CN112817189A

CN112817189A - Electrochromic glass

Info

Publication number: CN112817189A
Application number: CN202110248454.0A
Authority: CN
Inventors: 曾小绵; 白振中
Original assignee: Changxing Qibin Energy Saving Glass Co ltd; Hunan Qibin Energy Saving Glass Co ltd; Guangdong Kibing Energy Saving Glass Co ltd
Current assignee: Changxing Qibin Energy Saving Glass Co ltd; Hunan Qibin Energy Saving Glass Co ltd; Guangdong Kibing Energy Saving Glass Co ltd
Priority date: 2021-03-05
Filing date: 2021-03-05
Publication date: 2021-05-18

Abstract

The invention provides electrochromic glass which comprises first conductive glass, second conductive glass, an ion storage layer, an electrochromic layer and a gel electrolyte layer, wherein the ion storage layer and the electrochromic layer are clamped between the first conductive glass and the second conductive glass, the gel electrolyte layer is clamped between the ion storage layer and the electrochromic layer, and the gel electrolyte layer comprises an organic solvent, a polymer matrix, electrolyte salt and a solid conductive additive. The electrochromic glass takes the gel as the electrolyte, and has the advantages of simple preparation process, good buffer performance and the like, wherein the electrolyte salt is added to provide mobile ions for the ion storage layer and the electrochromic layer, and the solid conductive additive is added to provide more transmission channels for the mobile ions and increase the ionic conductivity, so that the electrochromic efficiency of the electrochromic glass is improved.

Description

Electrochromic glass

Technical Field

The invention relates to the technical field of glass, in particular to electrochromic glass.

Background

Along with the increasing severity of global energy crisis and environmental crisis problems, energy conservation and emission reduction are not slow, the intelligent glass represented by electrochromic glass absorbs the advantages of the energy-saving glass, the transmission light and the reflection light are continuously and dynamically regulated by automatic or artificial active control of a sensor, the electrochromic glass becomes a market bright spot and is widely applied to the field of intelligent buildings and automobiles, and the development of the global electrochromic glass market is promoted together.

The typical electrochromic glass has a five-layer structure, and is composed of two glass substrates and five thin film materials sandwiched between the two glass substrates, namely a transparent conductive layer (TC), an ion storage layer (CE), an ion conductor layer (IC), an electronic color changing layer (EC) and a transparent conductive layer (TC).

The structure, substance, thickness, state and crystal form of the ion conductor layer directly affect the performance and application of the inorganic electrochromic device. The ion conductor layer may be classified into a liquid electrolyte, a solid electrolyte, and a gel electrolyte according to the state. The liquid electrolyte is difficult to package, is easy to leak, and has certain dissolution and corrosion effects on the film layer. The solid electrolyte is typically Li-containing⁺Mainly LiTaO is used as the inorganic salt ion conductor of (1)₃、LiNbO₃LiPON can prepare crystalline or amorphous films through a magnetron sputtering method, is an ion conductor layer widely used by all-solid-state electrochromic devices, but the problems of long discoloration response time and poor discoloration uniformity of solid electrolytes due to poor ion transmission capability are solved. The gel electrolyte has the advantages of good processability, simple process of the color-changing device and the like, and can buffer mechanical stress on the device. However, gel electrolytes have various problems, such as low electrochromic efficiency, and also limit the scaling.

Disclosure of Invention

The invention mainly aims to provide electrochromic glass, which aims to increase the ionic conductivity and promote the transmission of ions so as to improve the electrochromic efficiency.

To achieve the above object, the present invention provides an electrochromic glass comprising:

a first conductive glass and a second conductive glass;

the ion storage layer and the electrochromic layer are clamped between the first conductive glass and the second conductive glass; and the number of the first and second groups,

a gel electrolyte layer sandwiched between the ion storage layer and the electrochromic layer, the gel electrolyte layer comprising organic solvent, polymer matrix, electrolyte salt and solid conductive additive

Optionally, the solid conductive additive is selected from any one or more of graphene, carbon nanotubes, amorphous carbon, mesocarbon microbeads, natural graphite, artificial graphite, carbon fibers, and carbon composites.

Optionally, the components of the gel electrolyte layer further comprise an ultraviolet absorber.

