CN115073505A - Electrochromic material, thin film, device and application thereof - Google Patents

Electrochromic material, thin film, device and application thereof Download PDF

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CN115073505A
CN115073505A CN202210639887.3A CN202210639887A CN115073505A CN 115073505 A CN115073505 A CN 115073505A CN 202210639887 A CN202210639887 A CN 202210639887A CN 115073505 A CN115073505 A CN 115073505A
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electrochromic
film
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electrochromic material
electrochromic device
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张宇模
杨佰鸽
张晓安
李成龙
王悦
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Jilin University
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
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    • G—PHYSICS
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    • 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
    • G02F1/1514—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
    • 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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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
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    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms

Abstract

The invention provides an electrochromic material, a film, a device and application thereof, wherein the electrochromic material comprises an electrochromic Lewis base and a Lewis acid; wherein the Lewis acid comprises multiple resonance boron nitrogen doped triaryl borane and derivatives thereof. The invention can realize reversible optical property adjustment under the condition of electrical stimulation by combining the triaryl borane with narrow-band emissive texture multiple resonance boron-nitrogen doping and the derivative thereof with the electro-Lewis base to form the electrochromic material, and when the electrochromic material is used for preparing an electrochromic device, the electrochromic material has narrow-band spectral property, thereby having high color purity and electroluminescent property, and being beneficial to improving the application prospect of the electrochromic device in the display field.

Description

Electrochromic material, thin film, device and application thereof
Technical Field
The invention relates to the technical field of functional materials, in particular to an electrochromic material, a thin film, a device and application thereof.
Background
The electrochromic material can reversibly adjust optical properties (such as color existence, color intensity, transmittance, reflectivity, absorbance and the like) of the electrochromic material under the stimulation of electricity. The optical fiber has abundant optical property changes and has good application prospects in the fields of anti-counterfeiting, information storage, information display, sensing and the like, so that the optical fiber is widely researched. Existing electrochromic materials can be broadly classified into two categories according to mechanisms: one is that the molecule has redox activity and different redox states of the molecule correspond to different optical properties; the other is to introduce an acid-base response dye into an electrochromic system by utilizing an electro-acid-base mechanism, and realize the switching of optical properties through intermolecular proton transfer electron coupling.
However, most of the above two types of materials have large conjugated structures, and the highest occupied molecular orbital and the lowest vacant molecular orbital of the molecule are distributed on the whole molecule, thereby resulting in a broad spectrum. The wide spectrum of light results in low color purity, which is a significant obstacle to limiting the application of electrochromic materials in the display field. Therefore, an electrochromic system with a narrow-band spectrum needs to be developed, and the application prospect of the electrochromic material in the display field is improved.
Disclosure of Invention
The invention solves the problem of how to provide an electrochromic system with narrow-band spectrum, improve the color purity and improve the application prospect of electrochromic materials in the display field.
To solve at least one aspect of the above problems, the present invention provides an electrochromic material including an electrogenerated lewis base and a lewis acid; wherein the Lewis acid comprises triarylborane doped with multiple resonance boron nitrogen and derivatives thereof.
Preferably, the lewis base comprises at least one of benzoquinone and its derivatives, anthraquinone and its derivatives, or naphthoquinone and its derivatives.
Preferably, the mass ratio of the Lewis base and the Lewis acid is 1: 0.01-1000.
The invention can realize reversible optical property adjustment under the condition of electrical stimulation by combining the triaryl borane with narrow-band emissive texture multiple resonance boron-nitrogen doping and derivatives thereof with the electro-Lewis base to form the electrochromic material, and when the electrochromic material is used for preparing an electrochromic device, the electrochromic material has narrow-band spectral properties, thereby having high color purity and simultaneously having the electroluminescent photochromic properties and being beneficial to improving the application prospect of the electrochromic device in the display field.
Another object of the present invention is to provide an electrochromic film comprising the above electrochromic material, a film-forming substance, a plasticizer and an electrolyte.
Preferably, the plasticizer comprises at least one of gamma-butyrolactone, gamma-valerolactone, propylene carbonate, cyclohexanone, N dimethylformamide, dimethyl sulfoxide, toluene, xylene, mesitylene, 1, 3-trimethylcyclohexenone, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, diphenyl ether, dodecane, and glycerol.
