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CN108251100B - Self-repairing electrochromic solution capable of gelling at room temperature and application thereof - Google Patents

Self-repairing electrochromic solution capable of gelling at room temperature and application thereof Download PDF

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CN108251100B
CN108251100B CN201611245485.6A CN201611245485A CN108251100B CN 108251100 B CN108251100 B CN 108251100B CN 201611245485 A CN201611245485 A CN 201611245485A CN 108251100 B CN108251100 B CN 108251100B
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CN108251100A (en
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曹贞虎
胡珊珊
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Ningbo Ninuo Electronic Technology Co ltd
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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    • G02F1/1516—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
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Abstract

The present invention relates to an electrochromic solution comprising: a solvent, an anodic electroactive material, a cathodic electroactive material, and a polymer comprising diarylbenzofuranone groups. The electrochromic solution can be gelled at room temperature, and the gel can be self-repaired at room temperature and has no influence on the electrochromic performance of the electrochromic solution. The invention also relates to an electrochromic device filled with the electrochromic solution.

Description

Self-repairing electrochromic solution capable of gelling at room temperature and application thereof
Technical Field
The present invention relates to the field of electrochromism, and more particularly to electrochromic solutions in electrochromic devices.
Background
Electrochromism is an electrically driven color changing technology, and is a process that the color of a material is changed by getting and losing electrons under the action of an external voltage. The material has great application value in electrochromic windows, automobile rearview mirrors, electrochromic glasses, high-resolution photoelectric camera equipment, photoelectric chemical energy conversion/storage devices, military camouflage, decorative materials and the like.
The basic structure of the electrochromic device is similar to a sandwich, and the electrochromic medium is arranged between two substrates plated with conductive materials. Electrochromic devices can be classified into 3 types according to the physical state of an electrochromic medium, and one type is a solution type electrochromic device, wherein an electrochromic material is always dissolved in a solvent. The second type is a semi-solution type electrochromic device, which is accompanied by the transmission of electrons and the change of the chemical properties of materials in the process of switching between a colored state and a transparent state, and when the device is in the transparent state, the electrochromic material is dissolved in a solvent; when the device is in the colored state, the electrochromic material will concentrate at the electrode surface. The third type is an all-solid-state electrochromic device, and the electrochromic material is always in a solid state in the whole process of device color change.
Among the three types of electrochromic devices, the solution type electrochromic device has the characteristics of simple structure, simple and convenient preparation process, short response time and the like, so that the solution type electrochromic device is always a hotspot of the research of the electrochromic device and is widely applied. However, during long-term use, the electrochromic solution may cause phase separation, deposition, or defects to affect vision; furthermore, due to unavoidable external forces, the electrochromic device may be broken, thereby leaking toxic electrochromic solutions and possibly compromising the safety of the driver or other personnel.
In order to overcome the above problems, US5801873 uses an acrylic polymer as a thickener of an electrochromic solution, thereby increasing the viscosity of the solution, preventing phase separation or deposition in the electrochromic device, and reducing the flow rate of the solution, so that it is convenient to clean and reduce the damage of toxic substances to people after the electrochromic device is broken. Although the concentration is high (the optimum concentration is 7-15% (w/w)), the gelation ability of the solution is limited because of no crosslinking; also, in terms of processing, it is first to make a polyacrylic film on the conductive layer of the glass substrate by solvent evaporation, adding to the complexity of the process. US patent 8928966 adds a cross-linked polymer electrolyte having creep resistance properties to the electrochromic solution, but the polymer electrolyte may be electrically conductive and may have some effect on the performance of the electrochromic device. The acrylic acid derivative which can be crosslinked by ultraviolet light is introduced into the electrochromic solution in the Chinese patent CN201410165629.1, the formed gel has good stability and simple process, can inhibit the solution from flowing out after the electrochromic device is broken, and is difficult to repair the gel breakage caused by impact.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an electrochromic solution which can be gelled and can self-repair at room temperature after gel fracture. In addition, the invention also provides a solution type electrochromic device containing the electrochromic solution.