Optionally, the ultraviolet absorbent is selected from any one or more of phenyl hydroxybenzoate, benzophenone, benzotriazole and substituted acrylonitrile ultraviolet absorbent.

Optionally, the composition of the gel electrolyte layer further comprises an organic electrolyte solvent.

Optionally, the organic electrolyte solvent is selected from any one or more of Ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC).

Optionally, the components of the gel electrolyte layer further comprise a stabilizer, which is triphenyl phosphite.

Optionally, the gel electrolyte layer comprises, by mass, 10% to 30% of a polymer matrix, 15% to 50% of an organic solvent, 5% to 10% of an organic electrolyte solvent, 0.3% to 1% of an ultraviolet absorber, 3% to 5% of a solid conductive additive, 0.1% to 1% of a stabilizer, and 5% to 15% of an electrolyte salt.

Optionally, the polymer matrix is selected from any one of polymethyl methacrylate, starch, polycarbonate, inkstone, polyimide, polyarylether and polyaramide; the components of the gel electrolyte layer further comprise an organic solvent selected from propylene carbonate, isopropanol, pyridine, phenol, halogenated hydrocarbons, cyclohexanone, methyl acetateAny one or more of benzene; the electrolyte salt is selected from LiPF₆、LiClO₄、LiPON、LiTaO₃、LiNbO₃、LiMn₂O₄、LiFePO₄、LiCoO₂Any one or more of them.

Optionally, the thickness of the ion storage layer is in a range of 70-150 nm; the thickness range of the electrochromic layer is 70-150 nm; the thickness range of the gel electrolyte layer is 10-50 nm.

According to the technical scheme, the gel electrolyte layer is arranged between the ion storage layer and the electrochromic layer and serves as an ion conductor layer, and the gel electrolyte layer comprises a polymer matrix, electrolyte salt and a solid conductive additive. The electrochromic glass takes the gel as the electrolyte, and has the advantages of simple preparation process, good buffer performance and the like, wherein the electrolyte salt is added to provide mobile ions for the ion storage layer and the electrochromic layer, and the solid conductive additive is added to provide more transmission channels for the mobile ions and increase the ionic conductivity, so that the electrochromic efficiency of the electrochromic glass is improved.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.

Fig. 1 is a schematic structural diagram of electrochromic glass in one embodiment of the present invention.

The reference numbers illustrate:

reference numerals	Name (R)	Reference numerals	Name (R)
				100	First conductive glass	200	Second conductive glass
300	Ion storage layer	400	Electrochromic layer
				500	Gel electrolyte layer

The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It should be noted that, if directional indications (such as up, down, left, right, front, and back … …) are involved in the embodiment of the present invention, the directional indications are only used to explain the relative positional relationship between the components, the movement situation, and the like in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indications are changed accordingly.

In addition, if there is a description of "first", "second", etc. in an embodiment of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, the meaning of "and/or" appearing throughout is to include three juxtapositions, exemplified by "A and/or B," including either the A or B arrangement, or both A and B satisfied arrangement. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.

The embodiment of the invention provides electrochromic glass.

In one embodiment of the present invention, as shown in fig. 1, the electrochromic glass includes:

a first conductive glass 100 and a second conductive glass 200;

an ion storage layer 300 and an electrochromic layer 400, both sandwiched between the first conductive glass 100 and the second conductive glass 200; and the number of the first and second groups,

the gel electrolyte layer 500 is sandwiched between the ion storage layer 300 and the electrochromic layer 400, and the components of the gel electrolyte layer 500 include an organic solvent, a polymer matrix, an electrolyte salt and a solid conductive additive.

It is understood that the electrochromic glass generally includes two glass substrates and five thin films sandwiched between the two glass substrates, the five thin films being a transparent conductive layer (TC), an ion storage layer 300(CE), an ion conductor layer (IC), an electrochromic layer 400(EC), and a transparent conductive layer (TC), respectively. One of the glass substrates and the adjacent transparent conductive layer form a first conductive glass 100, and the other glass substrate and the adjacent transparent conductive layer form a second conductive glass 200. In this embodiment, the two transparent conductive layers are both Indium Tin Oxide (ITO) conductive film layers, that is, the two conductive glasses are both ITO conductive glasses. Specifically, the ITO conductive glass is manufactured by plating an ITO conductive film layer on a soda-lime-based or borosilicate-based glass substrate by a magnetron sputtering method. It should be noted that, both the two conductive glasses are transparent, but the present invention does not limit the transparency of the two conductive glasses as long as the conductive glass can allow light to pass through and does not affect the color display of the color-changing layer.

