, 2023, 969: 172406.

Na₄Fe_xP₄O₁₂₊_x/C钠离子电池正极材料的结构演变及其电化学性能

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

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