An electrochromic solution in an electrochromic device comprising a solvent, an anodic electroactive material, a cathodic electroactive material, and a polymer comprising structural units of formula 1;
Figure 953682DEST_PATH_IMAGE001
formula 1
In the formula 1, R1And R2Independently selected from H orC1~20A hydrocarbon group of (1).
The polymer containing the structural unit of the formula 1 (also referred to as a polymer containing diaryl benzofuranone group in the invention) can generate equilibrium reaction of automatic bond breaking and bonding at room temperature, and the mechanism is shown as the following formula, thereby endowing gel formation and self-repairing functions.
Figure 608785DEST_PATH_IMAGE002
Preferably, in formula 1, R1And R2Is H or tert-butyl.
The polymer containing the structural unit shown in the formula 1 can be a polymer with a main chain containing the structural unit shown in the formula 1 or a polymer with a side group containing the structural unit shown in the formula 1.
Further preferably, the electrochromic solution preferably comprises hyperbranched polymers having structural segments of formulas 2 and 3:
Figure 3994DEST_PATH_IMAGE003
Figure 756050DEST_PATH_IMAGE004
formula 2 formula 3
The hyperbranched polymer has high branching degree and less molecular chain entanglement, so compared with a linear polymer with the same molecular weight, the hyperbranched polymer has much lower viscosity and good solubility and is convenient to inject into an electrochromic device; and secondly, the hyperbranched polymer has a high branched structure and small shrinkage rate during curing.
In the invention, the concentration of the polymer containing the structural unit shown in the formula 1 in the electrochromic solution is 1-15% (w/v);
the unit% (w/v) means the mass of the polymer containing the structural unit of formula 1 divided by the volume of the electrochromic solution; when the concentration of the polymer containing the structural unit of the formula 1 is lower than 1% (w/v), the gel strength is poor and the self-repairing is slow; when the concentration of the polymer having the structural unit of formula 1 is more than 15% (w/v), the degree of crosslinking is high to cause a gel shrinkage phenomenon.
In the electrochromic solution, the concentration of the polymer containing the structural unit shown in the formula 1 is more preferably 2-5% (w/v).
In the present invention, the polymer having the structural unit of formula 1 is preferably a polymer having an amide bond, an imide bond, an ether bond, an ester bond, an urethane bond, a hydroxyl group, a ketone group, a carboxyl group, a nitro group, a cyano group or a mercapto group, and the presence of the above groups contributes to dissolution of the polymer having the structural unit of formula 1 in a polar solvent of a common electrochromic solution.
The anode electroactive material is at least one selected from triphenylamine, substituted triphenylamine, ferrocene, substituted ferrocene, ferrocenium salt, substituted ferrocenium salt, phenothiazine, substituted phenothiazine, kadethia, substituted kadethia, phenazine and substituted phenazine.
Preferably, the concentration of the anode electroactive material in the electrochromic solution is 0.001-0.5 mol/L, and more preferably 0.002-0.1 mol/L.
Preferably, the cathodic electroactive material is at least one selected from viologen, substituted viologen, alliquinone and substituted anthraquinone.
Preferably, in the electrochromic solution, the concentration of the cathode electroactive material is 0.001-0.55 mol/L, and more preferably 0.002-0.1 mol/L.
In the present invention, the solvent is selected from chemical agents having good dissolving or swelling ability and no chemical reaction with the polymer containing the structural unit of formula 1, the anodic electroactive material and the cathodic electroactive material.
Preferably, the solvent is at least one of propylene carbonate, butyrolactone, 2-acetylbutyrolactone, gamma-valerolactone, ethylene carbonate, sulfolane, 3-methylsulfolane, dimethylacetamide, dimethylformamide, acetonitrile, glutaronitrile, 2-methylglutaronitrile, 3-hydroxypropionitrile, tetraglyme, dimethyl sulfoxide, ethoxyethanol and cyclopentanone.