Preferably, the electrolyte comprises at least one of an inorganic metal salt containing metal ions, an organic metal salt containing metal ions, a tetraalkylammonium salt, and an ionic liquid, wherein the metal ions comprise at least one of Li, Na, K, Rb, Cs, Cu, and Ag salts; the ionic liquid comprises at least one of 1-butyl pyridine bromide, 1-butyl-4-methylpyridine hexafluorophosphate, 1-butyl-3-methylpyridine bis (trifluoromethanesulfonyl) imide and 1-butyl-4-methylpyridine tetrafluoroborate.
Preferably, the mass ratio of the electrochromic material, the film-forming substance, the plasticizer and the electrolyte is 1:0.1-1000:0.1-1000: 0.01-1000.
According to the invention, multiple resonance boron-nitrogen doped triaryl borane with narrow-band spectral properties and derivatives thereof are introduced into an electrochromic system, reversible optical property adjustment can be realized under an electrical stimulation condition by utilizing the coordination effect between the triaryl borane and an electro-Lewis base, and the prepared electrochromic film also has narrow-band spectral properties, has high color purity, and is beneficial to the promotion of the application prospect of the electrochromic film in the display field; in addition, the film forming material can improve the film forming performance, the plasticizer can improve the mixing effect, and the electrolyte has an ion transmission effect, so that the electrochromic film can be adjusted through electrical stimulation; in addition, the film has the property of electrochromism, and the bifunctional film has wide application prospects in the aspects of information storage, anti-counterfeiting, sensing display and the like.
Another object of the present invention is to provide an electrochromic device comprising the above electrochromic film and an electrode; wherein the electrochromic film is located between the two electrodes.
Preferably, the electrochromic device further comprises an ion storage film and/or an ion conductive film.
The electrochromic device provided by the invention has a narrow-band spectrum, and simultaneously has electrochromic and electroluminescent photochromic properties, and compared with the prior art, the electrochromic device has the same beneficial effects as an electrochromic film, and is not repeated herein.
It is a further object of the present invention to provide applications of the above electrochromic device in the fields of information storage, anti-counterfeiting, sensing and display.
Compared with the prior art, the application of the electrochromic device in the optical regulation device has the same beneficial effects as the electrochromic device, and the details are not repeated.
Drawings
FIG. 1 is a schematic representation of a prior art electrochromic device based on a redox mechanism;
FIG. 2 is a schematic diagram of a prior art electrochromic device based on acid-base regulation;
FIG. 3 is a diagram illustrating the mechanism of the conversion of the optical properties of multiple resonance boron-nitrogen doped triarylborane and its derivatives with an electro-Lewis base in an embodiment of the present invention;
FIG. 4 is a schematic flow chart of a method for manufacturing an electrochromic device according to an embodiment of the present invention;
fig. 5 is an absorption spectrum and an emission spectrum of multiple resonance boron-nitrogen doped triarylborane and methoxy p-benzoquinone in an electrochromic device in example 1 under voltage stimulation;
FIG. 6 is a spectrum of an electrochromic device under voltage stimulation in example 1 of the present invention;
FIG. 7 is a schematic structural view of an electrochromic device in example 2 of the present invention;
FIG. 8 is a spectrum of an electrochromic device under voltage stimulation in example 2 of the present invention;
FIG. 9 is a schematic structural view of an electrochromic device in example 3 of the present invention;
fig. 10 is a graph showing the change of the spectral intensity of the electrochromic device under voltage stimulation in example 3 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments thereof are described in detail below.
It should be noted that the features in the embodiments of the present invention may be combined with each other without conflict. The terms "comprising," "including," "containing," and "having" are intended to be inclusive, i.e., that additional steps and other ingredients may be added without affecting the result. The above terms encompass the terms "consisting of … …" and "consisting essentially of … …". Materials, equipment and reagents are commercially available unless otherwise specified.
In the prior art, electrochromic materials are roughly classified into two types according to mechanisms: one is that the molecule has redox activity and different redox states of the molecule correspond to different optical properties; the second type is that an acid-base response dye is introduced into an electrochromic system by utilizing an electro-acid-base mechanism, and the optical property is switched by intermolecular proton transfer electron coupling.
