CN110646996A - Ultraviolet curing viologen-based electrochromic device and preparation method thereof - Google Patents
Ultraviolet curing viologen-based electrochromic device and preparation method thereof Download PDFInfo
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- CN110646996A CN110646996A CN201910935635.3A CN201910935635A CN110646996A CN 110646996 A CN110646996 A CN 110646996A CN 201910935635 A CN201910935635 A CN 201910935635A CN 110646996 A CN110646996 A CN 110646996A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
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Abstract
The invention relates to an ultraviolet curing viologen-based electrochromic device and a preparation method thereof. The assembled electrochromic device has the advantages of simple structure, good color-changing performance and potential for automatic, flow and batch production and application.
Description
Technical Field
The invention belongs to the field of electrochromic materials, and particularly relates to an ultraviolet curing viologen-based electrochromic device and a preparation method thereof.
Background
Viologen materials are one of the most widely used electrochromic materials at present. People often compound the electrochromic material with inorganic fillers, polymers, organic solvents and the like, and encapsulate the electrochromic material among conductive substrates to construct an integrated structural electrochromic device. The viologen-based color-changing device not only has the advantages of rich colors, stable circulation and the like, but also is easy to prepare the electrochromic film with light weight and good flexibility. However, few researches on the preparation of the viologen-based flexible color-changing film are carried out, and the preparation process mostly adopts a heat curing mode. For example, patent CN109557740 discloses a method for preparing a viologen-based flexible color-changing sheet, wherein PVDF is added to prepare an electrochromic film with an integrated structure through thermal curing, and the method adopts an adhesive tape to control the thickness, so that the electrochromic device is difficult to prepare in batch and automatically, and has the problems of uneven coloring and the like.
Unlike the conventional thermal curing method, the photo-curing method is regarded as a more convenient and efficient film-forming method. The ultraviolet curing is one of the most common light curing modes, namely, light with the wavelength of 200-450 nm is used for irradiating curing glue, so that an internal photoinitiator absorbs light energy, and then intramolecular or intermolecular polymerization or crosslinking is induced to generate insoluble substances with a three-dimensional network structure. The ultraviolet curing method has the characteristics of high efficiency, wide adaptability, economy, energy conservation and environmental protection. Compared with a thermal curing method, the method is simpler and easier, can reduce the curing process, saves time, and realizes batch and automatic production. For example, patent CN103992434 discloses an ultraviolet curing electrolyte gel and its application in electrochromic devices, the method is through ultraviolet curing crosslinking, the process is simple, the formed gel has good stability, and shows excellent stability in electrochemical cycling of electrochromic devices. However, at present, few researches on preparing the viologen-based flexible color-changing device by using an ultraviolet curing method are available.
The glass beads are mainly processed from borosilicate, have the granularity of 10-250 mu m, have the advantages of light weight, low heat conduction, higher strength, good chemical stability and the like, have oleophylic hydrophobicity after the surface is specially treated, are easy to disperse in an organic material system, are usually applied to a PDLC liquid crystal film and are used for controlling the thickness of the film, and the patent CN106336875 discloses a preparation method of a trans-polymer dispersed liquid crystal film. The defects of the method are that the thermal polymerization time before the ultraviolet curing is long, the synthesis process of the ultraviolet curing agent is complicated, and the cost is high.
Disclosure of Invention
The invention aims to solve the technical problem of providing an ultraviolet curing viologen-based electrochromic device and a preparation method thereof, which adopt a convenient and efficient ultraviolet curing method and a process of doping glass beads, are beneficial to the improvement of the light modulation range of the electrochromic device, can effectively control the thickness of the electrochromic device, and are more beneficial to the automatic and batch production of the obtained electrochromic device.
The invention provides an ultraviolet curing viologen-based electrochromic device which is obtained by adding an ultraviolet curing agent and glass beads into viologen-based electrochromic solution, assembling the device through coating and finally performing ultraviolet curing.
The invention also provides a preparation method of the ultraviolet curing viologen-based electrochromic device, which comprises the following steps:
(1) dissolving 1, 1-diethyl-4.4-bipyridine dibromide EtVio and ferrocene Fc in propylene carbonate PC and 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt [ EMIM]NTF2Performing ultrasonic dispersion on the mixed solution to obtain a viologen-based color-changing solution;
(2) adding an ultraviolet curing agent and glass beads into the viologen-based color-changing solution obtained in the step (1), uniformly stirring, and performing vacuum defoaming to obtain a color-changing precursor mixed solution; wherein, the glass beads account for 0.4 to 0.5 percent of the total mass of the color-changing precursor solution;
(3) and (3) coating the color-changing precursor mixed liquor obtained in the step (2) between two pieces of ITO-PET, compacting, and finally carrying out ultraviolet curing to obtain the color-changing precursor mixed liquor.
