阅读说明：本技术 一种可阻隔近红外光的电致变色器件及其制备与应用 (Near-infrared light-blocking electrochromic device and preparation and application thereof ) 是由 王宏志 刘自豪 白智元 李耀刚 侯成义 张青红 李贤英 于 2020-03-25 设计创作，主要内容包括：本发明涉及一种可阻隔近红外光的电致变色器件及其制备与应用,所述器件由纳米氧化锡锑ATO/紫精的混合溶液与透明导电玻璃组成,通过注射法组装变色器件。本发明的器件应用于建筑节能窗领域。在本发明中,添加ATO不仅提升了所得器件的变色性能,而且赋予器件阻隔红外的功能。另外,采用注射法,不仅组装工艺简单,而且有效消除了组装过程中的多余气泡。因此,本发明可有力推动电致变色器件在建筑节能窗领域的进一步发展。(The invention relates to an electrochromic device capable of blocking near infrared light, and preparation and application thereof. The device is applied to the field of building energy-saving windows. In the invention, the addition of ATO not only improves the color change performance of the obtained device, but also endows the device with the infrared-blocking function. In addition, the injection method is adopted, so that the assembly process is simple, and redundant bubbles in the assembly process are effectively eliminated. Therefore, the invention can powerfully promote the further development of the electrochromic device in the field of building energy-saving windows.)

1. The electrochromic material comprises components and contents of nano tin antimony oxide ATO, a viologen compound, ionic liquid and an organic solvent, wherein the volume ratio of the organic solvent to the ionic liquid is 1-5: 1, the ATO content is 0.01-0.18 wt%, and the concentration of the viologen compound is 10-20 mmol/L.

2. The material of claim 1, wherein the viologen compound is 1, 1-diethyl-4.4-bipyridine dibromide EtVio; the ionic liquid is 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt [ BMIM ]]TF₂N; the organic solvent is carbonic acid propylene glycolEster PC; the electrochromic material also contained dimethylferrocene dmFc.

3. The material as claimed in claim 1, wherein the nano tin antimony oxide ATO has a particle diameter of 30-50 nm.

4. An electrochromic device, characterized in that the device comprises, in order, a transparent conductive glass, the electrochromic material of claim 1, a transparent conductive glass; wherein the electrochromic material is injected and sealed in the middle of the transparent conductive glass.

5. A method for preparing an electrochromic device comprises the following steps:

(1) dissolving 1, 1-diethyl-4.4-bipyridine dibromide EtVio, dimethylferrocene dmFc in propylene carbonate PC and 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt [ BMIM ]]TF₂In the mixed solution of N, carrying out ultrasonic dispersion to obtain a viologen color-changing solution;

(2) adding nanometer tin antimony oxide ATO into the viologen discoloration solution, stirring, and defoaming in vacuum to obtain a nanometer tin antimony oxide ATO/viologen mixed solution;

(3) and (3) injecting the mixed solution of the nano tin antimony oxide ATO/viologen in the step (2) between two pieces of conductive glass, discharging redundant bubbles through an air outlet, and sealing to obtain the electrochromic device.

6. The preparation method according to claim 5, wherein the amount of 1, 1-diethyl-4.4-bipyridyl dibromide Etvio used in the step (1) is 20-40 mmol/L, and the amount of dimethylferrocene dmFc is 10-20 mmol/L.

7. The preparation method according to claim 5, wherein the mass ratio of ATO particles to the purpurine discoloring solution in the step (2) is 0.1-0.3%.

8. The preparation method according to claim 5, wherein an injection port, an air outlet and a 0.3-2 cm contact electrode are reserved between the two pieces of conductive glass in the step (3); the sealing is ultraviolet curing glue with the viscosity of 1400-2800 mPas.

9. An electrochromic device prepared by the method of claim 5.

10. Use of the electrochromic device according to claim 4 in the field of architectural energy saving windows.

Technical Field

The invention belongs to the field of electrochromic devices and preparation and application thereof, and particularly relates to an electrochromic device capable of blocking near infrared light and preparation and application thereof.