Illustratively, the step of preparing an electrochromic device based on a direct redox mechanism comprises:
1. CN-PTPA was dissolved in chloroform (CHCl) at 25mg/mL 3 ) Obtaining electrochromic functional solution;
wherein, the structural general formula of CN-PTPA is shown as formula (1):
Figure BDA0003683405270000041
2. dissolving 3g of polymethyl methacrylate (PMMA) and 0.3g of lithium perchlorate in Propylene Carbonate (PC) to obtain a gel electrolyte layer solution;
3. the ITO glass electrode is sequentially and respectively cleaned by water, acetone and isopropanol for 15min in an ultrasonic way;
4. taking a clean ITO glass substrate, coating an electrochromic functional solution on the clean ITO glass substrate, and drying the ITO glass substrate in a vacuum environment to obtain an electrochromic film; applying a gel electrolyte layer to the dried electrochromic film; and then, attaching the other clean ITO glass substrate to the device, and sealing the device by using a sealant to obtain the electrochromic device. The structure of the obtained electrochromic device is shown in fig. 1.
The preparation method of the electrochromic device based on the regulation and control of the electro-acid and the alkali comprises the following steps:
1. curing 15-20 parts of PMMA, 5-8 parts of an electro-acid base, 10-18 parts of electrolyte, 3-5 parts of a pH color-changing response dye matched with the electro-acid base and 2-4 parts of a light stabilizer to obtain an electro-acid base color-changing film;
2. curing 10-15 parts of PMMA, 3-6 parts of an electro-acid base, 8-12 parts of an electrolyte and 1-3 parts of a light stabilizer to obtain an ion storage film;
3. and finally, buckling the two conductive films with each other to obtain the electrochromic device based on the electro-acid-base. The structure of the obtained electrochromic device is shown in fig. 2.
Because the material used in the preparation process is a large conjugated structure, the highest molecular occupied orbit and the lowest molecular vacant orbit of the molecule are distributed on the whole molecule, so that a wide spectrum is caused, and the obtained electrochromic device has low color purity and is limited in application in the display field.
The embodiment of the invention provides an electrochromic material, which comprises an electro Lewis base and a Lewis acid; wherein the Lewis acid comprises multiple resonance boron nitrogen doped triaryl borane and derivatives thereof.
The structural general formula of the multiple resonance boron-nitrogen doped triaryl borane and the derivative thereof is shown as the formula (2) or (3):
Figure BDA0003683405270000051
in the formula, R 1 -R 21 Selected from-H, -OCH 3 ，-N(C 2 H 5 ) 2 ，-N(C 4 H 9 ) 2 ,，-OH，-ph-CH 3 ，
-N(ph) 2 Or an aromatic ring.
Wherein, the electrogenerated Lewis base comprises at least one of benzoquinone and derivatives thereof, anthraquinone and derivatives thereof or naphthoquinone and derivatives thereof; the structural general formula of the electro-Lewis base is shown as any one of formulas (4) to (9):
Figure BDA0003683405270000061
in the formula, R 1 -R 8 Selected from-H, -OCH 3 ，-N(C 2 H 5 ) 2 ，-N(C 4 H 9 ) 2 ,，-OH，-ph-CH 3 ，-N(ph) 2 Or an aromatic ring.
The mass ratio of the electrogenerated Lewis base to the Lewis acid is 1: 0.01-1000; preferably 1: 1-100.
The triaryl borane doped with multiple resonances boron and nitrogen and the derivatives thereof can induce the separation of the occupied orbitals of the highest molecules and the empty orbitals of the lowest molecules, have the property of narrow-band spectrum and do not have the property of electrochromism. However, the invention discovers SP in molecules of multiple resonance boron-nitrogen doped triaryl borane and derivatives thereof through research 2 Hybrid boron above idle P railThe tract is rendered lewis acidic so that it can coordinate with a lewis base, thereby enabling a change in optical properties.
Based on the above, the invention firstly provides the method for introducing the triaryl borane doped with multiple resonance boron nitrogen and the derivative thereof with narrow-band spectrum into an electrochromic system by utilizing an electro-Lewis acid-base mechanism and taking the triaryl borane as the electrochromic material, and the aim of realizing color change under electric stimulation is fulfilled by the coordination of the triaryl borane and the derivative thereof with the electro-Lewis base. Wherein, the electro-Lewis base is a material capable of changing the electron cloud density under the stimulation of voltage, and comprises at least one of benzoquinone and derivatives thereof, anthraquinone and derivatives thereof or naphthoquinone and derivatives thereof.
