Electrochromic glass and preparation method thereof

Abstract

The present invention provides an electrochromic glass, comprising a first conductive glass, a second conductive glass, an ion storage layer, an electrochromic layer, at least one ion conductor layer and at least one ion vacancy layer. The ion storage layer and the electrochromic layer are both sandwiched between the first conductive glass and the second conductive glass; the ion conductor layer and the ion vacancy layer are both sandwiched between the ion storage layer and the electrochromic layer, the ion conductor layer and the ion vacancy layer are adjacently stacked, the ion conductor layer is used to provide migrating ions, and the ion vacancy layer is used for migrating ions to be embedded or de-embedded. The present invention also provides a method for preparing electrochromic glass. The technical solution of the present invention facilitates the rapid embedding and de-embedding of migrating ions by adding an ion vacancy layer, reduces the movement path of migrating ions, and enables the concentration of migrating ions in the two color-changing layers to be maintained at a high concentration to complete electrochromism, thereby increasing the number of cycles of the electrochromic glass.

Description

Technical Field

[0001] The present invention relates to the technical field of glass, and in particular to electrochromic glass and a preparation method thereof. Background Art

[0002] Electrochromism refers to the phenomenon in which a material's optical properties (reflectivity, transmittance, absorptivity, etc.) undergo a stable, reversible color change under the influence of an applied electric field. This phenomenon manifests itself as a reversible change in color and transparency. Materials with electrochromic properties are called electrochromic materials. Electrochromic materials are a new type of functional material with a wide range of applications in information technology, electronics, energy, construction, and national defense. Devices made with electrochromic materials are called electrochromic devices.

[0003] Electrochromic glass combines the latest technologies in electrochromic thin film materials, glass packaging, and electronic control to achieve intelligent control of sunshade, privacy, and energy-saving effects on glass. Electrochromic glass represents the future development direction of glass and will contribute to energy conservation and intelligent color change in global buildings. The basic structure of electrochromic glass is composed of two glass substrates and five layers of thin film materials sandwiched between them: a transparent conductive layer (TC), an ion storage layer (CE), an ion conductor layer (IC), an electrochromic layer (EC), and a transparent conductive layer (TC).

[0004] However, at present, as the number of cycles of the electrochromic device increases, its current density will decrease sharply, and the color-changing effect of the ion storage layer and the electrochromic layer will become worse and worse. This is because the migration path of the migrating ions between the two color-changing film layers is long, and as the number of cycles increases, the morphology of the two color-changing film layers will change and gradually become dense, making it impossible for the migrating ions to be completely embedded and de-embedded in the two color-changing film layers, resulting in insufficient concentration of migrating ions in the two color-changing film layers and unable to fully cause their chemical reaction. For example, the colorless W in the WO3 film (electrochromic layer) 6+ Cannot be restored to blue W 5+ , colorless Ni in NiO film (ion storage layer) 2+ Can't be gray or brown Ni 3+ , that is, the color-changing function of the electrochromic device disappears. Summary of the Invention

[0005] The main purpose of the present invention is to provide an electrochromic glass and a preparation method thereof, aiming to reduce the migration path of migrating ions, increase the concentration of migrating ions in the color-changing layer, and thus increase the number of cycles of the electrochromic glass.

[0006] To achieve the above object, the present invention provides an electrochromic glass, comprising:

[0007] a first conductive glass and a second conductive glass;

[0008] an ion storage layer and an electrochromic layer, both of which are sandwiched between the first conductive glass and the second conductive glass; and

[0009] At least one ion conductor layer and at least one ion vacancy layer are both sandwiched between the ion storage layer and the electrochromic layer. The ion conductor layer and the ion vacancy layer are stacked adjacent to each other. The ion conductor layer is used to provide mobile ions, and the ion vacancy layer is used for embedding or de-embedding the mobile ions.

[0010] Optionally, the electrochromic glass includes an ion conductor layer and an ion vacancy layer, wherein the ion vacancy layer is sandwiched between the ion storage layer and the ion conductor layer; or, the ion vacancy layer is sandwiched between the ion conductor layer and the electrochromic layer.

[0011] Optionally, the electrochromic glass includes two ion conductor layers and an ion vacancy layer, and the ion vacancy layer is sandwiched between the two ion conductor layers.

[0012] Optionally, the electrochromic glass includes an ion conductor layer and two ion vacancy layers, and the ion conductor layer is sandwiched between the two ion vacancy layers.

[0013] Optionally, the ion vacancy layer is a carbon-based material layer, a silicon-based material layer, or a tin-based material layer.

[0014] Optionally, the material of the carbon-based material layer is selected from any one or more of graphene, amorphous carbon, mesocarbon microbeads, natural graphite and artificial graphite.

[0015] Optionally, the material of the ion storage layer is selected from any one or more of NiO, IrO2, Cr2O5, V2O5, Co2O3, and Rh2O3; the material of the electrochromic layer is selected from any one or more of WO3, MoO3, TiO2, Nb2O5, MnO2, Ta2O5, violaceous acid, polyaniline, violaceous acid, pyrazoline, and polypyrrole; the material of the ion conductor layer is selected from any one or more of LiPON, LiTaO3, LiNbO3, LiMn2O4, LiFePO4, LiCoO2, sodium manganate, sodium cobaltate, sodium vanadate, aluminum ion-doped LiTaO3, aluminum ion-doped LiNbO3, and acidified polymer electrolyte; the migrating ions are any one or more of lithium ions, sodium ions, aluminum ions, and hydrogen ions.

