Na3V2（PO4）3@C用作水系锌离子电池正极材料的研究

doi:10.19799/j.cnki.2095-4239.2021.0056

摘要/Abstract

摘要：

水系锌离子电池（AZIBs）是未来大型储能领域中具有吸引力的选择之一。但合适的用于锌离子存储的正极材料少之又少。本工作以NASICON结构的正极材料Na₃V₂（PO₄）₃（NVP）作为储锌正极材料，在高浓度的电解液中可以实现高效的Zn²⁺存储并展现出超长的循环性能。本研究采用简单的溶胶凝胶法制备出均匀碳包覆的NVP，并借助X射线衍射（XRD）、扫描电子显微镜（SEM）、恒流充放电等表征测试手段，分析NVP材料的结构、形貌和用作AZIBs正极时表现出的电化学性能。同时，本工作研究了不同浓度的电解液对电化学性能的影响。结果表明，电解液浓度提升后NVP材料可以展现出更高的容量存储、卓越的倍率性能和超长的循环寿命。在2000 mA/g的超高电流密度下循环1000圈之后，容量保持率仍为77.8%，并且在循环过程中材料的每圈库仑效率接近100%。此外，通过循环伏安法（CV）和恒电流间歇滴定法（GITT）进一步探索了NVP电极的动力学过程并得出，NVP材料出色的电化学性能的表现归因于其稳定和开放的NASICON框架和优异的动力学行为。

关键词: 水系锌离子电池, 正极材料, 磷酸钒钠, 高浓度电解液, 长循环寿命

Abstract:

Aqueous zinc-ion batteries (AZIBs) are an attractive choice for large-scale energy storage in the future. However, suitable cathode materials for Zn²⁺ storage are lacking. This work finds that the cathode material Na₃V₂(PO₄)₃ (NVP) with the natrium super ionic conductor (NASICON) structure can achieve efficient Zn²⁺ storage and ultralong-cycle performance in high-concentration electrolytes. In this paper, a simple sol-gel method is used to prepare a uniform carbon-coated NVP. With the help of X-ray diffraction, scanning electron microscopy, constant current charge-discharge, and other characterization test methods, the structure, morphology, and performance of the NVP materials when used as cathode for AZIBs are analyzed. Additionally, the effects of different concentrations of electrolytes on the electrochemical performances are studied. The results show that NVP materials can provide high-capacity storage, excellent rate performance, and long-cycle life as the electrolyte concentration increases. After 1000 cycles at a high current density of 2000 mA·g^-1, the capacity retention rate is still 77.8%, and the coulombic efficiency per cycle of the material is close to 100%. Furthermore, the kinetic process of the NVP electrode is explored through cyclic voltammetry and galvanostatic intermittent titration technique. Experiments prove that these excellent electrochemical performances can be attributed to the stable and open NASICON framework and excellent kinetic behavior.

Key words: aqueous zinc-ion batteries, cathode materials, Na₃V₂(PO₄)₃, high concentration electrolyte, long cycle life

中图分类号:

O 646.21

衡永丽, 谷振一, 郭晋芝, 吴兴隆. Na₃V₂（PO₄）₃@C用作水系锌离子电池正极材料的研究[J]. 储能科学与技术, 2021, 10(3): 938-944.

Yongli HENG, Zhenyi GU, Jinzhi GUO, Xinglong WU. Na₃V₂（PO₄）₃@C cathode material for aqueous zinc-ion batteries[J]. Energy Storage Science and Technology, 2021, 10(3): 938-944.

