All-solid-state flexible small organic molecule electrochromic film as well as preparation method and application thereof

Abstract

The embodiment of the invention discloses an all-solid-state flexible small organic molecule electrochromic film as well as a preparation method and application thereof. The preparation method comprises the following steps: dropping an electrochromic solution containing a blocking agent between two flexible conductive substrates, wherein the electrochromic solution comprises a viologen electrochromic material, an anti-aging agent, a coupling agent, a photoinitiator, an ionizing agent and a resin monomer; wherein the concentration of the viologen electrochromic material is 0.1-0.3 mol / L, the mass content of the anti-aging agent is 0.3-0.5%, the mass content of the coupling agent is 0.3-0.6%, the mass content of the photoinitiator is 1.5-3%, and the volume ratio of the ionizing agent to the resin monomer is 1: (2-6); the blocking agent is a small sphere with the diameter of 100-200 microns; tightly extruding the two conductive substrates on the two sides of the electrochromic solution by using a hardening roller; irradiating the pressed conductive substrate by using an ultraviolet curing lamp to cure the electrochromic solution; and rolling to obtain the all-solid-state flexible organic micromolecule electrochromic film with a three-layer structure.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromic materials, and in particular relates to an all-solid-state flexible organic small molecule electrochromic film and a preparation method and application thereof. Background Art

[0002] Electrochromism is a technology that can change color under the action of an electric field, thereby achieving a change in transmittance. The electrochromic film manufactured using this technology can achieve automatic or on-demand color change, and no longer requires the use of sunshade curtains or external sunshade grilles for shading or heat insulation. While integrating the internal space with the external light, it controls glare and heat, and effectively reduces energy consumption.

[0003] According to the different materials used, electrochromic devices are divided into two categories: organic and inorganic. All along, the electrolytes used in organic electrochromic devices are in liquid or gel state. Such electrolytes cannot be used in flexible electrochromic films, and there is a large leakage current during use, resulting in the size of organic electrochromic devices not being able to reach the level of inorganic electrochromic devices. The use of liquid or gel electrolytes also makes the production process of electrochromic windows complicated. The specific implementation process is as follows:

[0004] Use a glass cutter to cut the conductive glass into the required size and shape, then use a glue dispenser to apply a circle of dam glue on the conductive surface of a piece of glass and leave a filling port of about 5 mm, evenly sprinkle the barrier agent of the required size on the dam glue, and then cover another piece of conductive glass on the glued glass according to the size. At this time, it should be noted that the conductive surfaces of the two pieces of glass are opposite and on the inside; solidify the sealant used according to its performance; place the prepared electrochromic solution in a container, place the filling port of the cured small box below the liquid level of the electrochromic solution and place them in the container, then place the container in a vacuum device and start the vacuum pump; after the vacuum degree reaches the predetermined value and is maintained for 10 to 15 minutes, slowly restore the atmospheric pressure. At this time, due to the atmospheric pressure, the electrochromic solution will enter the small box; after the solution is filled, take out the box and use glue to seal the filling port.

[0005] From the above process description, it can be seen that the traditional process of making small molecule electrochromic devices is complicated and the process is not conducive to mass production. In addition, after using liquid or gel electrolytes, the leakage current is large and the thermal expansion coefficient is large. If the electrochromic window is broken, the electrolyte will flow out and cause secondary pollution to the environment. Summary of the invention

[0006] In view of this, on the one hand, some embodiments disclose a method for preparing an all-solid-state flexible organic small molecule electrochromic film, comprising:

[0007] An electrochromic solution containing a barrier agent is dripped between two flexible conductive substrates, wherein the electrochromic solution includes a viologen electrochromic material, an anti-aging agent, a coupling agent, a photoinitiator, an ionizing agent and a resin monomer; wherein the concentration of the viologen electrochromic material is 0.1-0.3 mol / L, the mass content of the anti-aging agent is 3-5‰, the mass content of the coupling agent is 3-6‰, the mass content of the photoinitiator is 1.5-3%, and the volume ratio of the ionizing agent to the resin monomer is 1:2-6; the barrier agent is a small sphere with a diameter of 100-200 μm;

[0008] Using a hard roller, two flexible conductive substrates are tightly squeezed on both sides of the electrochromic solution;

[0009] The electrochromic solution is cured by irradiating the compressed flexible conductive substrate with an ultraviolet curing lamp;

[0010] Roll up to obtain a fully solid-state flexible organic small molecule electrochromic film.

