W掺杂纳米M相VO<sub>2</sub>的水热合成及其相变性能

杨雪; 邹建

doi:10.7513/j.issn.1004-7638.2022.06.004

W掺杂纳米M相VO₂的水热合成及其相变性能

doi: 10.7513/j.issn.1004-7638.2022.06.004

杨雪,
邹建

西南大学化学化工学院, 重庆 400715

基金项目: 重庆市基础与前沿研究计划项目（cstc2016jcyjA0027）；中央高校基本科研业务费项目（XDJK2020B026）

详细信息

作者简介:
杨雪，1998年出生，女，海南琼海人，硕士研究生，研究方向：无机材料，E-mail：yangxue98@email.swu.edu.cn

中图分类号: TF841.3,TB34
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出版历程
- 收稿日期: 2022-10-26
- 刊出日期: 2023-01-13

Hydrothermal synthesis and phase transformation properties of W-doped VO₂(M) nanoparticles

Yang Xue,
Zou Jian

School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China

摘要

摘要: 以偏钒酸铵为钒源，水合肼为还原剂，偏钨酸铵为掺杂剂，采用一步水热法在280 ℃制备了掺W量（原子分数表示）从0到2.0%的VO₂粉体，并将其加入到聚氨酯中，制备VO₂/PU复合薄膜。通过XRD、TEM、XPS、DSC对合成的样品进行了物相组成、形貌、元素价态和相变性能分析，利用紫外-可见-近红外光谱仪测定了薄膜的透射率。结果表明：随着W掺杂量从0增加到2.0%，二氧化钒升温时的相变温度从61.8 ℃降低至15 ℃。基于掺杂1.0%的二氧化钒粉体制备的VO₂/PU复合薄膜，ΔT_sol可达11.7%，基本满足智能窗的实际应用要求。
- 二氧化钒 /
- 一步水热法 /
- 钨掺杂 /
- 相变性能 /
- 薄膜
Abstract: In this paper, using ammonium metavanadate as the vanadium source, hydrazine monohydrate as the reducing agent and ammonium metatungstate as the dopant, the VO₂ powder doped with W from 0.0 to 2.0 at% was prepared by one-step hydrothermal method at 280 ℃, and was added to polyurethane to prepare VO₂/PU composite films. XRD, TEM, XPS and DSC were used to analyze the phase composition, morphology, element valence state and phase transformation performance of the synthesized samples. The transmittance of the films was measured by UV-Vis-NIR spectrometer. The results show that with W doping increasing from 0.0 to 2.0 at%, the phase transition temperature of vanadium dioxide decreases from 61.8 ℃ to 15 ℃. The composite film based on 1 at% W-doped vanadium dioxide powder shows a good solar modulating ability (ΔT_sol = 11.7%), which meets the practical application requirements of intelligent windows.
- vanadium dioxide /
- one-step hydrothermal treatment /
- W-doped /
- phase transformation properties /
- films

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图 1 280 ℃水热合成不同掺杂量二氧化钒的XRD谱

Figure 1. XRD patterns of VO₂ with different doping levels synthesized by hydrothermal method at 280 ℃

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图 2 不同掺杂量VO₂ 纳米颗粒的TEM图像及其相应的晶格分辨HRTEM图像

(a)、(d)未掺杂；(b)、(e)掺杂1.0 %；(c)、(f)掺杂2.0 %

Figure 2. TEM images and their corresponding lattice-resolved HRTEM images of VO₂ NPs with different W-doping contents

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图 3 掺钨1.0% VO₂样品的XPS谱

Figure 3. XPS spectrum of 1.0% W-doped VO₂ sample

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图 4 不同掺钨量的二氧化钒样品的DSC曲线和T_c-heating与掺杂量的线性拟合

Figure 4. DSC curves and T_c-heating data with linear fitting of the obtained VO₂ with different W-doping contents

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图 5 VO₂/PU 复合薄膜在20 ℃（实线）和100 ℃（虚线）的透射光谱

Figure 5. Transmission spectra of VO₂/PU composite films at the temperature of 20 ℃(solid line) and 100 ℃ (dash line) respectively

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表 1 具有不同掺钨量的样品的金属-绝缘体相变温度汇总

Table 1. Summary of metal insulator transition temperatures for samples with different W-doping concentrations

掺钨量/%	T_c-heating /℃	T_c-cooling /℃	T_c/℃	热滞宽度/℃	ΔH−_heating/ (J·g⁻¹)	ΔH−_cooling/ (J·g⁻¹)	ΔH/(J·g⁻¹)
0	61.8	33.1	47.5	28.7	30.19	−32.31	31.25
0.5	49.5	27.7	38.6	21.8	25.66	−26.22	25.94
1.0	40.3	19.4	29.9	20.9	23.36	−22.14	22.75
1.5	30.4	9.1	19.8	21.3	17.82	−16.39	17.11
2.0	25.3	4.7	15	20.6	13.96	−15.13	14.55
注：ΔH=(ΔH−_heating+\|ΔH−_cooling\|)/2 ； T_c= (T_c-heating + T_c-cooling)/2。

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表 2 不同掺钨量VO₂薄膜的热致变色性能

Table 2. Thermochromic properties of VO₂ films with different W-doping concentrations

掺钨量/%	涂膜浆料体积/mL	T_sol /%		T_lum /%		ΔT_sol /%
掺钨量/%	涂膜浆料体积/mL	20 ℃	100 ℃	20 ℃	100 ℃	ΔT_sol /%
0	0.8	57.5	43.7	53.0	52.3	13.8
0.5	0.8	53.6	45.3	51.2	54.6	8.3
	0.4+0.4+0.4	39.4	26.7	32.4	34.1	12.7
1.0	0.8	49.8	42.7	46.8	49.5	7.1
	0.4+0.4+0.4	41.8	30.1	37.1	37.9	11.7
1.5	0.8	43.5	42.4	41.4	46.3	1.1
	0.4+0.4+0.4	34.5	31.4	31.6	35.9	3.1

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