阳离子交换合成钒酸镁-钒酸钠复合材料纳米线作为锂离子电池电极材料

王然然; 方东; 游昕; 易健宏

doi:10.13801/j.cnki.fhclxb.20230215.002

阳离子交换合成钒酸镁-钒酸钠复合材料纳米线作为锂离子电池电极材料

doi: 10.13801/j.cnki.fhclxb.20230215.002

昆明理工大学　材料科学与工程学院，昆明 650093

基金项目: 国家科技部重点专项(中国：2021YFE0104300；乌兹别克斯坦：MUK-2021-45)；钒钛资源综合利用国家重点实验室开放课题(2021P4FZG09A)

详细信息

通讯作者:
方东，博士，教授，博士生导师，研究方向为钒酸盐应用于锂离子电池的储能性能研究　E-mail: fangdong@kmust.edu.cn

中图分类号: TB383.1；TB33
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- 被引次数: 0
出版历程
- 收稿日期: 2022-11-11
- 修回日期: 2023-01-07
- 录用日期: 2023-01-16
- 网络出版日期: 2023-02-16
- 刊出日期: 2023-11-01

Synthesis of magnesium vanadate-sodium vanadate composite nanowires by cation exchange as electrode materials for lithium ion batteries

School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, China

Funds: Key Special Projects of the Ministry of Science and Technology (China: 021YFE0104300; Uzbekistan: MUK-2021-45); Open Project of the State Key Laboratory for Comprehensive Utilization of Vanadium and Titanium Resources (2021P4FZG09A)

摘要

摘要: 为了满足对锂离子电池性能更好和更多样化的要求，研究了用于改善电池性能的电极材料，在众多电极材料中，钒基材料的价态变化丰富和种类繁多等优点使其适用于锂离子电池电极材料。以钒酸钠纳米线阵列为前驱体，采用离子交换法合成了钛箔上的钒酸镁(MgV₂O₆)-钒酸钠(NaV₆O₁₅)复合材料。后续在空气中煅烧，温度分别为300℃和500℃，随着煅烧温度的升高，纳米线的直径变大。对所制备样品的晶体结构、化学成分和微观形貌进行了详细的表征。其中，300℃煅烧制备的钒酸镁-钒酸钠复合材料的电化学储锂性能较好，在电流密度为50 mA·g⁻¹下首次放电容量为1144 mA·h·g⁻¹，经过100次循环后的放电比容量仍有837 mA·h·g⁻¹，表现出良好的循环稳定性，较钒酸钠前驱体的储锂性能有大幅提升，为镁离子合成碱土金属钒酸盐应用于电化学储能领域的研究提供了新思路。
- 阳离子交换 /
- 水热法 /
- 钒酸镁 /
- 钒酸钠 /
- 锂离子电池
Abstract: In order to meet the requirements for better and more diversified performance of lithium-ion batteries, electrode materials for improving battery performance were studied. Among many electrode materials, vanadium-based materials are suitable for lithium-ion battery electrode materials due to their rich valence changes and various types. Magnesium vanadate (MgV₂O₆)-sodium vanadate (NaV₆O₁₅) composites on titanium foil were synthesized by ion exchange method using sodium vanadate nanowar arrays as precursors. After calcination in air, the temperature was 300℃ and 500℃, respectively. With the increase of the calcination temperature, the diameter of the nanowires became larger. The crystal structure, chemical composition and microstructure of the prepared samples were characterized in detail. Among them, the magnesium vanadate and sodium vanadate composite prepared by calcination at 300℃ had better electrochemical lithium storage performance. The first discharge capacity was 1144 mA·h·g⁻¹ at the current density of 50 mA·g⁻¹, and the specific discharge capacity was still 837 mA·h·g⁻¹ after 100 cycles, showing good cycling stability. Compared with sodium vanadate precursor, the lithium storage performance was significantly improved. It provides a new idea for the application of alkaline earth vanadate synthesized by magnesium ions in the field of electrochemical energy storage.
- cation exchange /
- hydrothermal method /
- magnesium vanadate /
- sodium vanadate /
- lithium ion battery

HTML全文

图 1 MgV₂O₆-NaV₆O₁₅复合材料的制备流程图

Figure 1. Schematic illustration for the synthesis of MgV₂O₆-NaV₆O₁₅composite material

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图 2 直接制备的Na₅V₁₂O₃₂纳米线、未退火MgV₂O₆-NaV₆O₁₅和MgV₂O₆-NaV₆O₁₅-300、MgV₂O₆-NaV₆O₁₅-500复合材料的XRD图谱