[0011] Some embodiments disclose a method for preparing an all-solid-state flexible organic small molecule electrochromic film, wherein the viologen electrochromic material is 1-1'-dimethyl-4-4'-bipyridyl dichloride, 1-1'-diethyl-4-4'-bipyridyl phosphate or 1,1'-dibenzyl-4,4'-bipyridylium dichloride.

[0012] In some embodiments of the method for preparing an all-solid-state flexible organic small molecule electrochromic film, the anti-aging agent is a UV absorber.

[0013] Some embodiments disclose a method for preparing a fully solid-state flexible organic small molecule electrochromic film, wherein the coupling agent is a silane coupling agent

[0014] In some embodiments, the preparation method of the all-solid-state flexible organic small molecule electrochromic film is disclosed, wherein the initiator is a high-efficiency ultraviolet initiator.

[0015] In some embodiments of the method for preparing an all-solid-state flexible organic small molecule electrochromic film, the ionizing agent is acetonitrile, γ-caprolactone or propylene carbonate.

[0016] In some embodiments of the method for preparing an all-solid-state flexible organic small molecule electrochromic film, the resin monomer is a modified acrylic monomer.

[0017] On the other hand, some embodiments disclose an all-solid-state flexible organic small molecule electrochromic film obtained by a method for preparing the all-solid-state flexible organic small molecule electrochromic film.

[0018] Some embodiments disclose that the all-solid-state flexible organic small molecule electrochromic film has a three-layer structure, wherein the three-layer structure includes a first flexible conductive layer, an electrochromic layer, and a second flexible conductive layer arranged in sequence.

[0019] Some embodiments disclose the application of all-solid-state flexible organic small molecule electrochromic films, which are applied to electrochromic glass. Generally, the electrochromic glass can be straight glass or curved glass.

[0020] The method for preparing the all-solid-state flexible organic small molecule electrochromic film disclosed in the embodiment of the present invention uses a roll-to-roll method to evenly spread the electrochromic solution between two conductive film substrates, and then cure it with ultraviolet light to obtain an all-solid-state organic flexible electrochromic film. This method simplifies the production process of the organic small molecule electrochromic film. The produced flexible electrochromic film has only a three-layer structure, namely, two upper and lower flexible conductive substrates and an electrochromic layer in the middle, which simplifies the five-layer structure of the solid-state electrochromic device in the prior art. The solidified electrochromic film layer has a small leakage current, which expands the size of the organic small molecule electrochromic film and solves the risk of secondary pollution. It has good application prospects in the field of electrochromic glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Schematic diagram of the structure of the all-solid-state flexible organic small molecule electrochromic film disclosed in some embodiments;

[0022] Figure 2 Schematic diagram of the preparation process of the all-solid-state flexible organic small molecule electrochromic film disclosed in some embodiments.

[0023] Reference numerals

[0024] 1 First flexible conductive electrode 2 Second flexible conductive electrode

[0025] 3 Electrochromic film 11 First guide roller

[0026] 12 Second guide roller 13 Hardened roller group

[0027] 14 Glue tank 15 UV curing lamp

[0028] 16 The third guide roller 100 All-solid-state flexible organic small molecule electrovariable

[0029] color film DETAILED DESCRIPTION

[0030] The word "embodiment" used herein as an "exemplary" does not necessarily mean that any embodiment described is superior or better than other embodiments. Performance index tests in the embodiments of the present invention are performed using conventional test methods in the art unless otherwise specified. It should be understood that the terms described in the embodiments of the present invention are only used to describe specific implementation methods and are not intended to limit the contents disclosed in the embodiments of the present invention.

