Nb掺杂Na3V2O2 （PO4 ） 2F空心微球钠离子电池正极材料的制备与性能

doi:10.19799/j.cnki.2095-4239.2023.0177

摘要/Abstract

摘要：

Na₃V₂O₂(PO₄)₂F(NVOPF)具有较稳定的聚阴离子结构、较高的工作电压和理论比能量，是一种具有良好应用前景的钠离子电池正极材料。但该材料在合成过程中易发生不规则团聚，且本征电导率低，导致材料的实际比容量较小，倍率性能和循环性能有待提高。通过离子掺杂以及合成具有微纳结构的材料可以有效提高这类材料的结构稳定性和电导率。本工作首次报道了多元醇辅助水热法合成具有空心微球结构的Nb⁵⁺掺杂NVOPF[NVNOPF，Na₃V_2-_x Nb _x O₂(PO₄)₂F(0≤x≤0.15)]材料。所制备的NVOPF和NVNOPF是尺寸为0.7～1.0 μm的具有中空结构的微球。可以发现微球由尺寸小于100 nm的纳米颗粒组成。纳米颗粒缩短钠离子的扩散距离，并且缓冲了由于钠离子的嵌入/脱出所导致的体积变化，提高了材料的循环稳定性。同时，掺杂Nb⁵⁺增大了NVOPF的晶格参数，增大了Na⁺扩散通道，将Na⁺在NVOPF中的固相扩散系数由Na₃V₂O₂(PO₄)₂F的6.46×10^-16 cm²/s提高至Na₃V_1.90Nb_0.10O₂(PO₄)₂F的3.52×10^-15 cm²/s。Na₃V_1.90Nb_0.10O₂(PO₄)₂F材料以0.1 C倍率放电，首次放电比容量达126.4 mAh/g；以10 C倍率放电，初始比容量为98.1 mAh/g，500周循环后的容量保持率为95.2%，明显优于未掺杂材料的66.8%。研究结果显示掺杂Nb⁵⁺的空心球形微纳结构有效提高了NVOPF材料的电化学性能和循环稳定性。

关键词: 钠离子电池正极材料, Na₃V₂O₂(PO₄)₂F, 多元醇辅助水热法, 空心微球, 铌掺杂

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

中图分类号:

TM 911.1

张梓楠, 陈剑. Nb掺杂Na₃V₂O₂ （PO₄ ） ₂F空心微球钠离子电池正极材料的制备与性能[J]. 储能科学与技术, 2023, 12(8): 2370-2381.

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.

图/表 18

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表3

四种材料的阻抗拟合参数和Na+ 的扩散系数"

