二氧化钒-聚二乙炔热致变色复合薄膜及其调光性能

王彬彬; 高阳; 杨帅军; 徐慧妍; 聂永; 蒋绪川

doi:10.13801/j.cnki.fhclxb.20221028.002

二氧化钒-聚二乙炔热致变色复合薄膜及其调光性能

doi: 10.13801/j.cnki.fhclxb.20221028.002

王彬彬^1,,
高阳¹,
杨帅军^1, ,,
徐慧妍¹,
聂永¹,
蒋绪川^{1, 2, ,}

1.
济南大学　智能材料与工程研究院，济南 250022
2.
济南大学　材料科学与工程学院，济南 250022

基金项目: 国家自然科学基金 (21805045)；济南大学科技计划项目(XKY2067)；济南大学学科重大课题

详细信息

通讯作者:
杨帅军，博士，讲师，硕士生导师，研究方向为有机-无机复合功能材料　E-mail: ism_yangsj@ujn.edu.cn

蒋绪川，博士，教授，博士生导师，研究方向为光、热、电、磁等外界刺激响应型无机功能材料；隔热节能玻璃的工程化　E-mail: ism_jiangxc@ujn.edu.cn

中图分类号: TB381；TB332
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出版历程
- 收稿日期: 2022-07-07
- 修回日期: 2022-10-18
- 录用日期: 2022-10-22
- 网络出版日期: 2022-10-31
- 刊出日期: 2023-06-15

Vanadium dioxide-polydiacetylene thermochromic composite films and their solar regulation properties

WANG Binbin^1
,,
GAO Yang¹,
YANG Shuaijun^{1
, ,},
XU Huiyan¹,
NIE Yong¹,
JIANG Xuchuan^{1, 2
, ,}

1.
Institute for Smart Materials & Engineering, University of Jinan, Jinan 250002, China
2.
School of Materials Science & Engineering, University of Jinan, Jinan 250002, China

Funds: National Natural Science Foundation of China (21805045); Science and Technology Program of University of Jinan (XKY2067); The Major Subject Project of the University of Jinan

摘要

摘要: 热致相变二氧化钒(VO₂)具有良好的近红外光调制能力，被广泛应用于智能窗领域，但在实际应用中VO₂基智能窗仍面临诸多挑战，其中VO₂薄膜不太美观的棕黄色及相变前后无可视的颜色变化是限制其应用的重要因素。为解决上述问题，本文将具有可逆颜色变化(由蓝到红)的聚二乙炔(PDA-1)与VO₂复合，成功制备了具有双层结构的多功能复合薄膜，该复合薄膜中PDA-1可改善薄膜颜色，并起到指示变色效果，VO₂可调节近红外光透过率，起到调温作用；所得复合薄膜不仅表现出较易接受的灰蓝色，还表现出良好的调光性能(太阳光调制能力ΔT_sol=7.64%，低温下可见光透射率T_{l, lum}=56.23%，高温下可见光透射率T_{h, lum}=62.37%)。此外，PDA-1的变色温度与单斜相VO₂的相变温度(~68℃)接近，随着温度升高，复合薄膜在调节近红外光透过率的同时，其外观颜色可由灰蓝色变为红色，有利于智能窗自动调温功能的直观展示及进一步推广和应用。
- 聚二乙炔 /
- 二氧化钒 /
- 热致变色 /
- 复合薄膜 /
- 智能窗
Abstract: Vanadium dioxide (VO₂) with thermally induced phase transition has demonstrated a good regulation ability in the range of near-infrared light, and widely used in smart windows. However, the VO₂-based smart windows still face critical challenges in practical use, such as the unfavorable brown-yellow color of the VO₂ thin film, and lack of indicative color-changing for the phase transition process, which are key factors limiting its applications in smart glass. Combining VO₂ with other chromogenic materials could effectively improve the appearance color of smart window coatings and endow it indicative color-changing function. In this study, it is successful to obtain VO₂ multifunctional composite film with reversible thermochromic polydiacetylene (PDA-1, from blue to red) through a bilayer structure strategy. The composite film not only shows favorable grayish-blue color, but also exhibits good solar light regulation ability and luminescence transmittance (solar light regulation ability ΔT_sol=7.64%, luminescence transmittance at low temperature T_{l, lum}=56.23%, luminescence transmittance at high temperature T_{h, lum}=62.37%). In addition, the thermochromic temperature of the PDA-1 is close to the phase transition temperature of monoclinic VO₂ (~68℃). With the temperature increases, the appearance color of the composite film can change from grayish-blue to red color, and also regulating the near-infrared transmittance, which is conducive to the visual display and further promotion for the thermochromic smart windows.
- polydiacetylene /
- vanadium dioxide (VO₂) /
- thermochromism /
- composite films /
- smart windows

HTML全文

图 1 含有乙二胺基团的聚二乙炔(PDA-1)(EDA-6,8-19-DA)的合成路线

Figure 1. Synthetic route of monomer polydiacetylene (PDA-1) with ethylenediamine group (EDA-6,8-19-DA)

DCC—Dicyclohexylcarbodimide; EDA—Ethylenediamine; DA—Diactylene; RT—Room temperature

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图 2 EDA-6,8-19-DA的白色粉末和其聚合物PDA-1的热致变色照片

Figure 2. Images of EDA-6,8-19-DA as white powder and corresponding polymer PDA-1 exhibiting thermochromic behavior

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图 3 (a) PDA-1的DSC曲线；(b) PDA-1的TGA和DTG曲线