[0031] Unless otherwise specified, the technical and scientific terms used herein have the same meanings as commonly understood by ordinary technicians in the technical field to which the embodiments of the present invention belong; other experimental methods and technical means not specifically specified in the embodiments of the present invention refer to experimental methods and technical means commonly used by ordinary technicians in the field.

[0032] The terms "substantially" and "approximately" used herein are used to describe small fluctuations. For example, they can refer to less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1%, such as less than or equal to ±0.05%. The numerical data represented or presented in the range format herein are used only for convenience and brevity, and should therefore be flexibly interpreted as including not only the values ​​clearly listed as the limits of the range, but also all independent values ​​or sub-ranges contained in the range. For example, the numerical range of "1-5%" should be interpreted as including not only the clearly listed values ​​of 1% to 5%, but also the independent values ​​and sub-ranges within the range shown. Therefore, independent values ​​such as 2%, 3.5% and 4% and sub-ranges such as 1%-3%, 2%-4% and 3%-5% are included in this numerical range. This principle also applies to the range of only one numerical value. In addition, such an interpretation applies regardless of the width of the range or the characteristics described.

[0033] In this document, including in the claims, transitional words such as "comprises," "includes," "with," "having," "containing," "involving," "accommodating," etc. are understood to be open-ended, i.e., meaning "including but not limited to." Only the transitional words "consisting of" and "composed of" are closed transitional words.

[0034] In order to better illustrate the present invention, numerous specific details are provided in the specific examples below. It should be understood by those skilled in the art that the present invention can be implemented without certain specific details. In the embodiments, some methods, means, instruments, equipment, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.

[0035] Under the premise of no conflict, the technical features disclosed in the embodiments of the present invention may be arbitrarily combined, and the resulting technical solutions belong to the contents disclosed in the embodiments of the present invention.

[0036] In some embodiments, the method for preparing the all-solid-state flexible organic small molecule electrochromic film comprises:

[0037] An electrochromic solution containing a barrier agent is dripped between two flexible conductive substrates, wherein the electrochromic solution includes a viologen electrochromic material, an anti-aging agent, a coupling agent, a photoinitiator, an ionizing agent and a resin monomer; wherein the concentration of the viologen electrochromic material is 0.1-0.3 mol / L, the mass content of the anti-aging agent is 3-5‰, the mass content of the coupling agent is 3-6‰, the mass content of the photoinitiator is 1.5-3%, and the volume ratio of the ionizing agent to the resin monomer is 1:2-6; the barrier agent is a small sphere with a diameter of 100-200 μm;

[0038] The two flexible conductive substrates are tightly squeezed on both sides of the electrochromic solution by using a hard roller; the electrochromic solution is evenly dispersed between the two flexible conductive substrates to form a uniform electrochromic liquid film;

[0039] The compressed flexible conductive substrate is irradiated with an ultraviolet curing lamp to solidify the electrochromic liquid film to form an electrochromic film; the electrochromic film is sandwiched between two flexible conductive substrates to form a sandwich three-layer structure;

[0040] Rolling up to obtain a fully solid-state flexible organic small molecule electrochromic film. Usually the conductive substrate is a flexible conductive material. After the electrochromic solution film is solidified to form an electrochromic film, the conductive substrate acts as a flexible conductive electrode, and the electrochromic film sandwiched between two flexible conductive electrodes forms a fully solid-state flexible organic small molecule electrochromic film with an integrated structure.

[0041] Some embodiments disclose a method for preparing an all-solid-state flexible organic small molecule electrochromic film, wherein the viologen electrochromic material is 1-1'-dimethyl-4-4'-bipyridyl dichloride, 1-1'-diethyl-4-4'-bipyridyl phosphate or 1,1'-dibenzyl-4,4'-bipyridylium dichloride.

[0042] In the preparation method of the all-solid-state flexible organic small molecule electrochromic film disclosed in some embodiments, the anti-aging agent is a UV absorber. Generally, the UV absorber includes octocrylene, phenyl o-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone, and the like.

[0043] In some embodiments of the method for preparing the all-solid-state flexible organic small molecule electrochromic film, the coupling agent is a silane coupling agent. Generally, the silane coupling agent includes dodecyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, etc.

