钒酸钠中钠离子脱嵌诱导结构相变的电子显微学表征

钒酸钠中钠离子脱嵌诱导结构相变的电子显微学表征

杜文龙^#，赵培丽^#，赵  振，王怀远，唐  真，贾双凤，郑  赫^*，王建波^*

（1.武汉大学物理科学与技术学院，电子显微镜中心，人工微结构教育部重点实验室和高等研究院，湖北 武汉 430072；2. 武汉大学科研公共服务条件平台，湖北 武汉 430072）

摘  要  本文采用溶胶-凝胶法结合固相烧结法制备了钒酸钠纳米线，通过X射线衍射学和电子显微学确定了制备产物为层状结构Na_1.25V₃O₈和通道结构NaV₆O₁₅。利用电子束辐照诱导钠离子脱嵌对Na_1.25V₃O₈和NaV₆O₁₅的结构稳定性进行了研究。结果表明，Na_1.25V₃O₈和NaV₆O₁₅经电子束辐照后均会转化成岩盐结构的VO。论文结果有助于理解钠离子脱嵌对钠离子电池正极材料结构稳定性的影响机理，为高性能钠离子电池的复杂设计提供参考。

关键词   钒酸钠；电子束辐照；相变；透射电子显微学（TEM）

中图分类号:TG115. 21⁺ 5. 3; O766⁺.1; O799; O722⁺.4; O739; TN16      文献标识码: A     doi：10.3969/j.issn.1000-6281.2024.05.002

Electron microscopy characterization of structural evolution caused by sodium ion migration in sodium vanadate

DU Wenlong^1#, ZHAO Peili^1#, ZHAO Zhen¹,WANG Huaiyuan¹, TANG Zhen¹, JIA Shuangfeng¹, ZHENG He^1*, WANG Jianbo^1，2*

（1. School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Institute for Advanced Studies, Wuhan University, Wuhan Hubei 430072; 2. Core Facility of Wuhan University, Wuhan Hubei 430072, China）

Abstract   This study highlighted the synthesis and structural evolution of sodium vanadate nanowires using a sol-gel method combined with solid-state sintering. The materials were identified as layered Na₁.₂₅V₃O₈ and tunnel-structured NaV₆O₁₅ through X-ray diffraction (XRD) and transmission electron microscopy (TEM). The structural evolutions due to sodium ion deintercalation induced by e-beam irradiation was investigated. Both Na₁.₂₅V₃O₈ and NaV₆O₁₅ transformed into a rock salt-structured vanadium oxide (VO) after e-beam irradiation. This study contributes to the fundamental understanding of the material science involved in sodium-ion batteries, which is vital for advancing energy storage technologies.

Keywords   sodium vanadate; electron beam irradiation; phase transition; transmission electron microscopy (TEM)

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[1]    ZHU G, TIAN X, TAI H-C, et al. Rechargeable Na/Cl₂ and Li/Cl₂ batteries [J]. Nature, 2021, 596(7873): 525-530.

[2]    GUO Y-J, WANG P-F, NIU Y-B, et al. Boron-doped sodium layered oxide for reversible oxygen redox reaction in Na-ion battery cathodes [J]. Nature Communications, 2021, 12(1): 5267.

[3]    WANG D, WEI C, LIN M, et al. Advanced rechargeable aluminium ion battery with a high-quality natural graphite cathode [J]. Nature Communications, 2017, 8(8): 14283.

[4]    GIORDANI V, TOZIER D, UDDIN J, et al. Rechargeable-battery chemistry based on lithium oxide growth through nitrate anion redox [J]. Nature Chemistry, 2019, 11(12): 1133-1138.

[5]    CHI X, LI M, DI J, et al. A highly stable and flexible zeolite electrolyte solid-state Li–air battery [J]. Nature, 2021, 592(7855): 551-557.

[6]    ETACHERI V, MAROM R, ELAZARI R, et al. Challenges in the development of advanced Li-ion batteries: A review [J]. Energy & Environmental Science, 2011, 4(9): 3243.

[7]    LIN M-C, GONG M, LU B, et al. An ultrafast rechargeable aluminium-ion battery [J]. Nature, 2015, 520(7547): 324-328.

[8]    LI M, LU J, CHEN Z, et al. 30 years of lithium‐ion batteries [J]. Advanced Materials, 2018, 30(33): 1800561.

[9]    YE Y, CHOU L-Y, LIU Y, et al. Ultralight and fire-extinguishing current collectors for high-energy and high-safety lithium-ion batteries [J]. Nature Energy, 2020, 5(10): 786-793.