Figure 3. (a) DSC curves of PDA-1；(b) TGA and DTG curves of PDA-1

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图 4 PDA-1薄膜的制备及其热致变色现象

Figure 4. Preparation and thermochromic behavior of PDA-1 thin film

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图 5 (a) PDA-1薄膜的透过率随温度变化图；(b) 薄膜在542 nm、565 nm和619 nm处的透过率随温度变化的曲线

Figure 5. (a) Transmittance spectra of PDA-1 film as a function of temperature; (b) Plot of film transmittance at 542 nm, 565 nm and 619 nm as a function of temperature

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图 6 (a) VO₂纳米粒子的XRD图谱；(b) VO₂纳米粒子的DSC曲线

Figure 6. (a) XRD pattern of VO₂ nanoparticles; (b) DSC curve of VO₂ nanoparticles

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图 7 VO₂纳米粒子的SEM图像 (a) 及其粒径分布 (b)

Figure 7. SEM image (a) and size distribution (b) of VO₂ nanoparticles

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图 8 VO₂-PDA-1复合薄膜结构和制备示意图

Figure 8. Schematic diagram of structure and preparation of VO₂-PDA-1 composite film

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图 9 VO₂-PDA-1复合薄膜的SEM图像及EDS元素映射图

Figure 9. SEM image and EDS element mapping images of VO₂-PDA-1 composite film

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图 10 VO₂-PDA-1复合薄膜截面的SEM图像

Figure 10. SEM image of the cross-section of VO₂-PDA-1 composite film

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图 11 VO₂薄膜 (a)、PDA-1薄膜 (b)、VO₂-PDA-1复合薄膜 (c)在20℃(上)和80℃(下)时的照片

Figure 11. Photographs of VO₂ film (a), PDA-1 film (b), VO₂-PDA-1 composite film (c) at 20℃ (top) and 80℃ (bottom)

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图 12 VO₂薄膜、PDA-1薄膜和VO₂-PDA-1复合薄膜在20℃和80℃下的透射光谱

Figure 12. Transmittance spectra of VO₂ film, PDA-1 film, VO₂-PDA-1 composite film at 20℃ and 80℃

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图 13 VO₂薄膜和不同单体溶液浓度制备的VO₂-PDA-1复合薄膜在20℃和80℃时的照片

Figure 13. Photographs of VO₂ film and VO₂-PDA-1 composite films prepared by monomer solutions with different concentrations at 20℃ and 80℃

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图 14 (a) 不同单体溶液浓度制备的VO₂-PDA-1复合薄膜的透射光谱图；(b) 复合薄膜的T_lum、T_sol及ΔT_sol随单体浓度变化的曲线

Figure 14. (a) Transmittance spectra of VO₂-PDA-1 composite films prepared using monomer solutions with different concentrations; (b) Plot of T_lum, T_sol and ΔT_sol of the composite films as a function of monomer concentration

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图 15 VO₂薄膜截面的SEM图像

Figure 15. SEM images of the cross-section of VO₂ films

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图 16 不同VO₂厚度的复合薄膜的热致变色照片

Figure 16. Photographs of thermochromic VO₂-PDA-1 composite films with different thicknesses of VO₂ layers

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图 17 (a) 不同VO₂厚度的复合薄膜在20℃和80℃下的透射光图谱；(b) 复合薄膜的T_lum、T_sol及ΔT_sol随VO₂厚度变化的曲线

Figure 17. (a) Transmittance spectra of thermochromic VO₂-PDA-1 composite films with different VO₂ thickness; (b) Plot of T_lum, T_sol and ΔT_sol of the composite films as a function of the thickness of VO₂ layer

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表 1 VO₂薄膜、PDA-1薄膜和VO₂-PDA-1复合薄膜的可见光透过率(T_lum)、太阳光透过率(T_sol)和太阳光调制能力(ΔT_sol)

Table 1. Visible transmittance (T_lum), solar transmittance (T_sol) and solar modulation ability (ΔT_sol) of VO₂ film, PDA-1 film, and VO₂-PDA-1 composite film

films	T_lum/%		T_sol/%		ΔT_sol/%
films	20℃	80℃	20℃	80℃	ΔT_sol/%
VO₂	67.15	68.98	80.16	71.74	8.42
PDA-1	83.97	87.02	95.98	96.53	−0.54
VO₂-PDA-1	56.23	62.37	76.65	69.01	7.64

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表 2 不同单体EDA-6,8-19-DA浓度(20、30和40 mg/mL)和不同VO₂层厚度(2.2、4.0和5.2 μm)复合薄膜的可见光透光率(T_lum)、太阳光透过率(T_sol)和太阳光调节能力(ΔT_sol)

Table 2. Visible transmittance (T_lum), solar transmittance (T_sol) and solar modulation abilities (ΔT_sol) of the composite films prepared with different concentrations of monomer EDA-6,8-19-DA (20, 30 and 40 mg/mL) and different thickness of VO₂ layer (2.2, 4.0, and 5.2 μm)

No.	Composite films		T_lum/%		T_sol/%		ΔT_sol/%
No.	VO₂/μm	EDA-6,8-19 DA/(mg·mL⁻¹)	20℃	80℃	20℃	80℃	ΔT_sol/%
1	5.2	20	56.23	62.37	76.65	69.01	7.64
2	5.2	30	53.99	60.77	75.81	68.99	6.81
3	5.2	40	41.57	48.40	68.25	62.15	6.10
4	2.2	20	57.67	64.40	81.01	76.99	4.02
5	4.0	20	57.11	63.71	78.91	72.38	6.53

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