[0044] In some embodiments, the preparation method of the all-solid-state flexible organic small molecule electrochromic film is disclosed, wherein the initiator is a high-efficiency ultraviolet initiator. Generally, the high-efficiency ultraviolet initiator includes 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, 1-hydroxy-cyclohexyl-benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and the like.

[0045] In some embodiments of the method for preparing an all-solid-state flexible organic small molecule electrochromic film, the ionizing agent is acetonitrile, γ-caprolactone or propylene carbonate.

[0046] In the preparation method of the all-solid-state flexible organic small molecule electrochromic film disclosed in some embodiments, the resin monomer is a modified acrylic monomer. Generally, the modified acrylic monomer includes methyl methacrylate, hydroxyethyl methacrylate, diethylene glycol phthalate diacrylate, etc.

[0047] In some embodiments of the method for preparing an all-solid-state flexible organic small molecule electrochromic film, the barrier agent is an organic polymer sphere or an inorganic material sphere, for example, the barrier agent can be a polystyrene sphere, a polymethyl methacrylate sphere, or a silica sphere.

[0048] The all-solid-state flexible organic small molecule electrochromic film disclosed in some embodiments is obtained by a preparation method of the all-solid-state flexible organic small molecule electrochromic film.

[0049] Some embodiments disclose an all-solid-state flexible organic small molecule electrochromic film having a three-layer structure, which is a first flexible conductive layer, an electrochromic layer, and a second flexible conductive layer arranged in sequence. Usually, the conductive substrate is a flexible conductive material. After the electrochromic solution is solidified to form the electrochromic film, the conductive substrate serves as the first flexible conductive electrode and the second flexible conductive electrode; the two flexible conductive electrodes and the electrochromic film form a sandwich-type all-solid-state flexible organic small molecule electrochromic film with an integrated structure. Figure 1 As shown, the first flexible conductive electrode 1, the electrochromic film 3 and the second flexible conductive electrode 2 are arranged in sequence to form a fully solid-state flexible organic small molecule electrochromic film with a three-layer structure.

[0050] In some embodiments, Figure 2 As shown, the preparation method of the all-solid-state flexible organic small molecule electrochromic film includes:

[0051] The first guide roller 11 and the second guide roller 12 are respectively arranged to release the first flexible conductive electrode 1 and the second flexible conductive electrode 2, and the released flexible conductive electrodes 1 and the second flexible conductive electrodes 2 overlap each other and enter the hardening roller group 13;

[0052] The electrochromic solution containing the barrier agent is injected into the glue tank 14 of the hard roller glue machine, and after adjusting the dripping speed, it is evenly dripped between the first flexible conductive electrode 1 and the second flexible conductive electrode 2, wherein the electrochromic solution comprises a viologen electrochromic material, an anti-aging agent, a coupling agent, a photoinitiator, an ionizing agent and a resin monomer; wherein the concentration of the viologen electrochromic material is 0.1-0.3 mol / L, the mass content of the anti-aging agent is 3-5‰, the mass content of the coupling agent is 3-6‰, the mass content of the photoinitiator is 1.5-3%, and the volume ratio of the ionizing agent to the resin monomer is 1:2-6; the barrier agent is a polystyrene ball with a diameter of 100-200 μm;

[0053] The first flexible conductive electrode 1 and the second flexible conductive electrode 2 are tightly squeezed on both sides of the electrochromic solution by using a hardened roller group 13; the electrochromic solution is continuously and evenly dispersed between the two flexible conductive electrodes to form a uniform electrochromic solution liquid film;

[0054] Using an ultraviolet curing lamp 15 to irradiate the compacted conductive substrate to solidify the electrochromic solution film between the first flexible conductive electrode 1 and the second flexible conductive electrode 2;

[0055] The third guide roller 16 is used to roll up the film, thereby obtaining a fully solid-state flexible organic small molecule electrochromic film 100 .