The dosage of the Etvio in the step (1) is 20-40 mmol/L; the dosage of Fc is 10-20 mmol/L (based on the total volume of the viologen-based color-changing solution).
[ EMIM ] in the step (1)]NTF2The volume ratio of the PC to the PC is 1: 1-1: 5.
The volume ratio of the ultraviolet curing agent to the viologen-based color-changing solution in the step (2) is 1: 1-1: 4.
The ultraviolet curing agent does not have special requirements, and the conventional ultraviolet curing agent in the industry can be used.
And (3) the vacuum defoaming pressure in the step (2) is-0.8 to-1 KPa, and the defoaming time is 0.5 to 2 hours.
And (3) compacting two sheets of ITO-PET by adopting a pressing roller.
The ultraviolet curing in the step (3) adopts an LED ultraviolet curing device, the power is 20-30W, and the wavelength is 365 nm; the ultraviolet curing time is 0.5-3 min.
The experimental environment in the step (1), the step (2) and the step (3) is free of strong light, and the stirring time in the step (2) is 1-5 hours.
Advantageous effects
(1) The invention adopts the ultraviolet curing method to prepare the electrochromic device, and has the advantages of high efficiency, wide application range, simple process, cost saving and the like.
(2) The invention realizes the regulation and control of the thickness of the electrochromic device by adding the glass beads.
(3) According to the invention, the electrochromic device with good film forming property, adjustable mechanical property and adjustable light modulation range can be prepared by adjusting and controlling the proportion of the ultraviolet curing agent and the color-changing solution, and the obtained device has excellent color-changing property (the maximum light modulation range can reach 79 percent) and good bending resistance, has good comprehensive performance and is suitable for market application.
Drawings
FIG. 1 is a digital photograph of a quasi-solid hybrid color-changing gel prepared according to the present invention.
FIG. 2 is a schematic structural diagram of a color-changing device according to the present invention.
Figure 3 is a digital photograph of the assembled electrochromic device of example 1 in the bleached and colored states.
Fig. 4 is a graph of the uv-vis spectra of the colored and bleached states of the assembled electrochromic device of example 1.
FIG. 5 is a graph of in situ light transmittance at 605nm for a colored state versus a faded state for an assembled electrochromic device of example 1.
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.
Example 1
(1) Measuring 15mL of propylene glycol ester PC solution and 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt [ EMIM ] at room temperature]NTF25mL of ionic liquid is mixed and stirred uniformly in a 50mL brown bottle, 149.6mg of dry EtVio powder and 74.4mg of ferrocene powder are weighed, added into the brown bottle and mixed and stirred to obtain 20mL of viologen-based color-changing solution.
(2) Mixing 8g of the viologen-based color-changing liquid obtained in the step (1) with 2g of ultraviolet curing adhesive in an environment without strong light, adding 0.05g of glass beads (25 mu m), magnetically stirring for 1h, putting into a vacuum kettle, pumping to-1 KPa, defoaming for 0.5h, and obtaining a color-changing precursor mixed solution.
(3) And (3) paving the color-changing precursor mixed solution obtained in the step (2) between two pieces of ITO-PET, compacting by a press roller, immediately placing under 365nm ultraviolet light, and irradiating for 0.5min to obtain the ultraviolet curing viologen-based electrochromic device.
The digital photo of the quasi-solid mixed color-changing gel prepared by ultraviolet curing in this example is shown in fig. 1, and it can be seen that the color-changing gel has good flexibility and can ensure the bending resistance of the final device. Fig. 2 is a schematic structural diagram of an ultraviolet-cured viologen-based color-changing device, and it can be known that the structure of the device assembled by the ultraviolet-cured viologen-based color-changing device is a typical 'sandwich' structure.
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 faded state and colored state are shown in fig. 3. The results show that the device turned blue when 1.5V 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 the wavelength band of 300-800 nm, and reaches 79% at the position of λ 605nm, as shown in fig. 4. The coloring time of the device is 8s, the fading time is about 60s, and the response time is controlled within 70 s.
The electrochromic device assembled in the embodiment has stable cycle performance and wide light modulation range, as shown in fig. 5. The thickness of the color-changing device is controlled within 425 μm (wherein the film matrix is about 300 μm), and the color-changing device has good bending resistance and can be bent for multiple times without attenuation of color-changing performance.
Example 2
(1) At room temperature, 10mL of PC solution and [ EMIM ] were measured]NTF210mL of ionic liquid is mixed and stirred uniformly in a 50mL brown bottle, 598.4mg of dry EtVio powder and 37.2mg of ferrocene powder are weighed, added into the brown bottle and mixed and stirred to obtain 30mL of viologen-based color-changing liquid.