图/表 6

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参考文献 37

1	FANG G Z, ZHOU J, PAN A Q, et al. Recent advances in aqueous zinc-ion batteries[J]. ACS Energy Letters, 2018, 3(10): 2480-2501.
2	SONG M, TAN H, CHAO D L, et al. Recent advances in Zn-ion batteries[J]. Advanced Functional Materials, 2018, 28(41): doi: 10.1002/j.adfm.201802564.
3	LI H F, MA L T, HAN C P, et al. Advanced rechargeable zinc-based batteries: Recent progress and future perspectives[J]. Nano Energy, 2019, 62: 550-587.
4	MING J, GUO J, XIA C, et al. Zinc-ion batteries: Materials, mechanisms, and applications[J]. Materials Science and Engineering: Reports, 2019, 135: 58-84.
5	SELVAKUMARAN D, PAN A Q, LIANG S Q, et al. A review on recent developments and challenges of cathode materials for rechargeable aqueous Zn-ion batteries[J]. Journal of Materials Chemistry A, 2019, 7(31): 18209-18236.
6	LIU Z X, HUANG Y, HUANG Y, et al. Voltage issue of aqueous rechargeable metal-ion batteries[J]. Chemical Society Reviews, 2020, 49(1): 180-232.
7	YU P, ZENG Y X, ZHANG H Z, et al. Flexible Zn-ion batteries: Recent progresses and challenges[J]. Small, 2019, 15(7): doi: 10.1002/smll.201804760.
8	TROCOLI R, LA MANTIA F. An aqueous zinc-ion battery based on copper hexacyanoferrate[J]. ChemSusChem, 2015, 8(3): 481-485.
9	ZHANG L Y, CHEN L, ZHOU X F, et al. Towards high-voltage aqueous metal-ion batteries beyond 1.5 V: The zinc/zinc hexacyanoferrate system[J]. Advanced Energy Materials, 2015, 5(2): doi: 10.1002/aenm.201400930.
10	GUO C, LIU H M, LI J F, et al. Ultrathin δ-MnO₂ nanosheets as cathode for aqueous rechargeable zinc ion battery[J]. Electrochimica Acta, 2019, 304: 370-377.
11	KHAMSANGA S, PORNPRASERTSUK R, YONEZAWA T, et al. δ-MnO₂ nanoflower/graphite cathode for rechargeable aqueous zinc ion batteries[J]. Scientific Reports, 2019, 9(1): doi: 10.1038/s41598-019-44915-8.
12	WANG C Y, WANG M Q, HE Z C, et al. Rechargeable aqueous zinc-manganese dioxide/graphene batteries with high rate capability and large capacity[J]. ACS Applied Energy Materials, 2020, 3(2): 1742-1748.
13	CHEN L L, YANG Z H, HUANG Y G. Monoclinic VO₂(D) hollow nanospheres with super-long cycle life for aqueous zinc ion batteries[J]. Nanoscale, 2019, 11(27): 13032-13039.
14	JIA D D, ZHENG K, SONG M, et al. VO₂·0.2H₂O nanocuboids anchored onto graphene sheets as the cathode material for ultrahigh capacity aqueous zinc ion batteries[J]. Nano Research, 2020, 13(1): 215-224.
15	ZHANG L S, MIAO L, ZHANG B, et al. A durable VO₂(M)/Zn battery with ultrahigh rate capability enabled by pseudocapacitive proton insertion[J]. Journal of Materials Chemistry A, 2020, 8(4): 1731-1740.
16	YAN M Y, HE P, CHEN Y, et al. Water-lubricated intercalation in V₂O₅·nH₂O for high capacity and high-rate aqueous rechargeable zinc batteries[J]. Advanced Materials, 2018, 30(1): doi: 10.1002/adma.201703725.
17	ZHANG N, DONG Y, JIA M, et al. Rechargeable aqueous Zn-V₂O₅ battery with high energy density and long cycle life[J]. ACS Energy Letters, 2018, 3(6): 1366-1372.
18	CHEN L L, YANG Z H, CUI F, et al. Enhanced rate and cycling performances of hollow V₂O₅ nanospheres for aqueous zinc ion battery cathode[J]. Applied Surface Science, 2020, 507: doi: 10.1016/j.apsusc.2019.145137.
19	JAVED M S, LEI H, WANG Z L, et al. 2D V₂O₅ nanosheets as a binder-free high-energy cathode for ultrafast aqueous and flexible Zn-ion batteries[J]. Nano Energy, 2020, 70: doi: 10.1016/j.nanoen.2020.104573.
20	WANG X Y, MA L W, ZHANG P C, et al. Vanadium pentoxide nanosheets as cathodes for aqueous zinc-ion batteries with high rate capability and long durability[J]. Applied Surface Science, 2020, 502: doi: 10.1016/j.apsusc.2019.144207.