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

表3

参考文献 58

1	OBAMA B. The irreversible momentum of clean energy[J]. Science, 2017, 355(6321): 126-129.
2	SCROSATI B, GARCHE J. Lithium batteries: Status, prospects and future[J]. Journal of Power Sources, 2010, 195(9): 2419-2430.
3	CRABTREE G. Perspective: The energy-storage revolution[J]. Nature, 2015, 526(7575): doi: 10.1038/526S92a.
4	LARCHER D, TARASCON J M. Towards greener and more sustainable batteries for electrical energy storage[J]. Nature Chemistry, 2015, 7(1): 19-29.
5	LIU C, LI F, MA L P, et al. Advanced materials for energy storage[J]. Advanced Materials, 2010, 22(8): doi: 10.1002/adma.200903328.
6	GUPTA P, PUSHPAKANTH S, HAIDER M A, et al. Understanding the design of cathode materials for Na-ion batteries[J]. ACS Omega, 2022, 7(7): 5605-5614.
7	MAO Z F, WANG R, HE B B, et al. Large-area, uniform, aligned arrays of Na₃(VO)₂(PO₄)₂F on carbon nanofiber for quasi-solid-state sodium-ion hybrid capacitors[J]. Small, 2019, 15(36): doi: 10.1002/smll.201902466.
8	XIAO J, LI X, TANG K K, et al. Recent progress of emerging cathode materials for sodium ion batteries[J]. Materials Chemistry Frontiers, 2021, 5(10): 3735-3764.
9	BAI Q A, YANG L F, CHEN H L, et al. Computational studies of electrode materials in sodium-ion batteries[J]. Advanced Energy Materials, 2018, 8(17): doi: 10.1002/aenm.201702998.
10	YAN R B, ZHAN G H, LIAO W H, et al. Uniform Na₃V₂(PO₄)₂O₂F microcubes enhanced by ionic liquid-modified multi-walled carbon nanotubes as a superior cathode for sodium-ion batteries[J]. Electrochimica Acta, 2023, 439: doi: 10.1016/j.‍electacta.‍2022. 141671.
11	JIN H Y, LIU M, UCHAKER E, et al. Nanoporous carbon leading to the high performance of a Na₃V₂O₂(PO₄)₂F@carbon/graphene cathode in a sodium ion battery[J]. CrystEngComm, 2017, 19(30): 4287-4293.
12	YIN Y M, PEI C Y, LIAO X B, et al. Revealing the multi-electron reaction mechanism of Na₃V₂O₂ (PO₄)₂F towards improved lithium storage[J]. ChemSusChem, 2021, 14(14): 2984-2991.
13	LI X Y, JIANG S L, LI S Y, et al. Overcoming the rate-determining kinetics of the Na₃V₂O₂(PO₄)₂F cathode for ultrafast sodium storage by heterostructured dual-carbon decoration[J]. Journal of Materials Chemistry A, 2021, 9(19): 11827-11838.
14	ZHANG L L, LIU J, WEI C, et al. N/P-dual-doped carbon-coated Na₃V₂(PO₄)₂O₂F microspheres as a high-performance cathode material for sodium-ion batteries[J]. ACS Applied Materials & Interfaces, 2020, 12(3): 3670-3680.
15	LEE J, PARK S, PARK Y, et al. Chromium doping into NASICON-structured Na₃V₂(PO₄)₃ cathode for high-power Na-ion batteries[J]. Chemical Engineering Journal, 2021, 422: doi: 10.1016/j.‍cej.‍2021. 130052.
16	DU P, MI K, HU F D, et al. Mn-doped hollow Na₃V₂O₂(PO₄)₂F as a high performance cathode material for sodium ion batteries[J]. European Journal of Inorganic Chemistry, 2021, 2021(13): 1256-1262.
17	LI H X, JIN T, CHEN X B, et al. Rational architecture design enables superior Na storage in greener NASICON-Na₄ MnV(PO₄)₃ cathode[J]. Advanced Energy Materials, 2018, 8(24): doi: 10.1002/aenm.201801418.
18	WANG S T, ZHAO L J, DONG Y H, et al. Pre-zeolite framework super-MIEC anodes for high-rate lithium-ion batteries[J]. Energy & Environmental Science, 2023, 16(1): 241-251.
19	FANG Y J, YU X Y, LOU X W D. A practical high-energy cathode for sodium-ion batteries based on uniform P2-Na_0.7CoO₂ microspheres[J]. Angewandte Chemie International Edition, 2017, 56(21): 5801-5805.
20	QI Y R, MU L Q, ZHAO J M, et al. pH-regulative synthesis of Na₃(VPO₄)₂F₃ nanoflowers and their improved Na cycling stability[J]. Journal of Materials Chemistry A, 2016, 4(19): 7178-7184.
21	QI Y R, TONG Z Z, ZHAO J M, et al. Scalable room-temperature synthesis of multi-shelled Na₃(VOPO₄)₂F microsphere cathodes[J]. Joule, 2018, 2(11): 2348-2363.
22	GUO F F, FAN M H, JIN P P, et al. Precursor-mediated synthesis of double-shelled V₂O₅ hollow nanospheres as cathode material for lithium-ion batteries[J]. CrystEngComm, 2016, 18(22): 4068-4073.