The term "electroactive" is defined herein as undergoing a change in its oxidation state when exposed to a particular potential difference. The cathode electroactive material is reduced by accepting electrons from the cathode under the action of an electric field; the anode electroactive material is oxidized by supplying electrons to the anode under the action of an electric field. The cathode electroactive material and the anode electroactive material are matched to play a role in balancing charges. Wherein at least one of the anode electroactive material and the cathode electroactive material is an electrochromic material, namely, has electrochromic performance.
The polymer comprising the structural unit of formula 1 may be synthesized prior to mixing with the solvent, the anodic electroactive material, and the cathodic electroactive material, or may be formed by reacting monomers and after mixing with the solvent, the anodic electroactive material, and the cathodic electroactive material.
Preferably, the polymer containing the structural unit of formula 1 is formed by monomer reaction after being mixed with the solvent, the anodic electroactive material and the cathodic electroactive material, and the method can reduce the initial viscosity of the electrochromic solution and facilitate the injection into an electrochromic device.
Other functional materials such as ultraviolet light stabilizers, heat stabilizers, antioxidants, thickeners, viscosity modifiers, and redox stabilizers may also be added to the electrochromic solution.
The invention also includes an electrochromic device comprising a front substrate and a back substrate; one surface of the front substrate is plated with a conductive material, and one surface of the rear substrate is plated with a conductive material; the surface of the conductive material of the front substrate and the surface of the conductive material of the rear substrate are oppositely arranged and are bonded by a sealing adhesive to form a sealed cavity, and the electrochromic solution is filled in the sealed cavity.
The front or back substrate may be made of any material that has sufficient strength and can be processed into a predetermined shape for the electrochromic device to be used in the exposed environment.
Preferably, the front substrate and the rear substrate are independently selected from organic polymer materials such as polymethyl methacrylate, polyester, polyvinyl chloride, polyvinylidene chloride, polyamide, polyimide, polypropylene, polyethylene, polycarbonate and the like, and at least one of glass, ceramic and metal.
Further preferably, the front substrate and the rear substrate are made of the same material;
preferably, the front substrate and the rear substrate are glass.
Preferably, the conductive material plated on the front substrate and the rear substrate is independently selected from at least one of tin oxide, zinc oxide, indium tin oxide, indium gallium zinc oxide compound, fluorine-doped tin oxide, aluminum-doped zinc oxide and fluorine-doped zinc oxide.
Besides the conductive material, according to the requirements on functions and performance in specific use, functional materials such as a reflecting material, an anti-reflecting material, a hydrophilic material, an ultraviolet light blocking material and the like can be coated on the substrate;
for example, to meet the specific functional and performance requirements, the conductive material is plated on the surface of the front and rear substrates after at least one functional material such as a reflective material, an anti-reflective material, a hydrophilic material, an ultraviolet blocking material, etc. is plated thereon.
The invention also comprises the application of the solution type electrochromic device, and the solution type electrochromic device is applied to rearview mirrors of vehicles, windows of buildings and airplanes, optical filters, decorative materials, stealth materials, information display, military technologies and the like.
The electrochromic device is preferably used for assembling and preparing building gradual change glass, intelligent color change windows for vehicles, aircraft portholes, color change sunglasses or automobile anti-chordal rearview mirrors.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through controlling the components and concentration of the electrochromic solution, a cross-linked network structure can be formed at room temperature, and the gelation of the electrochromic solution in the solution type electrochromic device is realized, so that the phenomena of phase separation or deposition in the electrochromic solution, solution leakage and the like when the electrochromic device is broken are inhibited. Moreover, the self-healing can be realized at room temperature for microcracks caused by external impact and the like, so that the service life of the electrochromic device is prolonged remarkably.
Drawings
Fig. 1 is a cross-sectional view of an electrochromic device according to an application example of the invention. In the drawings, 1 and 2 are glass substrates; 3 and 4 are transparent conductive materials plated on a glass substrate; 5 is frame glue; and 6 is a cavity filled with electrochromic solution.
FIG. 2 is a graph showing gel repair as described in application example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which should be noted that the present invention is only illustrative and should not be construed as limiting the scope of the present invention.