21	HU F, XIE D, ZHAO F, et al. Na₂V₆O₁₆∙2.14H₂O nanobelts as a stable cathode for aqueous zinc-ion batteries with long-term cycling performance[J]. Journal of Energy Chemistry, 2019, 38: 185-191.
22	MING F W, LIANG H F, LEI Y J, et al. Layered MgxV₂O₅·nH₂O as cathode material for high-performance aqueous zinc ion batteries[J]. ACS Energy Letters, 2018, 3(10): 2602-2609.
23	HE P, YAN M Y, ZHANG G B, et al. Layered VS₂ nanosheet-based aqueous Zn ion battery cathode[J]. Advanced Energy Materials, 2017, 7(11): doi: 10.1002/aenm.201601920.
24	黄永烽, 黄文婷, 刘文宝, 等. 锌离子电池正极材料V₂O₅的储能机理和容量衰减原因[J]. 高等学校化学学报, 2020, 41(8): 1859-1865.HUANG Y F, HUANG W T, LIU W B, et al. Mechanism of storage and capacity attenuation of V₂O₅ as cathode of zinc-ion battery[J]. Chemical Journal of Chinese Universities, 2020, 41(8): 1859-1865.
25	WAN F, NIU Z Q. Design strategies for vanadium-based aqueous zinc-ion batteries[J]. Angewandte Chemie International Edition, 2019, 58(46): 16358-16367.
26	JIN T LI H X, ZHU K J, et al. Polyanion-type cathode materials for sodium-ion batteries[J]. Chemical Society Reviews, 2020, 49(8): 2342-2377.
27	ZHANG J, LIU Y C, ZHAO X D, et al. A novel NASICON-type Na₄MnCr(PO₄)₃ demonstrating the energy density record of phosphate cathodes for sodium-ion batteries[J]. Advanced Materials, 2020, 32(11): doi: 10.1002/adma.201906348.
28	ZHENG Q, YI H M, LI X F, et al. Progress and prospect for NASICON-type Na₃V₂(PO₄)₃ for electrochemical energy storage[J]. Journal of Energy Chemistry, 2018, 27(6): 1597-1617.
29	ZHANG X X, MA J, HU P, et al. An insight into failure mechanism of NASICON-structured Na₃V₂(PO₄)₃ in hybrid aqueous rechargeable battery[J]. Journal of Energy Chemistry, 2019, 32: 1-7.
30	易红明, 吕志强, 张华民, 等. 钠离子电池钒基聚阴离子型正极材料的发展现状与应用挑战[J]. 储能科学与技术, 2020, 9(5): 1350-1369.YI H M, LYU Z Q, ZHANG H M, et al. Recent progress and application challenges in V-based polyanionic compounds for cathodes of sodium-ion batteries[J]. Energy Storage Science and Technology, 2020, 9(5): 1350-1369.
31	LI G L, YANG Z, JIANG Y, et al. Towards polyvalent ion batteries: A zinc-ion battery based on NASICON structured Na₃V₂(PO₄)₃[J]. Nano Energy, 2016, 25: 211-217.
32	HU P, ZHU T, WANG X P, et al. Aqueous Zn//Zn(CF₃SO₃)₂//Na₃V₂(PO₄)₃ batteries with simultaneous Zn²⁺/Na⁺ intercalation/de-intercalation[J]. Nano Energy, 2019, 58: 492-498.
33	HU P, YAN M Y, ZHU T, et al. Zn/V₂O₅ aqueous hybrid-ion battery with high voltage platform and long cycle life[J]. ACS Applied Materials & Interfaces, 2017, 9(49): 42717-42722.
34	HUANG S, ZHU J C, TIAN J L, et al. Recent progress in the electrolytes of aqueous zinc-ion batteries[J]. Chemistry—A European Journal, 2019, 25(64): 14480-14494.
35	WAN F, ZHANG Y, ZHANG L L, et al. Reversible oxygen redox chemistry in aqueous zinc-ion batteries[J]. Angewandte Chemie International Edition, 2019, 58(21): 7062-7067.
36	LIU S C, ZHU H, ZHANG B H, et al. Tuning the kinetics of zinc-ion insertion/extraction in V₂O₅ by in situ polyaniline intercalation enables improved aqueous zinc-ion storage performance[J]. Advanced Materials, 2020, 32(26): doi: 10.1002/adma.202001113.
37	WANG X Y, MA L W, SUN J C. Vanadium pentoxide nanosheets in-situ spaced with acetylene black as cathodes for high-performance zinc-ion batteries[J]. ACS Applied Materials & Interfaces, 2019, 11(44): 41297-41303.

CV峰	斜率	D×10^-11/cm²·s^-1
A1	0.21584	0.0032
A2	-2.09140	0.2976
C1	4.67428	1.4868
C2	-2.77174	0.5228
平均值	—	0.5776

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Na₃V₂（PO₄）₃@C用作水系锌离子电池正极材料的研究

Na₃V₂（PO₄）₃@C cathode material for aqueous zinc-ion batteries

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