[10] LI P, JIANG R, ZHAO L, et al. Cation defect mediated phase transition in potassium tungsten bronze [J]. Inorganic Chemistry, 2021, 60(23): 18199-18204.

[11] ALI G, ISLAM M, JUNG H-G, et al. Probing the sodium insertion/extraction mechanism in a layered NaVO₃ anode material [J]. ACS Applied Materials & Interfaces, 2018, 10(22): 18717-18725.

[12] CAO Y, YE Q, WANG F, et al. A new triclinic phase Na₂Ti₃O₇ anode for sodium‐ion battery [J]. Advanced Functional Materials, 2020, 30(39): 2003733.

[13] YAO L, ZOU P, WANG C, et al. High‐entropy and superstructure‐stabilized layered oxide cathodes for sodium‐ion batteries [J]. Advanced Energy Materials, 2022, 12(41): 2201989.

[14] MA Y, JI S, ZHOU H, et al. Synthesis of novel ammonium vanadium bronze (NH₄)_0.6V₂O₅ and its application in Li-ion battery [J]. RSC Advances, 2015, 5(110): 90888-90894.

[15] MERUM D, NALLAPUREDDY R R, PALLAVOLU M R, et al.Pseudocapacitive performance of freestanding Ni₃V₂O₈ nanosheets for high energy and power density asymmetric supercapacitors [J]. ACS Applied Energy Materials, 2022, 5(5): 5561-5578.

[16] BADDOUR-HADJEAN R,BOUDAOUD A, BACH S, et al. A comparative insight of potassium vanadates as positive electrode materials for Li batteries: Influence of the long-range and local structure [J]. Inorganic Chemistry, 2014, 53(3): 1764-1772.

[17] SONG X, LI X, SHAN H, et al. V-O-C bonding of heterointerface boosting kinetics of free‐standing Na₅V₁₂O₃₂ cathode for ultralong lifespan sodium‐ion batteries [J]. Advanced Functional Materials, 2023, 2303211.

[18] CHEN M, LIU Q, HU Z, et al. Designing advanced vanadium‐based materials to achieve electrochemically active multielectron reactions in sodium/potassium‐ion batteries [J]. Advanced Energy Materials, 2020, 10(42): 2002244.

[19] DONG Y, LI S, ZHAO K, et al. Hierarchical zigzag Na_1.25V₃O₈ nanowires with topotactically encoded superior performance for sodium-ion battery cathodes [J]. Energy & Environmental Science, 2015, 8(4): 1267-1275.

[20] GUO X, FANG G, ZHANG W, et al. Mechanistic insights of Zn²⁺ storage in sodium vanadates [J]. Advanced Energy Materials, 2018, 8(27): 101819.

[21] XIE D, HU F, YU X, et al. High-performance Na_1.25V₃O₈ nanosheets for aqueous zinc-ion battery by electrochemical induced de-sodium at high voltage [J]. Chinese Chemical Letters, 2020, 31(9): 2268-2274.

[22] LIANG S, CHEN T, PAN A, et al. Synthesis of Na_1.25V₃O₈ nanobelts with excellent long-term stability for rechargeable lithium-ion batteries [J]. ACS Applied Materials & Interfaces, 2013, 5(22): 11913-11917.

[23] SOUNDHARRAJAN V, SAMBANDAM B, KIM S, et al. Na₂V₆O₁₆·3H₂O barnesite nanorod: An open door to display a stable and high energy for aqueous rechargeable Zn-ion batteries as cathodes [J]. Nano Letters, 2018, 18(4): 2402-2410.

[24] HARTUNG S, BUCHER N, FRANKLIN J B, et al. Mechanism of Na⁺ insertion in alkali vanadates and its influence on battery performance [J]. Advanced Energy Materials, 2016, 6(9): 1502336.

[25] ZHUANG H, XU Y, ZHAO P. Effect of crystallinity on capacity and cyclic stability of Na_1.1V₃O_7.9 nanoplates as lithium-ion cathode materials [J]. Journal of Solid State Electro-chemistry, 2020, 24(1): 217-223.

[26] OSMAN S, ZUO S, XU X, et al. Freestanding sodium vanadate/carbon nanotube composite cathodes with excellent structural stability and high rate capability for sodium-ion batteries [J]. ACS Applied Materials & Interfaces, 2021, 13(1): 816-826.

[27] HE P, ZHANG G, LIAO X, et al. Sodium ion stabilized vanadium oxide nanowire cathode for high-performance zinc-ion batteries [J]. Advanced Energy Materials, 2018, 8(10): 1702463.