The electrochromic layer 400 is used to control the overall color of the electrochromic glass, the ion storage layer serves to store ions and balance charges, and the ion conductor layer is used to provide transport channels for ions and ions.

In the technical solution of the embodiment of the present invention, the gel electrolyte layer 500 is used as the ion conductor layer, and the components of the gel electrolyte layer 500 include an organic solvent, a polymer matrix, an electrolyte salt, and a solid conductive additive. The electrochromic glass takes gel as electrolyte, and has the advantages of simple preparation process, good buffer performance and the like, wherein the addition of electrolyte salt is used for providing mobile ions for the ion storage layer 300 and the electrochromic layer 400, and the addition of the solid conductive additive can provide more transmission channels for the mobile ions and increase the ionic conductivity, so that the electrochromic efficiency of the electrochromic glass is improved.

Specifically, the material of the ion storage layer 300 may be selected from NiO and IrO₂、Cr₂O₅、V₂O₅、Co₂O₃、Rh₂O₃Any one or more of; material WO of electrochromic layer 400₃、MoO₃、TiO₂、Nb₂O₅、MnO₂、Ta₂O₅Any one or more of violine, polyaniline, viologen, pyrazoline and polypyrrole; the electrolyte salt in the gel electrolyte layer 500 is selected from LiPF₆、LiClO₄、LiPON、LiTaO₃、LiNbO₃、LiMn₂O₄、LiFePO₄、LiCoO₂Sodium manganate, sodium cobaltate, sodium vanadate, aluminum ion doped LiTaO₃Aluminum ion doped LiNbO₃And the like; the migration ions are any one or more of lithium ions, sodium ions, aluminum ions, hydrogen ions and the like. It is understood that the type of mobile ion depends on the type of electrolyte salt. If the material of the electrolyte salt is LiPF₆、LiClO₄、LiPON、LiTaO₃、LiNbO₃、LiMn₂O₄、LiFePO₄、LiCoO₂And the lithium-containing electrolyte, then the mobile ions are lithium ions; if the electrolyte salt is sodium-containing electrolyte such as sodium manganate, sodium cobaltate, sodium vanadate and the like, the mobile ions are sodium ions; if the electrolyte salt is aluminum ion-doped LiTaO₃Aluminum ion doped LiNbO₃And the electrolyte containing aluminum and lithium, the mobile ions are aluminum ions and lithium ions.

In this embodiment, the conductive glass is ITO conductive glass, the ion storage layer 300 is a NiO layer, and the electrochromic layer 400 is WO₃Layer, the ion conductor layer is a gel electrolyte layer 500. Thus, the structure of the electrochromic glass is as follows: ITO conductive glass/NiO layer/gel electrolyte layer 500/WO₃layer/ITO conductive glass. The electrochromic glass has the following discoloration and fading processes: during the color change process, when the mobile ions in the gel electrolyte enter WO₃Layer of, cause W⁶⁺To W⁵⁺A transition of (a); during the bleaching process, mobile ions are removed from WO₃Layer deintercalation, causing W⁵⁺To W⁶⁺A transition of (a); and when the migration ions in the gel electrolyte enter the NiO layer, the NiO layer is caused to fade, and when the migration ions enter and are extracted from the NiO layer, the NiO layer is caused to be colored, so that the electrochromic reaction is completed.

Specifically, the polymer matrix is selected from one or more of polymethyl methacrylate, starch, polycarbonate, inkstone, polyimide, polyarylether, polyaramide and the like. Among them, polymethyl methacrylate is very suitable as a main component of a gel electrolyte because of its advantages such as excellent visible light transmittance, low cost, and easy machining.

The organic solvent is selected from one or more of propylene carbonate, isopropanol, pyridine, phenol, halogenated hydrocarbon, cyclohexanone and toluene. In this embodiment, the polymer matrix, the electrolyte salt, and the solid conductive additive are all soluble in an organic solvent. In this embodiment, propylene carbonate is used as the organic solvent of the gel electrolyte.