Example 1:
the method comprises the following steps of taking equimolar phenol and 4-hydroxymandelic acid as raw materials, glacial acetic acid as a solvent and methanesulfonic acid as a dehydrating agent, reacting at 95 ℃ for 3 hours, pouring a reaction solution into water after the reaction is finished, collecting solids, and recrystallizing with ethanol to obtain the compound shown in the structural formula 1. The compound shown in the structural formula 1, 2 times of molar weight of sodium hydroxide and 2.5 times of molar weight of 3-bromopropanol are subjected to reflux reaction in acetonitrile for 3 hours, after the reaction is finished, the reaction solution is poured into ethanol, and the solid is collected and recrystallized by the ethanol to obtain the compound shown in the structural formula 2 (the synthetic route is shown in the following formula).
Figure 578512DEST_PATH_IMAGE005
Dissolving a compound shown in a structural formula 2, 4',4' '-triphenylmethane triisocyanate, hexamethylene diisocyanate, a trace amount of organic tin catalyst dibutyltin dilaurate, 1' -dineopentyl-4, 4 '-bipyridyl bis (hexafluoroborate) and 5, 10-diisopropyl-5, 10-dimethylphenazine in propylene carbonate to prepare an electrochromic solution (the concentration of the compound shown in the structural formula 2 is 30 mmol/L; the concentration of 4,4',4'' -triphenylmethane triisocyanate is 6 mmol/L; the concentration of hexamethylene diisocyanate is 21 mmol/L; the concentration of 1,1 '-dineopentyl-4, 4' -bipyridyl bis (hexafluoroborate) is 50 mmol/L; the concentration of 5, 10-diisopropyl-5, 10-dimethylphenazine is 50 mmol/L), pouring the electrochromic solution into an electrochromic device shown in a figure 1, and sealing the electrochromic device by using glue to obtain the device with an electrochromic function.
And (3) testing results: placing the electrochromic solution at room temperature to 25 ℃ for 6 hours, and gelling; and (3) after the gel cracks, standing at room temperature-25 ℃ for 15 hours, and naturally repairing (as shown in figure 2). The reflectivity of the prepared electrochromic device for 500nm wavelength light measured under the condition of no external voltage is 76%, and the reflectivity of the prepared electrochromic device for 500nm wavelength light measured after electrification is 5.4%; the power is applied for 10000 times at room temperature (the power is off for 5 seconds after the electrochromic device is powered on for 5 seconds, and the cycle is one), the reflectivity of the light with the wavelength of 500nm is 75% measured under the condition of no external voltage, and the reflectivity of the light with the wavelength of 500nm is 5.8% measured after the power is applied.
Example 2:
the method comprises the following steps of taking equimolar 2, 4-di-tert-butylphenol and 4-hydroxymandelic acid as raw materials, taking glacial acetic acid as a solvent and methanesulfonic acid as a dehydrating agent, reacting for 3 hours at 95 ℃, pouring a reaction solution into water after the reaction is finished, collecting solids, and recrystallizing with ethanol to obtain the compound shown in the structural formula 3. And (3) carrying out reflux reaction on the compound shown in the structural formula 3, 2 times of molar weight of sodium hydroxide and 2.5 times of molar weight of 3-bromopropanol in acetonitrile for 3 hours, pouring the reaction solution into ethanol after the reaction is finished, collecting the solid, and recrystallizing with ethanol to obtain the compound shown in the structural formula 4 (the synthetic route is shown in the following formula).
Figure 786158DEST_PATH_IMAGE006
The compound shown in the structural formula 4, German Bayer N3300 aliphatic polyisocyanate (trifunctional isocyanate), polyethylene glycol with the molecular weight of about 500, a trace amount of dibutyltin dilaurate serving as an organotin catalyst, 1 '-dihexyl-4, 4' -bipyridine bis (trifluoromethanesulfonate) and 5, 10-dihydro-5, 10-dimethylphenazine are dissolved in butyrolactone to prepare an electrochromic solution (the concentration of the compound shown in the structural formula 4 is 20 mmol/L; the concentration of the German Bayer N3300 aliphatic polyisocyanate is 20 mmol/L; the concentration of the polyethylene glycol is 10 mmol/L; the concentration of the 1,1 '-dihexyl-4, 4' -bipyridine bis (trifluoromethanesulfonate) is 50 mmol/L; and the concentration of the 5, 10-dihydro-5, 10-dimethylphenazine is 50 mmol/L), the electrochromic device is filled in the electrochromic device shown in the figure 1, and then the device with the electrochromic function is sealed by glue, so that the device with the electrochromic function is obtained.