Another embodiment of the present invention provides an electrochromic film comprising the above electrochromic material, a film-forming substance, a plasticizer, and an electrolyte; wherein the mass ratio of the electrochromic material, the film-forming substance, the plasticizer and the electrolyte is 1:0.1-1000:0.1-1000: 0.01-1000; preferably 1:10-500:10-500: 0.1-100.
Wherein the film forming substance comprises at least one of polymethyl methacrylate and derivatives thereof, polyethylene glycol and derivatives thereof, polyamino acid and derivatives thereof, polypropylene and derivatives thereof, polyacrylic acid and derivatives thereof, polyacrylamide and derivatives thereof, polyacrylate and derivatives thereof, polyvinyl alcohol and derivatives thereof, polyimide and derivatives thereof, polyvinyl chloride and derivatives thereof, and polytetrafluoroethylene and derivatives thereof; the plasticizer is one or more of high boiling point organic liquids, for example, including at least one of butyrolactone, propylene carbonate, cyclohexanone, N dimethylformamide, dimethyl sulfoxide, toluene, xylene, mesitylene, 1, 3-trimethylcyclohexenone, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, diphenyl ether, dodecane, and glycerol; the electrolyte comprises at least one of inorganic metal salt of metal ions, organic metal salt containing metal ions, quaternary tetraalkylammonium salt and ionic liquid, wherein the metal ions are selected from one or more of Li, Na, K, Rb, Cs, Cu and Ag salt; the ionic liquid comprises at least one of 1-butyl pyridine bromide, 1-butyl-4-methylpyridine hexafluorophosphate, 1-butyl-3-methylpyridine bis (trifluoromethanesulfonyl) imide and 1-butyl-4-methylpyridine tetrafluoroborate. The film forming material can improve the film forming performance, the plasticizer can improve the material mixing effect, and the electrolyte has an ion transmission effect, so that the electrochromic film can be adjusted through electrical stimulation; in addition, the film has the property of electrofluorescent discoloration, and the bifunctional film has wide application prospects in the aspects of information storage, anti-counterfeiting, sensing display and the like.
Another embodiment of the present invention provides an electrochromic device comprising the above electrochromic film and an electrode; wherein the electrochromic film is located between the two electrodes. Namely, the electrochromic device having a single-layer structure.
In some embodiments, the electrochromic device further includes an ion storage thin film and/or an ion conductive thin film, wherein the electrochromic thin film is attached to the ion storage thin film or the ion conductive thin film and is located between the two electrodes, that is, the electrochromic device having a two-layer structure.
And the electrochromic film is attached to the ion storage film and the ion conductive film and is positioned between the two electrodes, namely the electrochromic device with a three-layer structure.
Due to the adoption of the electrochromic material based on multiple resonance boron-nitrogen doped triarylborane and derivatives thereof and the electro-Lewis base, the obtained electrochromic film and device have electrochromic and electro-fluorescent photochromic properties, narrow-band spectrum and high color purity, and can improve the application prospect of the electrochromic device in the display field.
Specifically, as shown in fig. 3, the switching principle of the electrochromic device provided in this embodiment is as follows: the multiple resonance boron nitrogen doped triaryl borane and the derivative thereof have narrow-band spectral properties, the initial state of the triaryl borane has color and fluorescence, when voltage stimulation is applied, the Lewis base in the device is reduced to generate a negative ion free radical with higher electron cloud density, and the negative ion free radical can be coordinated with the multiple resonance boron nitrogen doped triaryl borane and the derivative thereof which are in Lewis acidity, and the color and the fluorescence disappear at the moment; when a reverse voltage stimulus is applied, the negative ion free radicals can be reversibly oxidized into an initial state with low electron cloud density, so that the coordination between the electro-Lewis base and the triaryl borane doped with multiple resonance boron nitrogen and the derivative thereof is released, and the color and the fluorescence are re-displayed. That is, the color and fluorescence change of the device is realized by controlling the coordination of triaryl borane doped with multiple resonance boron nitrogen and derivatives thereof through the reversible redox of the electric stimulation electro-Lewis base. By providing an electro-Lewis acid-base coordination mechanism, a new dominant material can be introduced into an electrochromic system, so that an electrochromic device with more excellent performance is obtained, and the application of the electrochromic device in the display field is promoted.