In addition, the electrolyte salt is selected from LiPF₆、LiClO₄、LiPON、LiTaO₃、LiNbO₃、LiMn₂O₄、LiFePO₄、LiCoO₂I.e. the mobile ions are lithium ions.

Further, the solid conductive additive is selected from any one or more of graphene, carbon nanotubes, amorphous carbon, mesocarbon microbeads, natural graphite, artificial graphite, carbon fibers, carbon composites and the like. It can be understood that conductive additives such as carbon nanotubes, graphene, a combination of graphene and carbon nanotubes and the like are added into the gel electrolyte, the conductive additives have a layered structure, and the effective distance between layers is large, so that the transmission channel of lithium ions in the gel electrolyte is increased, the conductivity of the lithium ions is increased, and the electrochromic efficiency of the electrochromic glass is improved.

Further, the composition of the gel electrolyte layer 500 further includes an ultraviolet absorber. Optionally, the ultraviolet absorbent is selected from any one or more of phenyl o-hydroxybenzoate, benzophenone, benzotriazole and substituted acrylonitrile ultraviolet absorbent. It is understood that ultraviolet rays can cause aging and deterioration of the gel electrolyte. In the embodiment, the ultraviolet absorbent is added in the gel electrolyte, so that when ultraviolet rays irradiate on the gel electrolyte, the ultraviolet absorbent preferentially absorbs the ultraviolet rays by utilizing the special molecular structure of the ultraviolet absorbent, thereby effectively slowing down or avoiding the damage of the ultraviolet rays to the gel electrolyte and slowing down the aging and the deterioration of the gel electrolyte.

Further, the composition of the gel electrolyte layer 500 further includes an organic electrolyte solvent. Optionally, the organic electrolyte solvent is selected from any one or more of Ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC). Organic electrolyte solvents (EC, DEC, DMC, EC + DEC + DMC, etc.) are added into the gel electrolyte, and the molecular structures of the organic compounds are rod-shaped structures, so that the free path of ions in the gel electrolyte can be improved, and the electrochromic efficiency can be increased. Meanwhile, the organic compounds can form special protective layers on the surfaces of the electrochromic layer 400 and the ion storage layer 300, so that the crystal structures of the electrochromic layer 400 and the ion storage layer 300 are effectively protected, and better conditions are provided for the intercalation and deintercalation of ions by the electrochromic layer 400 and the ion storage layer 300.

Further, the components of the gel electrolyte layer 500 further include a stabilizer. The stabilizer has excellent electronegativity and weak polarity, and can effectively stabilize the gel electrolyte. In this example, the stabilizer is triphenyl phosphite.

In this embodiment, the gel electrolyte layer 500 is composed of a polymer matrix, an organic solvent, an organic electrolyte solvent, an ultraviolet absorber, a stabilizer, a solid conductive additive, and an electrolyte salt. According to the technical scheme, the solid conductive additive is added into the electrolyte, so that the lithium ion conductivity is effectively increased, and the electrochromic efficiency of the electrochromic glass is improved; meanwhile, the ultraviolet absorbent is used for absorbing ultraviolet rays, so that the damage of the ultraviolet rays to the gel electrolyte is effectively slowed down or avoided, and the aging and the deterioration of the gel electrolyte are slowed down; a special protective layer is also formed on the surfaces of the electrochromic layer 400 and the ion storage layer 300 by an organic electrolyte solvent, thereby effectively protecting the crystal structures of the electrochromic layer 400 and the ion storage layer 300. Therefore, the electrochromic glass using the gel electrolyte layer 500 has the characteristics of high electrochromic efficiency, uniform discoloration, increased cycle number and the like.

