二氧化钒粉体的高效制备工艺与优化研究

陈铭帝; 韩育席; 伍滨和

doi:10.7513/j.issn.1004-7638.2026.03.002

二氧化钒粉体的高效制备工艺与优化研究

doi: 10.7513/j.issn.1004-7638.2026.03.002

东华大学物理学院, 上海201620

基金项目: 国家自然科学基金（61975029）；上海市自然科学基金（24ZR1402600）；2024年度大学生创新创业项目（202410255082）。

详细信息

作者简介:
陈铭帝，2000年出生，男，山东泰安人，硕士研究生，研究方向：微纳光电材料与器件，E-mail：308995935@qq.com

通讯作者:
伍滨和，1976年出生，男，重庆石柱人，博士，研究员，研究方向：微纳光电材料与器件，E-mail：bhwu@dhu.edu.cn

中图分类号: TF841.3,TB383
计量
- 文章访问数: 2
- HTML全文浏览量: 0
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2025-04-21
- 录用日期: 2025-05-30
- 修回日期: 2025-05-13
- 刊出日期: 2026-06-29

The investigation of efficient preparation process and optimization of vanadium dioxide powder

College of Physics, Donghua University, Shanghai 201620, China

摘要

摘要: VO₂粉体具有比表面积大，吸附能力强和可逆绝缘-金属相变等特点，在气体传感、智能窗和光电开关等领域具有重要应用潜力。针对传统材料制备方法存在制备周期长、工艺参数不稳定等局限，以V₂O₅为钒源，采用优化的溶胶-凝胶法结合退火工艺制备了M相VO₂粉体。改进了前驱体制备工艺，缩短了制备周期，由以往的大于24 h缩短至8 h以内；采用静态空气氧化的方法，避免了产物的飞散；采用差示扫描量热法（DSC）的相变潜热作为材料性能的评价指标，系统研究和优化了退火温度和气压两个关键工艺参数，确定最佳退火温度为450 ℃，空气压强为1.5×10⁴ Pa。研究结果实现了M相VO₂粉体的高效、稳定制备，有助于该相变材料在光电功能器件中的进一步应用。
- VO₂粉体 /
- 溶胶—凝胶法 /
- 退火工艺 /
- 工艺优化 /
- M相VO₂ /
- 相变潜热
Abstract: VO₂ powder features high specific surface area, strong adsorption capability, and reversible insulator–metal phase transition. These properties endow it with significant application potential in gas sensing, smart windows, and optoelectronic switches and other fields. To address the limitations of conventional fabrication routes, such as long preparation cycle and unstable process parameters, monoclinic-phase (M-phase) VO₂ powder was synthesized using V₂O₅ as vanadium source via an optimized sol–gel method combined with annealing process. The precursor preparation process was improved, resulting in a significant reduction in synthesis time, from over 24 hours to less than 8 hours. Static air oxidation was employed to prevent product dispersion during synthesis. The latent heat of the phase transition, as measured by differential scanning calorimetry (DSC), was employed as the performance evaluation indicator for material evaluation. Using this parameter, two critical processing variables, annealing temperature and ambient pressure, were systematically investigated and optimized. The optimal annealing conditions were determined to be 450 ℃ and 1.5 × 10⁴ Pa. The results of this study enabled the efficient and stable synthesis of monoclinic-phase (M-phase) VO₂ powder, facilitating further practical application of this phase-transition material in optoelectronic functional devices.
- VO₂ powder /
- sol-gel method /
- annealing process /
- process optimization /
- M-phase VO₂ /
- latent heat of phase transition

HTML全文

图 1 前驱体制备流程

Figure 1. Precursor preparation flowchart

下载: 全尺寸图片幻灯片

图 2 样品形貌

(a)前驱体粉末；(b) M相二氧化钒粉末

Figure 2. Sample morphology

下载: 全尺寸图片幻灯片

图 3 退火环境的优化示意

Figure 3. Optimization diagram of annealing environment

下载: 全尺寸图片幻灯片

图 4 前驱体的TGA曲线

Figure 4. TGA curves of the precursor

下载: 全尺寸图片幻灯片

图 5 不同退火温度和气压下样品的相变潜热

Figure 5. Phase transition latent heat of the samples under different annealing temperatures and pressures