The preparation method of the electrochromic device comprises the following steps:
step S1, adding the film forming substance, the plasticizer, the electrolyte and the electrochromic material into a solvent according to a ratio to prepare an electrochromic functional solution;
step S2, coating the electrochromic functional solution on the surface of an electrode, and obtaining an electrochromic film after the solvent is volatilized;
and step S3, preparing the electrochromic film to obtain the electrochromic device.
The electrochromic functional solution consisting of the film forming material, the plasticizer, the electrolyte and the electrochromic material is coated on the surface of an electrode, after the solvent is volatilized, the electrochromic film is formed by solidification, and then the electrochromic film is used for preparing an electrochromic device.
Wherein, in the step S1, the solvent comprises one or more of dichloromethane, acetonitrile, tetrahydrofuran and 1, 4-dioxane.
In the step S2, the method for coating the electrochromic functional solution on the surface of the electrode includes one or more of dropping coating, blade coating, spin coating, and LB draw film technology.
In addition, before the electrochromic functional solution is applied to the electrode, the electrode needs to be cleaned, for example, an Indium Tin Oxide (ITO) glass electrode, and the cleaning step includes: soaking the ITO glass electrode in a mixed solution of ammonia water and hydrogen peroxide in a volume ratio of 3:1 for 24 hours, then ultrasonically cleaning the ITO glass electrode for 5min by using deionized water, and repeating the cleaning for 3 times; then ultrasonically cleaning with acetone for 5min, and repeating for 3 times; finally, ultrasonically cleaning the mixture for 30min by using isopropanol, and drying the mixture by using nitrogen.
It is understood that the preparation method thereof is different according to the structure of the electrochromic device, and when preparing the electrochromic device having a single-layer structure, the following steps are included:
step S1, adding a film forming substance, a plasticizer, an electrolyte and the electrochromic material into a solvent according to a ratio to prepare an electrochromic functional solution;
step S2, coating the electrochromic functional solution on the surface of an electrode, and obtaining an electrochromic film after the solvent is volatilized;
and step S3, attaching the electrochromic film to another electrode to obtain the electrochromic device with a single-layer structure.
Accordingly, when an electrochromic device having a two-layer structure is prepared, the following steps are included:
step T1, adding a film forming substance, a plasticizer, an electrolyte and the electrochromic material into a solvent according to a ratio to prepare an electrochromic functional solution, and preparing an ion storage layer solution;
step T2, coating the electrochromic functional solution on the surface of an electrode, and obtaining an electrochromic film after the solvent is volatilized;
step T3, coating the ion storage layer solution on the surface of an electrode to obtain an ion storage film;
and T4, attaching the electrochromic film and the ion storage film to obtain the electrochromic device with the double-layer structure.
The ion storage layer solution is prepared by taking functional molecules with redox activity as main functional materials for balancing charges, and comprises at least one of hydroquinone and derivatives thereof, ferrocene and derivatives thereof, and 2,2,6, 6-tetramethyl piperidine oxynitride and derivatives thereof.
When an electrochromic device having a three-layer structure is prepared, the following steps are included:
step U1, adding a film forming substance, a plasticizer, an electrolyte and the electrochromic material into a solvent according to a ratio to prepare an electrochromic functional solution, and preparing an ion storage layer solution and an ion conducting layer solution;
step U2, coating the electrochromic functional solution on the surface of an electrode, and obtaining an electrochromic film after the solvent is volatilized;
step U3, coating the ion storage layer solution on the surface of an electrode, continuing to coat the ion conducting layer solution after the solvent is volatilized, and obtaining an ion storage film and an ion conducting film after the solvent is volatilized;
and step U4, sequentially attaching the electrochromic film, the ion conductive film and the ion storage film to obtain the electrochromic device with a three-layer structure.
In some embodiments, the mass ratio of each component is: 15-70% of film-forming material, 25-80% of plasticizer, 1-5% of electrolyte, 0.1-5% of electrogenerated Lewis base and 0.01-2% of Lewis acid; in order to improve the performance of the electrochromic device, different proportions are adopted when the electrochromic device with different structures is prepared.