And (3) testing results: placing the electrochromic solution at room temperature to 25 ℃ for 5 hours, and gelling; and (5) after the gel cracks, placing the gel at room temperature to 25 ℃ for 11 hours, and naturally repairing the gel. The reflectivity of the prepared electrochromic device for 500nm wavelength light measured under the condition of no external voltage is 69%, and the reflectivity of the prepared electrochromic device for 500nm wavelength light measured after electrification is 4.3%; the power is applied for 10000 times at room temperature (the power is off for 5 seconds after the electrochromic device is powered on for 5 seconds, and the cycle is one), the reflectivity of the light with the wavelength of 500nm measured under the condition of no external voltage is 67%, and the reflectivity of the light with the wavelength of 500nm measured after the power is applied is 4.6%.
The electrochromic solution in the embodiment is crosslinked and cured at normal temperature so as to realize the gelation of the solution, the process is simple, the formed gel has good self-repairability, and the performance of the electrochromic device is not influenced.

Claims (4)

1. A preparation method of electrochromic solution capable of gelling and self-repairing at room temperature is characterized by comprising the following steps: using equimolar phenol and 4-hydroxymandelic acid as raw materials, glacial acetic acid as a solvent and methanesulfonic acid as a dehydrating agent, reacting at 95 ℃ for 3 hours, pouring a reaction solution into water after the reaction is finished, collecting solids, and recrystallizing with ethanol to obtain a compound shown in a structural formula 1; refluxing and reacting the compound shown in the structural formula 1, 2 times of molar weight of sodium hydroxide and 2.5 times of molar weight of 3-bromopropanol in acetonitrile for 3 hours, pouring the reaction solution into ethanol after the reaction is finished, collecting solids, and recrystallizing with ethanol to obtain the compound shown in the structural formula 2;
Figure FDA0002494811190000011
dissolving a compound shown in a structural formula 2,4 '-triphenylmethane triisocyanate, hexamethylene diisocyanate, a trace amount of organic tin catalyst dibutyltin dilaurate, 1' -dineopentyl-4, 4 '-bipyridyl bis (hexafluoroborate) and 5, 10-diisopropyl-5, 10-dimethyl phenazine in propylene carbonate to prepare an electrochromic solution, wherein the concentration of the compound shown in the structural formula 2 is 30 mmol/L, the concentration of the 4,4' -triphenylmethane triisocyanate is 6 mmol/L, the concentration of the hexamethylene diisocyanate is 21 mmol/L, the concentration of the 1,1 '-dineopentyl-4, 4' -bipyridyl bis (hexafluoroborate) is 50 mmol/L, and the concentration of the 5, 10-diisopropyl-5, 10-dimethyl phenazine is 50 mmol/L.
2. A solution type electrochromic device is characterized by comprising a front substrate and a rear substrate; one surface of the front substrate is plated with a conductive material, and one surface of the rear substrate is plated with a conductive material; the surface of the conductive material of the front substrate and the surface of the conductive material of the rear substrate are compounded through a sealant to form a sealed chamber, and the electrochromic solution prepared according to the method in the claim 1 is filled in the sealed chamber.
3. The solution-type electrochromic device according to claim 2, wherein said front substrate and said rear substrate are plated with conductive materials independently selected from at least one of tin oxide, zinc oxide, indium tin oxide, indium gallium zinc oxide composite, fluorine-doped tin oxide, aluminum-doped zinc oxide, and fluorine-doped zinc oxide.
4. Use of the solution-type electrochromic device according to claim 2 or 3 for the assembly production of architectural glass, automotive smart color-changing windows, aircraft windows, color-changing sunglasses or automotive anti-chordal rearview mirrors.
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