下载: 全尺寸图片幻灯片

图 6 不同退火温度下样品的XRD谱

(a) 450 ℃; (b) 500 ℃; (c) 550 ℃; (d) 三个不同退火温度下的对比

Figure 6. XRD spectra of samples annealed at different temperatures

下载: 全尺寸图片幻灯片

图 7 不同退火温度下样品的DSC曲线

(a) 450 ℃; (b) 500 ℃; (c) 550 ℃; (d) 三个不同退火温度下的对比

Figure 7. DSC curves of samples annealed at different temperatures

下载: 全尺寸图片幻灯片

图 8 不同气压下样品的XRD谱

(a) 1.2×10⁴ Pa; (b) 1.5×10⁴ Pa; (c) 2.0×10⁴ Pa; (d) 三个不同气压下的对比

Figure 8. XRD spectra of samples at different gas pressures

下载: 全尺寸图片幻灯片

图 9 不同气压下样品的DSC曲线

(a) 1.2×10⁴ Pa; (b) 1.5×10⁴ Pa; (c) 2.0×10⁴ Pa; (d) 三个不同气压下的对比

Figure 9. DSC curves of samples at different gas pressures

下载: 全尺寸图片幻灯片

图 10 VO₂粉体的XRD谱

Figure 10. XRD spectra of VO₂ powder

下载: 全尺寸图片幻灯片

图 11 VO₂粉体的XPS谱

(a) 全谱图；(b) V2p峰的高分辨率光谱

Figure 11. XPS spectra of VO₂ powder

下载: 全尺寸图片幻灯片

图 12 VO₂粉体的FTIR图谱

Figure 12. FTIR spectra of VO₂ powder

下载: 全尺寸图片幻灯片

参考文献(26)