23	LIN B, LI Q F, LIU B D, et al. Biochemistry-directed hollow porous microspheres: Bottom-up self-assembled polyanion-based cathodes for sodium ion batteries[J]. Nanoscale, 2016, 8(15): 8178-8188.
24	LI Y, CHEN M H, LIU B, et al. Heteroatom doping: An effective way to boost sodium ion storage[J]. Advanced Energy Materials, 2020, 10(27): doi: 10.1002/aenm.202000927.
25	SUN X F, WANG Z K, HU Q D, et al. Oxygen-tuned Na₃V₂(PO₄)₂F_3-2 yO₂ y (0<y<1) as high-rate cathode materials for rechargeable sodium batteries[J]. ACS Applied Energy Materials, 2022, 5(12): 15799-15808.
26	HE J R, TAO T, YANG F, et al. Optimizing the electrolyte systems for Na₃(VO_1- xPO₄)₂F₁₊₂ x (0≤x≤1) cathode and understanding their interfacial chemistries towards high-rate sodium-ion batteries[J]. ChemSusChem, 2022, 15(8): doi: 10.1002/cssc.202200480.
27	ZHAO X X, GU Z Y, GUO J Z, et al. Dual anionic substitution engineering for an advanced NASICON phosphate cathode in sodium-ion batteries[J]. Materials Chemistry Frontiers, 2021, 5(15): 5671-5678.
28	GU Z Y, GUO J Z, SUN Z H, et al. Air/water/temperature-stable cathode for all-climate sodium-ion batteries[J]. Cell Reports Physical Science, 2021, 2(12): doi: 10.1016/j.xcrp.2021.100665.
29	ZHANG Y, GUO S R, XU H Y. Synthesis of uniform hierarchical Na₃V_1.95Mn_0.05(PO₄)₂F₃@C hollow microspheres as a cathode material for sodium-ion batteries[J]. Journal of Materials Chemistry A, 2018, 6(10): 4525-4534.
30	LI X, HUANG Y Y, WANG J S, et al. High valence Mo-doped Na₃V₂(PO₄)₃/C as a high rate and stable cycle-life cathode for sodium battery[J]. Journal of Materials Chemistry A, 2018, 6(4): 1390-1396.
31	LIU X H, FENG G L, WU Z G, et al. Enhanced sodium storage property of sodium vanadium phosphate via simultaneous carbon coating and Nb⁵⁺ doping[J]. Chemical Engineering Journal, 2020, 386: doi: 10.1016/j.cej.2019.123953.
32	YUN Y S, JIN H J. Sulfur-doped, reduced graphene oxide nanoribbons for sodium-ion batteries[J]. Materials Letters, 2017, 198: 106-109.
33	ZHANG Y Z, CHEN L, MENG Y, et al. Sodium storage in fluorine-rich mesoporous carbon fabricated by low-temperature carbonization of polyvinylidene fluoride with a silica template[J]. RSC Advances, 2016, 6(112): 110850-110857.
34	WANG H M, WANG H X, CHEN Y, et al. Phosphorus-doped graphene and (8, 0) carbon nanotube: Structural, electronic, magnetic properties, and chemical reactivity[J]. Applied Surface Science, 2013, 273: 302-309.
35	MASSA W, YAKUBOVICH O V, DIMITROVA O V. Crystal structure of a new sodium vanadyl(IV) fluoride phosphate Na₃{V₂O₂F[PO₄]₂}[J]. Solid State Sciences, 2002, 4(4): 495-501.
36	LI Z F, LUO C Y, WANG C X, et al. Effects of Nb substitution on structure and electrochemical properties of LiNi_0.7Mn_0.3O₂ cathode materials[J]. Journal of Solid State Electrochemistry, 2018, 22(9): 2811-2820.
37	NIU Y B, ZHANG Y, XU M W. A review on pyrophosphate framework cathode materials for sodium-ion batteries[J]. Journal of Materials Chemistry A, 2019, 7(25): 15006-15025.
38	YOO C Y, HONG K P, KIM S J. A new layered perovskite, KSrNb₂O₆F, by powder neutron diffraction[J]. Acta Crystallographica Section C Crystal Structure Communications, 2007, 63(8): doi: 10.1107/s0108270107029563.
39	LING M X, LI F, YI H M, et al. Superior Na-storage performance of molten-state-blending-synthesized monoclinic NaVPO₄F nanoplates for Na-ion batteries[J]. Journal of Materials Chemistry A, 2018, 6(47): 24201-24209.
40	GUO J Z, WANG P F, WU X L, et al. High-energy/power and low-temperature cathode for sodium-ion batteries: in situ XRD study and superior full-cell performance[J]. Advanced Materials, 2017, 29(33): doi: 10.1002/adma.201701968.
41	YANG H, WU X L, CAO M H, et al. Solvothermal synthesis of LiFePO₄ hierarchically dumbbell-like microstructures by nanoplate self-assembly and their application as a cathode material in lithium-ion batteries[J]. The Journal of Physical Chemistry C, 2009, 113(8): 3345-3351.