Specifically, the gel electrolyte layer 500 comprises, by mass, 10% to 30% of a polymer matrix, 15% to 50% of an organic solvent, 5% to 10% of an organic electrolyte solvent, 0.3% to 1% of an ultraviolet absorber, 3% to 5% of a solid conductive additive, 0.1% to 1% of a stabilizer, and 5% to 15% of an electrolyte salt. It should be noted that the mass ratio of the solid conductive additive is not too much or too little, when the mass ratio of the solid conductive additive is too much, the solid conductive additive cannot be sufficiently dissolved, so that the effect is deteriorated, when the mass ratio of the solid conductive additive is too little, the ionic conductivity cannot be obviously increased, and the electrochromic efficiency cannot be obviously improved; the mass ratio of the ultraviolet absorbent is not too much or too little, when the mass ratio of the ultraviolet absorbent is too much, the preparation cost of the gel electrolyte is obviously increased, and when the mass ratio of the ultraviolet absorbent is too little, the ultraviolet cannot be fully absorbed, so that the aging and the deterioration of the gel electrolyte are well slowed down; the mass ratio of the organic electrolyte solvent is not too high or too low, when the mass ratio of the organic electrolyte solvent is too high, the preparation cost of the gel electrolyte is obviously increased, and when the mass ratio of the organic electrolyte solvent is too low, the electrochromic layer 400 and the ion storage layer 300 cannot be well protected; the mass ratio of the organic solvent is not too much or too little, the gel electrolyte form is affected by too much organic solvent, the gel electrolyte is not in a gel state any more and becomes liquid, and each solute can not be fully dissolved by too little organic solvent, so that the conductive effect of the electrolyte solution is poor.

Further, the thickness of the ion storage layer 300 is in a range of 70-150 nm, and optionally, the thickness of the ion storage layer 300300 is 70nm, or 110nm, or 150 nm; the thickness of the electrochromic layer 400 is in a range of 70-150 nm, and optionally, the thickness of the electrochromic layer 400 is 70nm, or 110nm, or 150 nm. It is to be understood that the thicknesses of the ion storage layer 300 and the electrochromic layer 400 are not too thin nor too thick. Specifically, the ion-deintercalation process determining the reaction rate in the electrochromic reaction is diffusion-controlled, so that the color-changing effect depends on the diffusion coefficient of ions in the film layer and the specific surface area of the film, and if the film layer is too thin, the process is difficult to control, and the positions where mobile ions can be intercalated are few, thereby causing the application effect of the electrochromic layer 400 to be poor; the film layer is too thick, repeated film coating is needed, the cost is high, and the migration path of the migration ions is long and the participation reaction is slow due to the fact that the film layer is thick.

The thickness range of the gel electrolyte layer 500 is 10-50 nm, and optionally, the thickness of the ion conductor layer 500 is 50nm, or 100nm, or 150 nm. It is understood that the thickness of the gel electrolyte layer 500 is not too thin nor too thick. If the gel electrolyte layer 500 is too thin, the process may be difficult to control, and insufficient supply of mobile ions may result, making it difficult to completely cause discoloration; if the gel electrolyte layer 500 is too thick, the range of use of the electrochromic glass is also affected because electronic devices are now being sought to be thin and light.

The embodiment of the invention also provides a preparation method of the electrochromic glass, which comprises the following steps:

mixing a polymer matrix, electrolyte salt and a solid conductive additive to prepare a gel electrolyte;

plating an electrochromic layer on the first conductive glass or the second conductive glass through magnetron sputtering;

plating an ion storage layer on the first conductive glass or the second conductive glass through magnetron sputtering;

coating a gel electrolyte on the first conductive glass and/or the second conductive glass; and a process for the preparation of a coating,

and assembling the first conductive glass and the second conductive glass to obtain the electrochromic glass.

The method comprises the following steps of coating an ion storage layer on first conductive glass through magnetron sputtering, and coating an electrochromic layer on second conductive glass through magnetron sputtering: and cleaning the surfaces of the first conductive glass and the second conductive glass. Specifically, the ITO conductive glass is sequentially subjected to polyacrylamide and organic silicon oil to remove oil stains on the surface of the ITO conductive glass, then solutions such as acetone and ethanol are used to remove oil stains and impurities which are not cleaned, finally the ITO conductive glass is cleaned by an ultrasonic cleaner, and finally acetone and ethanol are used to wipe the surface of the ITO conductive glass, so that the surface of the ITO conductive glass is cleaned.

In the step of plating the electrochromic layer on the first conductive glass or the second conductive glass through magnetron sputtering, the sputtering power is 20-150 KW, the plating speed is 0.1-3 m/min, the argon flow is 300-1000 ml/min, and the oxygen flow is 500-700 ml/min;

in the step of plating the ion storage layer on the first conductive glass or the second conductive glass through magnetron sputtering, the sputtering power is 20-150 KW, the plating speed is 0.1-3 m/min, the argon flow is 300-1000 ml/min, and the oxygen flow is 500-700 ml/min.