[1]	ZHANG Y, XIONG W, CHEN W, et al. Recent progress on vanadium dioxide nanostructures and devices: Fabrication, properties, applications and perspectives[J]. Nanomaterials, 2021, 11(2): 338. doi: 10.3390/nano11020338
[2]	ROGERS K D. An X-ray diffraction study of semiconductor and metallic vanadium dioxide[J]. Powder Diffraction, 1993, 8(4): 240-244. doi: 10.1017/S0885715600019448
[3]	YAZDI S T, MOUSAVI M, KHORRAMI G H. Effect of Co-doping in V₂O₅ nanoparticles synthesized via a gelatin-based sol-gel method[J]. Materials Today Communications, 2021, 26: 101955. doi: 10.1016/j.mtcomm.2020.101955
[4]	ZHAO X, YAO W, SUN J, et al. Thermochromic composite film of VO₂ nanoparticles and [(C₂H₅)2NH₂]2NiBr₄@SiO₂ nanospheres for smart window applications[J]. Chemical Engineering Journal, 2023, 460: 141715. doi: 10.1016/j.cej.2023.141715
[5]	DU J J, LIU J T, ZHU J, et al. Preparation and properties of V_1-xTb_xO₂ (x=0, 1, 2, 3, 4) (M) thin films[J]. Iron Steel Vanadium Titanium, 2024, 45(6): 80-86. (杜金晶, 刘景田, 朱军, 等. V_1-xTb_xO₂(x=0, 1, 2, 3, 4)(M)薄膜的制备及其性能研究[J]. 钢铁钒钛, 2024, 45(6): 80-86. DU J J, LIU J T, ZHU J, et al. Preparation and properties of V_1-xTb_xO₂ (x=0, 1, 2, 3, 4) (M) thin films[J]. Iron Steel Vanadium Titanium, 2024, 45（6）: 80-86.
[6]	XU Z, YANG Q, XIE C, et al. Structure, luminescence properties and photocatalytic activity of europium doped-TiO₂ nanoparticles[J]. Journal of Materials Science, 2005, 40(6): 1539-1541. doi: 10.1007/s10853-005-0599-6
[7]	LU Y C, HSUEH C H. Subwavelength VO₂ nanoparticle films for smart window applications[J]. ACS Applied Nano Materials, 2022, 5(2): 2923-2934. doi: 10.1021/acsanm.2c00138
[8]	PAN G, YIN J, JI K, et al. Synthesis and thermochromic property studies on W doped VO₂ films fabricated by sol-gel method[J]. Scientific Reports, 2017, 7(1): 6132. doi: 10.1038/s41598-017-05229-9
[9]	SHI Q, HUANG W, ZHANG Y, et al. Giant phase transition properties at terahertz range in VO₂ films deposited by sol–gel method[J]. ACS Applied Materials & Interfaces, 2011, 3(9): 3523-3527. doi: 10.1021/am200734k
[10]	INOMATA N, USUDA T, YAMAMOTO Y, et al. Effects of temperature and doping concentration on the piezoresistive property of vanadium dioxide thin film[J]. Sensors and Actuators A: Physical, 2022, 346: 113823. doi: 10.1016/j.sna.2022.113823
[11]	OUTON J, BLANCO E, DOMINGUEZ M, et al. Tracking the optical constants of porous vanadium dioxide thin films during metal–insulator transition: Influence of processing conditions on their application in smart glasses[J]. Applied Surface Science, 2022, 580: 152228. doi: 10.1016/j.apsusc.2021.152228
[12]	WANG N, MAGDASSI S, MANDLER D, et al. Simple sol–gel process and one-step annealing of vanadium dioxide thin films: synthesis and thermochromic properties[J]. Thin Solid Films, 2013, 534: 594-598. doi: 10.1016/j.tsf.2013.01.074
[13]	WU J, HUANG W, SHI Q, et al. Effect of annealing temperature on thermochromic properties of vanadium dioxide thin films deposited by organic sol–gel method[J]. Applied Surface Science, 2013, 268: 556-560. doi: 10.1016/j.apsusc.2013.01.007
[14]	LIVAGE J. Sol-gel processes[J]. Current Opinion in Solid State and Materials Science, 1997, 2(2): 132-138. doi: 10.1007/978-3-319-19454-7_114-1
[15]	LI G, CHAO K, PENG H, et al. Low-valent vanadium oxide nanostructures with controlled crystal structures and morphologies[J]. Inorganic Chemistry, 2007, 46(14): 5787-5790. doi: 10.1021/ic070339n
[16]	TIMMERS K, CHOTE A, LEUFKENS L, et al. Hydrothermal synthesis of monoclinic VO₂ microparticles without use of hazardous reagents: a key role for the W-dopant[J]. Inorganic Chemistry, 2024, 63(12): 5400-5413. doi: 10.1021/acs.inorgchem.3c03999
[17]	YANG X, ZOU J. Hydrothermal synthesis and phase transition properties of W-doped nano M-phase VO₂[J]. Iron Steel Vanadium Titanium, 2022, 43(6): 24-30. (杨雪, 邹建. W掺杂纳米M相VO₂的水热合成及其相变性能[J]. 钢铁钒钛, 2022, 43(6): 24-30. YANG X, ZOU J. Hydrothermal synthesis and phase transition properties of W-doped nano M-phase VO₂[J]. Iron Steel Vanadium Titanium, 2022, 43（6）: 24-30.
[18]	ZHOU Q, LÜ W, QIU Q, et al. Boron doped M-phase VO₂ nanoparticles with low metal-insulator phase transition temperature for smart windows[J]. Ceramics International, 2020, 46(4): 4786-4794. doi: 10.1016/j.ceramint.2019.10.211
[19]	LI M, FANG C, CHENG Y, et al. A facile pathway to fabricate VO₂ (M) nanoparticles via sol-gel method for flexible thermochromic films with efficient infrared stealth[J]. Vacuum, 2024, 221: 112885. doi: 10.1016/j.vacuum.2023.112885
[20]	YIN X L, ZENG Z H, GAO R R, et al. Preparation of M-phase vanadium dioxide ultrafine particles by thermal decomposition under inert atmosphere[J]. Iron Steel Vanadium Titanium, 2022, 43(1): 1-6. (尹翔鹭, 曾泽华, 高荣荣, 等. 惰性气氛下热分解法制备M相二氧化钒超细颗粒[J]. 钢铁钒钛, 2022, 43(1): 1-6. YIN X L, ZENG Z H, GAO R R, et al. Preparation of M-phase vanadium dioxide ultrafine particles by thermal decomposition under inert atmosphere[J]. Iron Steel Vanadium Titanium, 2022, 43（1）: 1-6.
[21]	BUKHARI S A, KUMAR S, KUMAR P, et al. The effect of oxygen flow rate on metal–insulator transition (MIT) characteristics of vanadium dioxide (VO₂) thin films by pulsed laser deposition (PLD)[J]. Applied Surface Science, 2020, 529: 146995. doi: 10.1016/j.apsusc.2020.146995
[22]	KUMAR M, SINGH J P, CHAE K H, et al. Annealing effect on phase transition and thermochromic properties of VO₂ thin films[J]. Superlattices and Microstructures, 2020, 137: 106335. doi: 10.1016/j.spmi.2019.106335
[23]	PANBURANA P, CHATRAPHORN S, KITTIWATANAKUL S. Effect of annealing conditions on VO₂ thin films prepared by sol-gel method[C]// Journal of Physics: Conference Series. IOP Publishing, 2023, 2431(1): 012055.
[24]	ZHANG H, WU Z, WU X, et al. Transversal grain size effect on the phase-transition hysteresis width of vanadium dioxide films comprising spheroidal nanoparticles[J]. Vacuum, 2014, 104: 47-50. doi: 10.1016/j.vacuum.2014.01.003
[25]	NARAYAN J, BHOSLE V M. Phase transition and critical issues in structure-property correlations of vanadium oxide[J]. Journal of Applied Physics, 2006, 100(10).
[26]	CHEN Y, ZHANG S, KE F, et al. Pressure–temperature phase diagram of vanadium dioxide[J]. Nano Letters, 2017, 17(4): 2512-2516. doi: 10.1021/acs.nanolett.7b00233