42	XIAO Y H, LIU S J, LI F, et al. 3D hierarchical Co₃O₄ Twin-spheres with an urchin-like structure: Large-scale synthesis, multistep-splitting growth, and electrochemical pseudocapacitors[J]. Advanced Functional Materials, 2012, 22(19): 4052-4059.
43	CHEN J, WANG T, CHEN C, et al. Heteroatom doping hollow vanadium oxide/carbon composites as universal anode materials for efficient alkali-metal ion storage[J]. Carbon, 2022, 192: 30-40.
44	KIM D H, KIM J. Synthesis of LiFePO₄ nanoparticles in polyol medium and their electrochemical properties[J]. Electrochemical and Solid-State Letters, 2006, 9(9): doi: 10.1149/1.2218308.
45	ARAGÓN M J, GUTIÉRREZ J, KLEE R, et al. On the effect of carbon content for achieving a high performing Na₃V₂(PO₄)₃/C nanocomposite as cathode for sodium-ion batteries[J]. Journal of Electroanalytical Chemistry, 2017, 784: 47-54.
46	ZHU Q, WANG M, NAN B, et al. Core/shell nanostructured Na₃V₂(PO₄)₃/C/TiO₂ composite nanofibers as a stable anode for sodium-ion batteries[J]. Journal of Power Sources, 2017, 362: 147-159.
47	ZHAO L N, ZHAO H L, DU Z H, et al. Delicate lattice modulation enables superior Na storage performance of Na₃V₂(PO₄)₃ as both an anode and cathode material for sodium-ion batteries: Understanding the role of calcium substitution for vanadium[J]. Journal of Materials Chemistry A, 2019, 7(16): 9807-9814.
48	CHENG Q S, LIANG J W, LIN N, et al. Porous TiNb₂O₇ nanospheres as ultra long-life and high-power anodes for lithium-ion batteries[J]. Electrochimica Acta, 2015, 176: 456-462.
49	ZHAO X X, GU Z Y, LI W H, et al. Temperature-dependent electrochemical properties and electrode kinetics of Na₃V₂(PO₄)₂O₂F cathode for sodium-ion batteries with high energy density[J]. Chemistry-A European Journal, 2020, 26(35): 7823-7830.
50	YAN L T, CHEN G, SARKER S, et al. Ultrafine Nb₂O₅ nanocrystal coating on reduced graphene oxide as anode material for high performance sodium ion battery[J]. ACS Applied Materials & Interfaces, 2016, 8(34): 22213-22219.
51	KRETSCHMER K, SUN B, ZHANG J Q, et al. 3D interconnected carbon fiber network-enabled ultralong life Na₃V₂(PO₄)₃@Carbon paper cathode for sodium-ion batteries[J]. Small, 2017, 13(9): doi: 10.1002/smll.201603318.
52	WANG X Y, HAO H, LIU J L, et al. A novel method for preparation of macroposous lithium nickel manganese oxygen as cathode material for lithium ion batteries[J]. Electrochimica Acta, 2011, 56(11): 4065-4069.
53	LI S J, GE P, ZHANG C Y, et al. The electrochemical exploration of double carbon-wrapped Na₃V₂(PO₄)₃: Towards long-time cycling and superior rate sodium-ion battery cathode[J]. Journal of Power Sources, 2017, 366: 249-258.
54	ZHANG D X, WANG J, DONG K Z, et al. First principles investigation on the elastic and electronic properties of Mn, Co, Nb, Mo doped LiFePO₄[J]. Computational Materials Science, 2018, 155: 410-415.
55	LI X T, SHAO Z B, LIU K R, et al. Enhancement of Nb-doping on the properties of LiFePO₄/C prepared via a high-temperature ball milling-based method[J]. Journal of Solid State Electrochemistry, 2019, 23(2): 465-473.
56	KOYAMA C, NOZAWA J, MAEDA K, et al. Investigation of defect structure of impurity-doped lithium niobate by combining thermodynamic constraints with lattice constant variations[J]. Journal of Applied Physics, 2015, 117(1): doi: 10.1063/1.4905286.
57	CHEN B F, PENG Z B, YUAN Z Y. Constructing sandwich structure of Nb-substituted Na₃V₂(PO₄)₃/C nanoparticles enwrapped on three-dimensional graphene with superior sodium storage property[J]. Ceramics International, 2022, 48(22): 33957-33966.
58	BI L N, LIU X Q, LI X Y, et al. Modulation of the crystal structure and ultralong life span of a Na₃V₂(PO₄)₃-based cathode for a high-performance sodium-ion battery by niobium-vanadium substitution[J]. Industrial & Engineering Chemistry Research, 2020, 59(48): 21039-21046.

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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Nb掺杂Na₃V₂O₂ （PO₄ ） ₂F空心微球钠离子电池正极材料的制备与性能

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

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