The specific preparation process of the electrochromic glass is as follows:

adding a proper amount of electrolyte salt, a solid conductive additive and the like into a reaction container, mixing and stirring uniformly, then adding a proper amount of polymer matrix, controlling the rotating speed at 1000-1500 r/min, and stirring for 1-3 h. Further, an organic solvent, an organic electrolyte solvent, an ultraviolet absorbent and a stabilizer can be added for mixing and stirring, and the rotating speed is controlled to be 1000-1500 r/min until the solution is transparent and the preparation of the gel electrolyte is finished.

Then, the ITO conductive glass covering the electrochromic layer can be placed on a platform, then the gel electrolyte layer is coated, finally the ITO conductive glass covering the ion storage layer is placed, the 3M adhesive tape is placed in the middle of the ITO conductive glass, the thickness of the electrolyte layer is controlled, then the control circuit installation is completed, and the preparation of the electrochromic glass can be completed.

The electrochromic layer and the ion storage layer can be plated on the same conductive glass, and finally the conductive glass and another conductive glass are assembled; the electrochromic layer and the ion storage layer can also be respectively plated on different conductive glasses, and finally the two conductive glasses are assembled. Likewise, the gel electrolyte may be applied to either conductive glass or both conductive glasses.

The preparation of the electrochromic glazing, and the corresponding effects, will now be described with reference to specific examples.

Example 1

(1) Preparation of gel electrolyte layer

Adding a proper amount of propylene carbonate and graphene into a reaction container, stirring, adding a proper amount of polymethyl methacrylate after completely dissolving, controlling the rotating speed at 1000-1500 r/min, stirring for 3h, and then adding LiPF₆And then the mixture is stirred,the rotating speed is controlled to be 1000-1500 r/min until the solution is transparent and the preparation of the gel electrolyte is finished.

(2) Cleaning surface of ITO conductive glass

Sequentially passing a 20cm by 20cm glass sample wafer through polyacrylamide and organic silicone oil to remove oil stains on the surface of the ITO conductive glass, then passing solutions such as acetone and ethanol to remove uncleaned oil stains and impurities, finally cleaning for 3 hours through an ultrasonic cleaning machine, taking out the sample wafer, and wiping the sample wafer with acetone and ethanol to dry, and waiting for the next step.

(3) Preparation of the electrochromic layer

Taking a piece of cleaned ITO conductive glass, and plating WO on the ITO conductive glass by utilizing magnetron sputtering₃Controlling the sputtering power to be 100KW, the coating speed to be 0.15m/min, the Ar flow to be 700ml/min, O₂The flow rate was 500 ml/min.

(4) Preparation of ion storage layer

Taking another piece of cleaned ITO conductive glass, plating a NiO layer on the ITO conductive glass by magnetron sputtering, controlling the sputtering power to be 130KW, the film plating speed to be 2m/min, the Ar flow to be 700ml/min, and O₂The flow rate was 500 ml/min.

(5) Assembling electrochromic glass

Placing the ITO conductive glass covered with the electrochromic layer on a platform, then coating a gel electrolyte layer, finally placing the ITO conductive glass covered with the ion storage layer, placing a 3M adhesive tape in the middle of the ITO conductive glass, controlling the thickness of the electrolyte layer, then finishing the installation of a control circuit, and finishing the preparation of the electrochromic glass.

Example 2

(1) Preparation of gel electrolyte layer

Adding a proper amount of propylene carbonate and graphene into a reaction container, stirring, adding a proper amount of polymethyl methacrylate after completely dissolving, controlling the rotating speed at 1000-1500 r/min, stirring for 3h, and then adding LiPF₆And stirring the o-hydroxybenzoic acid phenyl ester at the rotating speed of 1000-1500 r/min until the solution is transparent and the preparation of the gel electrolyte is finished.

Steps (2) to (5) in example 2 correspond to those in example 1.