(2) And (2) mixing 5g of the viologen-based color-changing liquid obtained in the step (1) with 5g of ultraviolet curing adhesive in a non-bright light environment, adding 0.05g of glass beads (25 mu m), magnetically stirring for 3h, putting into a vacuum kettle, introducing a gas pump, pumping to-0.9 KPa, defoaming for 1h, and obtaining a color-changing precursor mixed solution.
(3) And (3) paving the color-changing precursor mixed solution obtained in the step (2) between two pieces of ITO-PET, compacting by a press roller, immediately placing under 365nm ultraviolet light, and irradiating for 1min to obtain the ultraviolet curing viologen-based electrochromic device.
The assembled electrochromic device of the embodiment can change from transparent to dark blue, and the light modulation range is 74 percent at most. The coloring time of the electrochromic device is 13s, and the fading time is 81 s. The method can be cycled for many times, the thickness of the color-changing device is controlled within 425 mu m, and the color-changing performance of the electrochromic device can be bent for many times without attenuation.
Example 3
(1) At room temperature, 25mL of PC solution and [ EMIM ] were measured]NTF25mL of ionic liquid is mixed and stirred uniformly in a 50mL brown bottle, 299.2mg of dry EtVio powder and 83.7mg of ferrocene powder are weighed, and the mixture is added into the brown bottle and mixed and stirred to obtain 30mL of viologen-based color-changing liquid.
(2) Mixing 6g of the viologen-based color-changing liquid obtained in the step (1) and 4g of ultraviolet curing adhesive in an environment without strong light, adding 0.05g of glass beads (25 mu m), magnetically stirring for 5h, putting into a vacuum kettle, introducing into a breather pump, pumping to-0.8 KPa, defoaming for 2h, and obtaining a color-changing precursor mixed liquid.
(3) And (3) paving the color-changing precursor mixed solution obtained in the step (2) between two pieces of ITO-PET, compacting by a press roller, immediately placing under 365nm ultraviolet light, and irradiating for 3min to obtain the ultraviolet curing viologen-based electrochromic device.
The assembled electrochromic device of the embodiment can change from transparent to dark blue, and the light modulation range is 76% at most. The coloring time of the electrochromic device is 11s, and the fading time is 77 s. The method can be cycled for many times, the thickness of the color-changing device is controlled within 425 mu m, and the color-changing performance of the electrochromic device can be bent for many times without attenuation.
Claims (8)
1. An ultraviolet curing viologen-based electrochromic device is characterized in that: the ultraviolet curing agent and the glass beads are added into the viologen-based color-changing solution, device assembly is carried out through coating, and finally ultraviolet curing is carried out to obtain the ultraviolet-curable color-changing solution.
2. A preparation method of an ultraviolet curing viologen-based electrochromic device comprises the following steps:
(1) dissolving 1, 1-diethyl-4.4-bipyridine dibromide EtVio and ferrocene Fc in propylene carbonate PC and 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt [ EMIM]NTF2Performing ultrasonic dispersion on the mixed solution to obtain a viologen-based color-changing solution;
(2) adding an ultraviolet curing agent and glass beads into the viologen-based color-changing solution obtained in the step (1), uniformly stirring, and performing vacuum defoaming to obtain a color-changing precursor mixed solution; wherein, the glass beads account for 0.4 to 0.5 percent of the total mass of the color-changing precursor solution;
(3) and (3) coating the color-changing precursor mixed liquor obtained in the step (2) between two pieces of ITO-PET, compacting, and finally carrying out ultraviolet curing to obtain the color-changing precursor mixed liquor.
3. The method of claim 2, wherein: the dosage of the Etvio in the step (1) is 20-40 mmol/L; the dosage of Fc is 10-20 mmol/L.
4. The method of claim 2, wherein: [ EMIM ] in the step (1)]NTF2The volume ratio of the PC to the PC is 1: 1-1: 5.
5. The method of claim 2, wherein: the volume ratio of the ultraviolet curing agent to the viologen-based color-changing solution in the step (2) is 1: 1-1: 4.
6. The method of claim 2, wherein: and (3) the vacuum defoaming pressure in the step (2) is-0.8 to-1 KPa, and the defoaming time is 0.5 to 2 hours.
7. The method of claim 2, wherein: and (3) compacting two sheets of ITO-PET by adopting a pressing roller.
8. The method of claim 2, wherein: the ultraviolet curing in the step (3) adopts an LED ultraviolet curing device, the power is 20-30W, and the wavelength is 365 nm; the ultraviolet curing time is 0.5-3 min.
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Cited By (2)
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CN111493633A (en) * | 2020-04-27 | 2020-08-07 | 东莞蓝海芯科技有限公司 | Intelligent control curtain with dimming function and intelligent control screen |
CN114316114A (en) * | 2021-12-29 | 2022-04-12 | 深圳市华科创智技术有限公司 | In-situ polymerized viologen integrated electrochromic gel and electrochromic device |
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