Figure 2. XRD patterns of Na₅V₁₂O₃₂ nanowires directly prepared, MgV₂O₆-NaV₆O₁₅ composites without annealing and MgV₂O₆-NaV₆O₁₅-300, MgV₂O₆-NaV₆O₁₅-500 composite material

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图 3 原始制备的Na₅V₁₂O₃₂((a), (b)) 和MgV₂O₆-NaV₆O₁₅复合物纳米线 ((c), (d))、MgV₂O₆-NaV₆O₁₅-300 ((e), (f)) 和MgV₂O₆-NaV₆O₁₅-500 ((g), (h)) 复合材料的SEM图像

Figure 3. SEM images of pristine Na₅V₁₂O₃₂ ((a), (b)) and MgV₂O₆-NaV₆O₁₅ nanowires ((c), (d)), MgV₂O₆-NaV₆O₁₅-300 ((e), (f)) and MgV₂O₆-NaV₆O₁₅-500 ((g), (h)) composites

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图 4 (a) MgV₂O₆-NaV₆O₁₅-300复合材料的SEM图像；V (b)、O (c)、Mg (d) 和Na (e) 的EDS面扫描

Figure 4. SEM image (a) and EDS element mappings of V (b), O (c), Mg (d) and Na (e) for MgV₂O₆-NaV₆O₁₅-300 composite

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图 5 MgV₂O₆-NaV₆O₁₅-300复合材料的TEM图像 ((a), (b))、EDS (c) 和HRTEM图像 ((d), (e)) 及傅里叶变换图(FFT) ((d₁), (d₂)) 和反傅里叶变换图(IFFT) ((e₁), (e₂))

Figure 5. TEM images ((a), (b)), EDS images (c), HRTEM images ((d), (e)) of MgV₂O₆-NaV₆O₁₅-300 composite; Regions reveal the existence of MgV₂O₆ and V₂O₅ by fast fourier transform (FFT) ((d₁), (d₂)) and inverse fast fourier transform (IFFT) ((e₁), (e₂)) methods, respectively

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图 6 MgV₂O₆-NaV₆O₁₅-300复合材料的全谱 (a)、Mg1s (b)、Na1s (c)、V2p (d) 和O1s (d) 的高分辨率XPS图谱

Figure 6. A survey (a), and high resolution XPS spectra of the Mg1s (b), Na1s (c), V2p (d) and O1s (d) of the MgV₂O₆-NaV₆O₁₅-300 composites

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图 7 电极在0.01~3 V电位范围内的动力学分析：(a) MgV₂O₆-NaV₆O₁₅-300电极前3圈CV曲线(0.1 mV·s⁻¹)；(b) 钒酸钠前驱体前3圈CV曲线(扫速: 0.1 mV·s⁻¹)； (c) MgV₂O₆-NaV₆O₁₅-300电极不同扫描速率下的CV曲线(0.2~1.0 mV·s⁻¹)；(d) MgV₂O₆-NaV₆O₁₅-300电极每个氧化还原峰的lgi和lgv图

i—Peak current; v—Sweep rate

Figure 7. Kinetic analysis electrode within the potential range of 0.01-3 V: (a) CV curves of the first three turns of MgV₂O₆-NaV₆O₁₅-300 electrode (0.1 mV·s⁻¹); (b) CV curves of the first three turns of Na₅V₁₂O₃₂ electrode (0.1 mV· s⁻¹); (c) CV curves in different scan rates of MgV₂O₆-NaV₆O₁₅-300 electrode (0.2-1.0 mV·s⁻¹); (c) lgi vs lgv plots at each redox peak of MgV₂O₆-NaV₆O₁₅-300 electrode

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图 8 电化学性能：(a) 充放电；(b) 长周期；(c) 速率能力；(d) 电化学阻抗谱(EIS)；(e) Na₅V₁₂O₃₂和MgV₂O₆-NaV₆O₁₅-300电极Warburg阻抗的线性拟合

R_s—Ohmic resistance of the electrolyte and electrode; R_ct—Charge-transfer resistance; Z_w—Warburg impedance; C_dl—Double layer capacitor; ω—Angular frequency

Figure 8. Electrochemical performance: (a) Charge-discharge; (b) Long cycle; (c) Rate capability; (d) Electrochemical impedance spectra (EIS); (e) Linear fitting of the Warburg impedance for Na₅V₁₂O₃₂ and MgV₂O₆-NaV₆O₁₅-300 electrodes

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表 1 不同温度处理的MgV₂O₆-NaV₆O₁₅电极材料

Table 1. MgV₂O₆-NaV₆O₁₅ electrode materials treated at different temperatures

Sample Treated temperature/℃

MgV₂O₆-NaV₆O₁₅-300 300

MgV₂O₆-NaV₆O₁₅-500 500

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