Example 3

(1) Preparation of gel electrolyte layer

Adding a proper amount of propylene carbonate, EC and graphene into a reaction container, stirring, adding a proper amount of polymethyl methacrylate after completely dissolving, controlling the rotating speed at 1000-1500 r/min, stirring for 3h, and then adding LiPF₆And stirring the o-hydroxybenzoic acid phenyl ester at the rotating speed of 1000-1500 r/min until the solution is transparent and the preparation of the gel electrolyte is finished.

Steps (2) to (5) in example 3 correspond to those in example 1.

Example 4

(1) Preparation of gel electrolyte layer

Adding a proper amount of propylene carbonate, EC + DMC, carbon nano tubes and triphenyl phosphite into a reaction vessel, stirring, adding a proper amount of polymethyl methacrylate after complete dissolution, controlling the rotating speed at 1000-1500 r/min, stirring for 3h, and then adding LiPF₆And stirring the o-hydroxybenzoic acid phenyl ester at the rotating speed of 1000-1500 r/min until the solution is transparent and the preparation of the gel electrolyte is finished.

Steps (2) to (5) in example 4 correspond to those in example 1.

Example 5

(1) Preparation of gel electrolyte layer

Adding a proper amount of propylene carbonate, EC + DEC, graphene and triphenyl phosphite into a reaction container, stirring, adding a proper amount of polymethyl methacrylate after completely dissolving, controlling the rotating speed at 1000-1500 r/min, stirring for 3h, and then adding LiClO₄And stirring the o-hydroxybenzoic acid phenyl ester at the rotating speed of 1000-1500 r/min until the solution is transparent and the preparation of the gel electrolyte is finished.

Steps (2) to (5) in example 5 correspond to those in example 1.

Example 6

(1) Preparation of gel electrolyte layer

Adding proper amount of propylene carbonate, EC + DEC + DMC, graphene + carbon nano tube and triphenyl phosphate into a reaction containerStirring the ester, adding a proper amount of polymethyl methacrylate after the ester is completely dissolved, controlling the rotating speed at 1000-1500 r/min, stirring for 3h, and then adding LiClO₄+LiPF₆And stirring the o-hydroxybenzoic acid phenyl ester at the rotating speed of 1000-1500 r/min until the solution is transparent and the preparation of the gel electrolyte is finished.

Steps (2) to (5) in example 6 correspond to those in example 1.

Comparative example 1

(1) Preparation of gel electrolyte layer

Adding a proper amount of propylene carbonate and polymethyl methacrylate into a reaction container, controlling the rotating speed at 1000-1500 r/min, stirring for 3h, and then adding LiPF₆Stirring, and controlling the rotating speed at 1000-1500 r/min until the solution is transparent, so that the preparation of the gel electrolyte is finished.

Adding proper amount of polymethyl methacrylate and LiPF into a reaction vessel₆And mixing and stirring the mixture, and controlling the rotating speed to be 1000-1500 r/min until the solution is transparent and the preparation of the gel electrolyte is finished.

Comparative example 1

Steps (2) to (5) in (a) are the same as those in example 1.

The response time and the cycle number of the electrochromic glass with different film thicknesses prepared in the table 1, the comparative example 1 and the examples 1-6 correspond to the electrochromic glass with different film thicknesses.

It should be noted that the response time of the electrochromic glazing includes the tinting time, which refers to the time required for the electrochromic glazing to go from the tinted state to the tinted state, and the fade time, which refers to the time required for the electrochromic glazing to switch from the tinted state to the faded state. In the above examples and comparative examples, the response time was expressed using the coloring time.

The cycle number of the electrochromic glass refers to the number of times that the electrochromic glass can be stably cycled, and after the electrochromic glass is cycled for many times, if the color change is slow, the electrochromic glass is not counted in the cycle number.

Comparing example 1 with comparative example 1, it can be seen that the response time and cycle number of the electrochromic glass of example 1 are better than those of the electrochromic glass of comparative example 1, because compared with the comparative example, the electrochromic glass of example 1 is added with the solid conductive additive in the gel electrolyte, which is beneficial to increasing the ionic conductivity, thereby improving the electrochromic efficiency of the electrochromic glass.