Specifically, when an electrochromic device having a single-layer structure is prepared, 15 to 40 wt% of a film-forming substance, 60 to 80 wt% of a plasticizer, 1 to 5 wt% of an electrolyte, 0.1 to 1 wt% of an electro-Lewis base, and 0.01 to 0.1 wt% of a Lewis acid are added to a solvent to prepare an electrochromic functional solution;
when preparing an electrochromic device having a double-layer structure, adding 15-40 wt% of a film-forming substance, 50-70 wt% of a plasticizer, 1-5 wt% of an electrolyte, 0.1-1 wt% of an electro-Lewis base, and 0.01-0.1 wt% of a Lewis acid to a solvent to prepare an electrochromic functional solution;
when an electrochromic device having a three-layer structure is prepared, 50-70 wt% of a film-forming substance, 25-40 wt% of a plasticizer, 1-5 wt% of an electrolyte, 1-5 wt% of an electro-Lewis base, and 0.5-2 wt% of a Lewis acid are added to a solvent to prepare an electrochromic functional solution.
Still another embodiment of the present invention is to provide the application of the above electrochromic device in the fields of information storage, anti-counterfeiting, sensing and display.
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. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer.
Example 1
1.1, 24.7 wt% of polymethyl methacrylate, 1.09 wt% of tetrabutylammonium hexafluorophosphate, 73.72 wt% of butyrolactone and 0.45 wt% of methoxy p-benzoquinone (BQ-OCH) 3 ) Dissolving 0.04 wt% of multiple resonance boron-nitrogen doped triaryl borane in a tetrahydrofuran solvent, stirring and dissolving to obtain a uniformly mixed solution, namely an electrochromic functional solution;
1.2, dissolving a copolymer of benzophenone and 2,2,6, 6-tetramethylpiperidine oxynitride in tetrahydrofuran to obtain a solution with the concentration of 20mg/mL, namely an ion storage layer solution;
1.3, soaking the ITO glass electrode in a mixed solution of ammonia water and hydrogen peroxide in a volume ratio of 3:1 for 24 hours, then ultrasonically cleaning the ITO glass electrode for 5min by using deionized water, and repeating the cleaning for 3 times; then ultrasonically cleaning with acetone for 5min, and repeating for 3 times; finally, ultrasonically cleaning the ITO electrode by using isopropanol for 30min, and drying the ITO electrode by using nitrogen to obtain a cleaned ITO electrode;
1.4, dripping the electrochromic functional solution on the surface of a clean ITO electrode, and volatilizing to obtain an electrochromic layer film;
1.5, coating the ion storage layer solution on the surface of a clean ITO glass electrode at the rotating speed of 500rpm, curing for 5-10min under 254nm ultraviolet light, and washing the surface of the film by dichloromethane to obtain an ion storage film;
and 1.6, bonding the prepared electrochromic film and the ion storage film together to obtain the electrochromic device with a two-layer structure.
The preparation flow of the electrochromic device having the two-layer structure provided in this example is shown in fig. 4.
The performance of the electrochromic device having a two-layer structure provided in this example was analyzed, the device had a narrow-band spectrum, as shown in fig. 5 and 6, the half-peak width thereof was only 30nm, the initial absorption peak of the device was 465nm, the color was quenched upon application of-0.9V, the color was recovered upon application of 0V, and in addition, the device had an electrochromic capability at the same time.
Example 2
2.1, dissolving 24.7 wt% of polymethyl methacrylate, 1.09 wt% of tetrabutylammonium hexafluorophosphate, 73.72 wt% of butyrolactone, 0.45 wt% of p-Benzoquinone (BQ) and 0.04 wt% of multiple resonance boron-nitrogen doped triarylborane in a mixed solvent of tetrahydrofuran and cyclohexanone, and stirring for dissolving to obtain a uniformly mixed solution, namely an electrochromic functional solution;
2.2, soaking the ITO glass electrode in a mixed solution of ammonia water and hydrogen peroxide in a volume ratio of 3:1 for 24 hours, then ultrasonically cleaning the ITO glass electrode for 5min by using deionized water, and repeating the cleaning for 3 times; then ultrasonically cleaning with acetone for 5min, and repeating for 3 times; finally, ultrasonically cleaning the ITO electrode by using isopropanol for 30min, and drying the ITO electrode by using nitrogen to obtain a cleaned ITO electrode;
2.3, dripping the electrochromic functional solution on the surface of a clean ITO electrode, and volatilizing to obtain an electrochromic layer film;
and 2.4, attaching the prepared electrochromic functional film and another clean ITO electrode together to obtain the electrochromic device with a single-layer structure.