[28] SUN D, JIN G, WANG H, et al. Aqueous rechargeable lithium batteries using NaV₆O₁₅ nanoflakes as high performance anodes [J]. Journal of Materials Chemistry A, 2014, 2(32): 12999-13005.

[29] WANG P-P, XU C-Y, MA F-X, et al. In situ soft-chemistry synthesis of β-Na_0.33V₂O₅ nanorods as high-performance cathode for lithium-ion batteries [J]. RSC Advances, 2016, 6(107): 105833-105839.

[30] YANG K, FANG G, ZHOU J, et al. Hydrothermal synthesis of sodium vanadate nanobelts as high-performance cathode materials for lithium batteries [J]. Journal of Power Sources, 2016, 325: 383-390.

[31] SCHINDLER M, HAWTHORNE F C, ALEXANDER M A, et al. Na-Li-[V₃O₈] insertion electrodes: structures and diffusion pathways [J]. Journal of Solid State Chemistry, 2006, 179(8): 2616-2628.

[32] SONG Y, WANG T, ZHU J, et al. Recent advances in LiV₃O₈ as anode material for aqueous lithium-ion batteries: Syntheses, modifications, and perspectives [J]. Journal of Alloys and Compounds, 2022, 897: 163065.

[33] WANG X, LIU Q, WANG H, et al. PVP-modulated synthesis of NaV₆O₁₅ nanorods as cathode materials for high-capacity sodium-ion batteries [J]. Journal of Materials Science, 2016, 51(19): 8986-8994.

[34] YUAN S, ZHAO Y,WANG Q. Layered Na₂V₆O₁₆ nanobelts as promising cathode and symmetric electrode for Na-ion batteries with high capacity [J]. Journal of Alloys and Compounds, 2016, 688: 55-60.

[35] YUAN S, LIU Y B, XU D, et al. Pure single‐crystalline Na_1.1V₃O_7.9 nanobelts as superior cathode materials for rechargeable sodium‐ion batteries [J]. Advanced Science, 2015, 2(3): 1400018.

[36] 陈树林, 高鹏. 原位电子显微学探索固体中的离子迁移行为[J]. 物理, 2019, 48(3): 168-179.

[37] JIANG R, LI P, GUAN X, et al. Na⁺ migration mediated phase transitions induced by electric field in the framework structured tungsten bronze [J]. The Journal of Physical Chemistry Letters, 2023, 14(13): 3152-3159.

[38] 吕英豪, 李露颖, 刘辉辉, 等. 钾钨青铜材料中的W空位有序[J]. 电子显微学报, 2018, 37(6): 571-577.

[39] 王严, 文广玉, 李雷, 等. 电子束诱导WO_2.72单晶生长与还原[J]. 电子显微学报, 2019, 38(6): 600-607.

[40] 王思铭, 彭华雨, 蒋仁辉, 等. 电子束辐照α-MoO₃原子尺度结构演变的原位表征[J]. 电子显微学报,2021, 40(5): 496-504.

[41] MENG Q, ZHUANG Y, JIANG R, et al. Atomistic observation of desodiation-induced phase transition in sodium tungsten bronze [J]. The Journal of Physical Chemistry Letters, 2021, 12(12): 3114-3119.

[42] 李敏敏, 曹凡, 贾双凤, 等. 电子束辐照制备钼酸锰纳米材料[J]. 电子显微学报, 2017, 36(4): 328-334.

[43] 马龙辉,孟爽, 蒋仁辉, 等. α-Fe₂O₃的原子尺度界面结构与演变[J]. 电子显微学报, 2021, 40(5): 529-536.

[44] CAO F, ZHENG H, JIA S, et al. Atomistic observation of phase transitions in calcium sulfates under electron irradiation [J]. The Journal of Physical Chemistry C, 2015, 119(38): 22244-22248.

[45] LU P, YAN P, ROMERO E, et al. Observation of electron-beam-induced phase evolution mimicking the effect of the charge-discharge cycle in Li-rich layered cathode materials used for Li ion batteries [J]. Chemistry of Materials, 2015, 27(4): 1375-1380.

[46] LIN F, MARKUS I M, DOEFF M M, et al. Chemical and structural stability of lithium-ion battery electrode materials under electron beam [J]. Scientific Reports, 2014, 4(1): 5694.

[47] 张锦平. 结构相变中晶体学群论问题的讨论[J]. 电子显微学报, 2020, 39(5): 567-576.

[48] LI S, LIU Z, YANG L, et al. Anionic redox reaction and structural evolution of Ni-rich layered oxide cathode material [J]. Nano Energy, 2022, 98: 107335.