It can be seen from comparing examples 1 and 2 that the cycle number of the electrochromic glass of example 2 is better than that of the electrochromic glass of example 1, because compared with example 1, the electrochromic glass of example 2 is additionally provided with an ultraviolet absorbent in the gel electrolyte, and the ultraviolet absorbent can absorb ultraviolet rays, so that the damage of the ultraviolet rays to the gel electrolyte is effectively reduced or avoided, the aging and the deterioration of the gel electrolyte are reduced, and the cycle number of the electrochromic glass is increased.

It can be found by comparing examples 2 and 3 that the cycle number of the electrochromic glass of example 3 is better than that of the electrochromic glass of example 2, because compared with example 2, in the electrochromic glass of example 3, an organic electrolyte solvent is further added in the gel electrolyte, the ultraviolet absorbent can absorb ultraviolet rays, the damage of the ultraviolet rays to the gel electrolyte is effectively slowed down or avoided, the organic electrolyte solvent forms a special protective layer on the surfaces of the electrochromic layer and the ion storage layer, the crystal structures of the electrochromic layer and the ion storage layer are effectively protected, and further the cycle number of the electrochromic glass is increased.

It can be seen from comparing examples 3, 4 and 6 that the cycle number of the electrochromic glass of examples 4 and 6 is better than that of the electrochromic glass of example 3, because the gel electrolyte is added with a stabilizer which can effectively stabilize the gel electrolyte, thereby increasing the cycle number of the electrochromic glass, compared with the electrochromic glass of examples 3 and 6. The electrochromic glass of example 5 was not cycled as in example 3 because LiClO was used as the electrolyte salt in example 6₄To do soExample 3 the electrolyte salt used was LiPF₄Compared with LiClO₄，LiPF₄More lithium ions can be electrolyzed, and the conductivity is better.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims

1. An electrochromic glazing, characterized in that it comprises:

a first conductive glass and a second conductive glass;

and the gel electrolyte layer is clamped between the ion storage layer and the electrochromic layer, and the components of the gel electrolyte layer comprise an organic solvent, a polymer matrix, electrolyte salt and a solid conductive additive.

2. The electrochromic glazing of claim 1 wherein the solid conductive additive is selected from any one or more of graphene, carbon nanotubes, amorphous carbon, mesocarbon microbeads, natural graphite, artificial graphite, carbon fibers, and carbon composites.

3. The electrochromic glazing of claim 1 wherein the components of the gel electrolyte layer further comprise an ultraviolet absorber.

4. The electrochromic glazing according to claim 3 wherein the UV absorber is selected from any one or more of phenyl ortho-hydroxybenzoate, benzophenone, benzotriazole, substituted acrylonitrile based UV absorbers.

5. The electrochromic glazing of claim 3 wherein the components of the gel electrolyte layer further comprise an organic electrolyte solvent.

6. The electrochromic glazing according to claim 5 wherein the organic electrolyte solvent is selected from any one or more of ethylene carbonate, diethyl carbonate and dimethyl carbonate.

7. The electrochromic glazing of claim 5 wherein the components of the gel electrolyte layer further comprise a stabilizer, the stabilizer being triphenyl phosphite.

8. The electrochromic glass according to claim 7, wherein the gel electrolyte layer comprises, in mass percent, 10% to 30% of a polymer matrix, 15% to 50% of an organic solvent, 5% to 10% of an organic electrolyte solvent, 0.3% to 1% of an ultraviolet absorber, 3% to 5% of a solid conductive additive, 0.1% to 1% of a stabilizer, and 5% to 15% of an electrolyte salt.

9. The electrochromic glazing according to any of claims 1 to 8, wherein the polymer matrix is selected from any one or more of polymethylmethacrylate, starch, polycarbonate, inkstone, polyimide, polyarylether, polyaramid; the organic solvent is selected from one or more of propylene carbonate, isopropanol, pyridine, phenol, halogenated hydrocarbon, cyclohexanone and toluene; the electrolyte salt is selected from LiPF₆、LiClO₄、LiPON、LiTaO₃、LiNbO₃、LiMn₂O₄、LiFePO₄、LiCoO₂Any one or more of them.

10. The electrochromic glazing according to any of claims 1 to 8, wherein the thickness of the ion storage layer is in the range of 70 to 150 nm; the thickness range of the electrochromic layer is 70-150 nm; the thickness range of the gel electrolyte layer is 10-50 nm.