The structure of the electrochromic device having a single-layer structure manufactured in this example is shown in fig. 7.
The performance of the electrochromic device having a single-layer structure provided in this example was analyzed, and the device had a narrow-band spectrum, as shown in fig. 8, with a half-peak width of only 30nm, and an initial operating voltage of the device of-1.9V to 0V, where color and fluorescence were quenched at-1.9V and color and fluorescence were recovered at 0V.
Example 3
3.1, dissolving 59.0 wt% of polymethyl methacrylate, 4.91 wt% of tetrabutylammonium hexafluorophosphate, 34.4 wt% of butyrolactone, 1.06 wt% of p-Benzoquinone (BQ) and 0.63 wt% of multiple resonance boron nitrogen doped triaryl borane in tetrahydrofuran, and stirring to dissolve to obtain a uniformly mixed solution, namely the electrochromic functional solution;
3.2, dissolving 60.2 wt% of polymethyl methacrylate, 25.1 wt% of tetrabutyl ammonium hexafluorophosphate and 14.7 wt% of butyrolactone in acetonitrile, and stirring for dissolving to obtain a uniformly mixed solution, namely an ion conducting layer solution;
3.3, adding 0.05mol/L of p-benzoquinone and 0.1mol/L of hydroquinone into the solution of the ion conducting layer, stirring and dissolving to obtain a uniformly mixed solution, namely the solution of the ion storage layer;
3.4, soaking the ITO glass electrode in a mixed solution of ammonia water and hydrogen peroxide in a volume ratio of 3:1 for 24 hours, then ultrasonically cleaning the ITO glass electrode for 5min by using deionized water, and repeating the cleaning for 3 times; then ultrasonically cleaning with acetone for 5min, and repeating for 3 times; finally, ultrasonically cleaning the ITO electrode by using isopropanol for 30min, and drying the ITO electrode by using nitrogen to obtain a cleaned ITO electrode;
3.5, dripping the electrochromic layer solution on the surface of a clean ITO electrode, and volatilizing to obtain an electrochromic film;
3.6, dripping the solution of the ion storage layer on the surface of a clean ITO glass electrode, and volatilizing to obtain an ion storage film; continuously dripping the ion conducting layer solution on the ion storage film, and volatilizing to obtain an ion storage film and an ion conducting film;
and 3.7, sequentially attaching the electrochromic film, the ion conductive film and the ion storage film together to obtain the electrochromic device with a three-layer structure.
The structure of the electrochromic device having a three-layer structure provided in this embodiment is shown in fig. 9.
The performance of the electrochromic device having a three-layer structure provided in this example was analyzed, and the device had a narrow-band spectrum, as shown in fig. 10, and the half-peak width thereof was only 30nm, and the operating voltage of the device was-1.5V to 0V, where color and fluorescence were quenched at-1.5V and color and fluorescence were recovered at 0V.
Example 4
4.1, dissolving 30 wt% of polymethyl methacrylate, 2 wt% of tetrabutylammonium hexafluorophosphate, 66.9 wt% of butyrolactone, 1 wt% of naphthoquinone and 0.1 wt% of multiple resonance boron-nitrogen doped methoxy triaryl borane in dichloromethane, and stirring to dissolve to obtain a uniformly mixed solution, namely an electrochromic functional solution;
4.2, dissolving 2,2,6, 6-tetramethylpiperidine oxynitride in acetonitrile to obtain a solution of the 2,2,6, 6-tetramethylpiperidine oxynitride with the concentration of 20mg/mL, namely the solution of the ion storage layer;
4.3, soaking the ITO glass electrode in a mixed solution of ammonia water and hydrogen peroxide in a volume ratio of 3:1 for 24 hours, then ultrasonically cleaning the ITO glass electrode for 5 minutes by using deionized water, and repeating the steps for 3 times; then ultrasonically cleaning with acetone for 5min, and repeating for 3 times; finally, ultrasonically cleaning the ITO electrode by using isopropanol for 30min, and drying the ITO electrode by using nitrogen to obtain a cleaned ITO electrode;
4.4, coating the electrochromic functional solution on the surface of an ITO electrode by scraping, and volatilizing to obtain an electrochromic film;
4.5, spin-coating the ion storage layer solution on the surface of a clean ITO glass electrode, and volatilizing to obtain an ion storage film;
and 4.6, bonding the prepared electrochromic film and the ion storage film together to obtain the electrochromic device with the two-layer structure.