Background

The electrochromic intelligent window can improve the energy utilization efficiency of buildings by actively adjusting the optical transmittance, so as to achieve the purposes of energy conservation and emission reduction. Conventional electrochromic devices are based on inorganic oxides such as WO₃Mainly, the viologen electrochromic device has a near-infrared blocking function, but has the problems of uneven coloring, high driving voltage and the like in large-area preparation, and compared with the traditional electrochromic device, the viologen electrochromic device has the advantages of high color changing speed, wide light modulation range, high cycling stability and the like, but does not have the blocking function in a near-infrared region, and has no large-scale application in the field of building energy-saving windows. For example, patent CN109557740 discloses a method for preparing a viologen-based flexible color-changing sheet, which mainly uses viologen materials to realize an electrochromic system, and the time required for preparing a device with 5cmx 5cm for coloring is about 30s, and the prepared device has no blocking effect in the near infrared band. At present, few researches on preparing electrochromic devices by using composite inorganic particles are carried out. Patent CN106479478 discloses a preparation method of an electrochromic material and a device based on metal nanoparticles, wherein metal nanoparticles are added and mixed with an ionic liquid electrolyte to enable the ionic liquid to serve as a silver nanoparticle protective agent and an electrolyte, so that the preparation of the electrochromic material is simplified and the stability of metal silver is improved by avoiding the addition of other stabilizers and electrolytes, but the electrochromic material has no obvious barrier in an infrared band, and the size of the driving voltage of the device is not mentioned in the patent. Patent CN109836979 discloses a nano tin antimony oxide coating, which uses water-based polyurethane as a main film forming substance, and the maximum temperature difference in a box can reach 4 ℃ under the sunshine condition of heat insulation test, but a device prepared by the method can not realize active control of optical transmittance.

Disclosure of Invention

The invention aims to solve the technical problem of providing an electrochromic device capable of blocking near infrared light and preparation and application thereof, overcoming the technical defect that the electrochromic device prepared from organic materials in the prior art has no obvious blocking in infrared bands, and not only improving the color-changing performance of the device by adding ATO, but also endowing the device with the infrared blocking function.

The electrochromic material comprises nanometer tin antimony oxide ATO, a viologen compound, an ionic liquid and an organic solvent, wherein the volume ratio of the organic solvent Propylene Carbonate (PC) to the ionic liquid (I L s) is 1-5: 1, the ATO content is 0.01-0.18 wt% (the content in the whole system), and the concentration of the viologen compound is 10-20 mmol/L (the concentration in the whole system).

The viologen compound is 1, 1-diethyl-4.4-dipyridyl dibromide EtVio; the ionic liquid is 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt [ BMIM ]]TF₂N; the organic solvent is propylene carbonate PC.

The electrochromic material also contains dimethyl ferrocene dmFc which has the function of reducing the driving voltage of a device.

The particle diameter of the nano tin antimony oxide ATO is 30-50 nm.

The invention provides an electrochromic device, which sequentially comprises transparent conductive glass, an electrochromic material and transparent conductive glass; wherein the electrochromic material is injected and sealed in the middle of the transparent conductive glass.

The invention discloses a preparation method of an electrochromic device, which comprises the following steps:

(1) dissolving 1, 1-diethyl-4.4-bipyridine dibromide EtVio, dimethylferrocene dmFc in propylene carbonate PC and 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt [ BMIM ]]TF₂In the mixed solution of N, carrying out ultrasonic dispersion to obtain a viologen color-changing solution;

(2) adding nanometer tin antimony oxide ATO into the viologen discoloration solution, stirring, and defoaming in vacuum to obtain a nanometer tin antimony oxide ATO/viologen mixed solution;

(3) assembling the color-changing device by an injection method: and (3) injecting the mixed solution of the nano tin antimony oxide ATO/viologen in the step (2) between two pieces of conductive glass, discharging redundant bubbles through an air outlet, and sealing to obtain the electrochromic device.

The preferred mode of the above preparation method is as follows:

in the step (1), the dosage of 1, 1-diethyl-4.4-bipyridine dibromide Etvio is 20-40 mmol/L, and the dosage of dimethylferrocene dmFc is 10-20 mmol/L.

In the step (2), the mass ratio of ATO particles to the viologen discoloration solution is 0.1-0.3%.

The technological parameters of vacuum defoaming in the step (2) are as follows: the vacuum pressure is-0.8 to-1 KPa, and the defoaming time is 0.5 to 2 hours.