[0056] Some embodiments disclose applications of all-solid-state flexible organic small molecule electrochromic films, and all-solid-state flexible organic small molecule electrochromic films are applied to electrochromic glass. Generally, the all-solid-state flexible organic small molecule electrochromic film is compounded with glass to obtain electrochromic glass.

[0057] The method for preparing the all-solid-state flexible organic small molecule electrochromic film disclosed in the embodiment of the present invention uses a roll-to-roll method to evenly spread the electrochromic solution between two conductive film substrates, and then cure it with ultraviolet light to obtain an all-solid-state organic flexible electrochromic film. This method simplifies the production process of the organic small molecule electrochromic film. The produced flexible electrochromic film has only a three-layer structure, namely, two upper and lower flexible conductive substrates and an electrochromic layer in the middle, which simplifies the five-layer structure of the solid-state electrochromic device in the prior art. The solidified electrochromic film layer has a small leakage current, which expands the size of the organic small molecule electrochromic film and solves the risk of secondary pollution. It has good application prospects in the field of electrochromic glass.

[0058] The technical solutions disclosed in the embodiments of the present invention and the technical details disclosed in the embodiments are merely illustrative of the inventive concept of the present invention and do not constitute a limitation on the technical solutions of the embodiments of the present invention. Any conventional changes, replacements or combinations of the technical details disclosed in the embodiments of the present invention have the same inventive concept as the present invention and are within the protection scope of the claims of the present invention.

Claims

1. A method for preparing an all-solid-state flexible organic small molecule electrochromic film, characterized in that: include: An electrochromic solution containing a barrier is dripped between two flexible conductive substrates; the electrochromic solution comprises a viologen electrochromic material, an anti-aging agent, a coupling agent, a photoinitiator, an ionizing agent and a resin monomer; wherein the concentration of the viologen electrochromic material is 0.1-0.3 mol / L, the mass content of the anti-aging agent is 3-5‰, the mass content of the coupling agent is 3-6‰, the mass content of the photoinitiator is 1.5-3%, and the volume ratio of the ionizing agent to the resin monomer is 1:2-6; the barrier is a small sphere with a diameter of 100-200 μm; Using a hard roller, two flexible conductive substrates are tightly squeezed on both sides of the electrochromic solution; Using an ultraviolet curing lamp to irradiate the compacted conductive substrate to cure the electrochromic solution; Roll up to obtain a fully solid-state flexible organic small molecule electrochromic film.

2. The method for preparing the all-solid-state flexible organic small molecule electrochromic film according to claim 1, characterized in that: The viologen electrochromic material is a 1-1'-dimethyl-4-4'-bipyridyl dichloride compound, a 1-1'-diethyl-4-4'-bipyridyl phosphate or a 1,1'-dibenzyl-4,4'-bipyridylium salt dichloride.

3. The method for preparing the all-solid-state flexible organic small molecule electrochromic film according to claim 1, characterized in that: The anti-aging agent is a UV absorber.

4. The method for preparing the all-solid-state flexible organic small molecule electrochromic film according to claim 1, characterized in that: The coupling agent is a silane coupling agent.

5. The method for preparing the all-solid-state flexible organic small molecule electrochromic film according to claim 1, characterized in that: The initiator is a high-efficiency ultraviolet initiator.

6. The method for preparing the all-solid-state flexible organic small molecule electrochromic film according to claim 1, characterized in that: The ionizing agent is acetonitrile, γ-caprolactone or propylene carbonate.

7. The method for preparing the all-solid-state flexible organic small molecule electrochromic film according to claim 1, characterized in that: The resin monomer is a modified acrylic monomer.

8. An all-solid-state flexible organic small molecule electrochromic film obtained by the preparation method of the all-solid-state flexible organic small molecule electrochromic film according to claim 1.

9. The all-solid-state flexible organic small molecule electrochromic film according to claim 8, characterized in that: The film has a three-layer structure, which includes a first flexible conductive layer, an electrochromic layer and a second flexible conductive layer which are arranged in sequence.

10. Application of all-solid-state flexible organic small molecule electrochromic film, characterized in that: The all-solid-state flexible organic small molecule electrochromic film is applied to electrochromic glass.

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