Example 5
5.1, dissolving 20 wt% of polymethyl methacrylate, 5 wt% of tetrabutylammonium hexafluorobromide, 73.5 wt% of propylene carbonate, 0.5 wt% of naphthoquinone and 1 wt% of multiple resonance boron nitrogen doped phenyl triaryl borane in a mixed solvent of tetrahydrofuran and acetonitrile, and stirring for dissolving to obtain a uniformly mixed solution, namely an electrochromic functional solution;
5.2, soaking the ITO glass electrode in a mixed solution of ammonia water and hydrogen peroxide in a volume ratio of 3:1 for 24 hours, then ultrasonically cleaning the ITO glass electrode for 5min by using deionized water, and repeating the cleaning for 3 times; then ultrasonically cleaning with acetone for 5min, and repeating for 3 times; finally, ultrasonically cleaning the ITO electrode by using isopropanol for 30min, and drying the ITO electrode by using nitrogen to obtain a cleaned ITO electrode;
5.3, dripping the electrochromic functional solution on the surface of a clean ITO electrode, and volatilizing to obtain an electrochromic layer film;
and 5.4, attaching the prepared electro-functional film and another clean ITO electrode together to obtain the electrochromic device with the single-layer structure.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications are intended to fall within the scope of the invention.

Claims (10)

1. An electrochromic material comprising an electrolewis base and a lewis acid; wherein the Lewis acid comprises multiple resonance boron nitrogen doped triaryl borane and derivatives thereof.
2. The electrochromic material of claim 1 wherein the electrolewis base comprises at least one of benzoquinone and derivatives thereof, anthraquinone and derivatives thereof, or naphthoquinone and derivatives thereof.
3. The electrochromic material according to claim 1, characterized in that the mass ratio of the electrolewis base and the lewis acid is 1: 0.01-1000.
4. An electrochromic film comprising the electrochromic material according to any one of claims 1 to 3, a film-forming substance, a plasticizer and an electrolyte.
5. The electrochromic film of claim 4, wherein the plasticizer comprises at least one of gamma butyrolactone, gamma valerolactone, propylene carbonate, cyclohexanone, N dimethylformamide, dimethyl sulfoxide, toluene, xylene, mesitylene, 1, 3-trimethylcyclohexenone, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, diphenyl ether, dodecane, and glycerol.
6. The electrochromic film of claim 4, wherein the electrolyte comprises at least one of an inorganic metal salt containing metal ions, an organic metal salt containing metal ions, a tetraalkylammonium salt, and an ionic liquid, wherein the metal ions comprise at least one of Li, Na, K, Rb, Cs, Cu, and Ag salts; the ionic liquid comprises at least one of 1-butyl pyridine bromide, 1-butyl-4-methylpyridine hexafluorophosphate, 1-butyl-3-methylpyridine bis (trifluoromethanesulfonyl) imide and 1-butyl-4-methylpyridine tetrafluoroborate.
7. The electrochromic film according to claim 4, wherein the mass ratio of the electrochromic material, the film-forming substance, the plasticizer, and the electrolyte is 1:0.1 to 1000:0.01 to 1000.
8. An electrochromic device comprising the electrochromic film according to any one of claims 4 to 7 and an electrode; wherein the electrochromic film is located between the two electrodes.
9. The electrochromic device according to claim 8, further comprising an ion storage film and/or an ion conducting film.
10. Use of an electrochromic device according to any one of claims 8 to 9 in the fields of information storage, security, sensing and display.
CN202210639887.3A 2022-06-08 2022-06-08 Electrochromic material, thin film, device and application thereof Pending CN115073505A (en)

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