An injection port, an air outlet and a 0.3-2 cm contact electrode are reserved between the two pieces of conductive glass in the step (3); the sealing is ultraviolet curing glue with the viscosity of 1400-2800 mPas.

The invention provides an electrochromic device prepared by the method.

The invention provides an application of the electrochromic device in the field of building energy-saving windows.

Advantageous effects

(1) The infrared blocking function is endowed to the device by adding ATO.

(2) The invention has simple assembly process by using an injection method and effectively eliminates redundant air bubbles in the assembly process.

(3) The driving voltage of the 10cm x 20cm electrochromic device is controlled to be about 2.5V by adding ATO and dmFc, the coloring speed reaches 17s as shown in figure 6, and the background transmittance expands the application range of the device, so that the device has a wide application prospect in the field of building energy-saving windows.

Drawings

FIG. 1 is a schematic diagram of an electrochromic device assembly process; wherein (a) is a schematic structural diagram; (b) a packaging schematic diagram;

FIG. 2 is a digital photograph of an assembled electrochromic device of example 1 in a bleached state (a) and a colored state (b);

FIG. 3 is an in situ light transmission curve for 100 previous cycles at 605nm for a colored state versus a bleached state for an assembled electrochromic device of example 1;

FIG. 4 is an in situ light transmission curve at 605nm for 2000-2100 cycles of colored versus bleached for an assembled electrochromic device of example 1;

figure 5 is a digital photograph of the assembled electrochromic device of example 2 in the bleached state (a) and the bleached state (b);

FIG. 6 is an in situ light transmittance curve at 605nm for the colored and bleached states for an assembled electrochromic device of example 2;

FIG. 7 is an in situ light transmission curve for the colored state versus the bleached state for the first 50 revolutions at 605nm for an assembled electrochromic device of example 2;

FIG. 8 is a graph showing the transmittance wavelength curves of 1000nm to 2500nm in the near infrared band of electrochromic devices prepared in examples 2 and 3 by adding different amounts of antimony tin oxide ATO.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Ethyl viologen dibromide, specification 98%, alatin; propylene carbonate, analytically pure, national pharmaceutical group; dimethylferrocene, analytically pure, group of national drugs; 1-butyl-3-methylimidazolium bistrifluoromethanesulfonimide salt, specification 99%, Mooney chemical example 1

(1) PC solutions 5m L and [ BMIM ] were measured at room temperature]TF₂The N ionic liquid 15m L was mixed and stirred uniformly in a 50m L brown bottle, dried EtVio powder 598.4mg and dimethyl ferrocene powder 37.2mg were weighed, added to the brown bottle and mixed and stirred to obtain a 30m L mixed color changing liquid.

(2) And (3) mixing 10g of mixed color-changing liquid obtained in the step (2) with a dispersion liquid containing 0.030g of ATO particles (40nm) to obtain a color-changing precursor mixed liquid.

(3) And (3) injecting the color-changing precursor mixed solution obtained in the step (2) into a space between two pieces of conductive glass through an injection port, discharging redundant bubbles through an air outlet, and sealing by using ultraviolet curing adhesive. Obtaining the 3cm x 5cm infrared-blocking viologen-based electrochromic device.

The packaging schematic diagram of the infrared-blocking viologen-based electrochromic device obtained by the injection packaging method in the embodiment is shown in fig. 1, and it can be known that the assembled device can eliminate redundant bubbles and the process is simple and convenient.

The two-electrode system of the electrochromic device assembled in this example was combined with an electrochemical workstation and an ultraviolet spectrophotometer to measure the change in light transmittance of the fabricated device, and digital photographs of the discolored state and the colored state are shown in fig. 2. The results show that the device turned blue when 1.3V was applied to the device and self-discolored when no voltage was applied.

The transmittance of the electrochromic device assembled in the embodiment is obviously changed in a wavelength band of 300-800 nm, reaches 37% at a position with lambda of 605nm, the coloring time of the device is 10s, the fading time is about 10s, the response time is controlled within 30s, the cycle performance of the electrochromic device assembled in the embodiment is stable, and the original 80% of the light modulation range is kept after 2000 cycles as shown in fig. 3 and 4.