[0016] Optionally, the thickness of the ion storage layer ranges from 70 to 150 nm; the thickness of the electrochromic layer ranges from 70 to 150 nm; the thickness of the ion conductor layer ranges from 50 to 150 nm; and the thickness of the ion vacancy layer ranges from 10 to 50 nm.

[0017] The present invention also provides a method for preparing electrochromic glass, the method comprising:

[0018] coating an electrochromic layer on the first conductive glass or the second conductive glass by magnetron sputtering;

[0019] coating an ion storage layer on the first conductive glass or the second conductive glass by magnetron sputtering;

[0020] coating an ion conductor layer on the first conductive glass and / or the second conductive glass by magnetron sputtering;

[0021] coating an ion vacancy layer on the first conductive glass and / or the first conductive glass by magnetron sputtering or spin coating;

[0022] The first conductive glass and the second conductive glass are assembled to obtain electrochromic glass.

[0023] Furthermore, in the step of coating the electrochromic layer on the first conductive glass or the second conductive glass by magnetron sputtering, the sputtering power is 20 to 150 kW, the coating rate is 0.1 to 3 m / min, the argon flow rate is 300 to 1000 ml / min, and the oxygen flow rate is 500 to 700 ml / min;

[0024] In the step of plating the ion storage layer on the first conductive glass or the second conductive glass by magnetron sputtering, the sputtering power is 20-150 kW, the plating rate is 0.15-3 m / min, the argon flow rate is 300-1000 ml / min, and the oxygen flow rate is 500-700 ml / min;

[0025] In the step of plating the ion conductor layer on the first conductive glass and / or the second conductive glass by magnetron sputtering, the sputtering power is 50 to 130 kW, the plating rate is 0.15 to 3 m / min, and the argon flow rate is 300 to 1000 ml / min;

[0026] In the step of plating an ion vacancy layer on the first conductive glass and / or the second conductive glass by magnetron sputtering or spin coating, the sputtering power is 10-50 KW, the plating rate is 0.15-1 m / min, and the argon flow rate is 100-500 ml / min.

[0027] The present invention provides an electrochromic glass, wherein an ion vacancy layer is added between the ion storage layer and the electrochromic layer, and an ion conductor layer and the ion vacancy layer are stacked adjacent to each other. The ion conductor layer is used to provide migrating ions, and the ion vacancy layer is used to allow the migrating ions to be embedded or de-embedded. In the technical solution of the present invention, after the ion vacancy layer is added between the ion storage layer and the ion vacancy layer, since the ion vacancy layer has a large number of defects and vacancies, it is convenient for the migrating ions to be quickly embedded and de-embedded, so that the migrating ions only need to migrate between the ion storage layer and the ion vacancy layer, or between the electrochromic layer and the ion vacancy layer, reducing the movement path of the migrating ions, so that the concentration of the migrating ions in the ion storage layer and the electrochromic layer can be maintained at a high concentration to complete electrochromism, thereby increasing the number of cycles of the electrochromic glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0029] Figure 1 This is a schematic structural diagram of an embodiment of the electrochromic glass of the present invention;

[0030] Figure 2 Schematic diagram of the structure of another embodiment of the electrochromic glass of the present invention;

[0031] Figure 3 This is a schematic structural diagram of another embodiment of the electrochromic glass of the present invention.

[0032] Description of Figure Numbers:

[0033] Label name Label name 100 The first conductive glass 200 Second conductive glass 300 ion storage layer 400 electrochromic layer 500 Ion conductor layer 600 ion vacancy layer

[0034] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings and in conjunction with the embodiments. DETAILED DESCRIPTION

[0035] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0036] It should be noted that if the embodiments of the present invention involve directional indications (such as up, down, left, right, front, back, etc.), the directional indications are only used to explain the relative position relationship, movement status, etc. between the various components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indications will also change accordingly.

[0037] In addition, if there are descriptions involving "first", "second", etc. in the embodiments of the present invention, the descriptions of "first", "second", etc. are only for descriptive purposes and cannot be understood as indicating or suggesting their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of such features. In addition, the meaning of "and / or" appearing in the full text is to include three parallel solutions. Taking "A and / or B as an example", it includes solution A, or solution B, or solutions that satisfy both A and B. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in this field to implement. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0038] An embodiment of the present invention provides an electrochromic glass.

[0039] In one embodiment of the present invention, Figures 1 to 3 As shown, the electrochromic glass includes:

[0040] A first conductive glass 100 and a second conductive glass 200;

[0041] The ion storage layer 300 and the electrochromic layer 400 are both sandwiched between the first conductive glass 100 and the second conductive glass 200; and

[0042] At least one ion conductor layer 500 and at least one ion vacancy layer 600 are both sandwiched between the ion storage layer 300 and the electrochromic layer 400. The ion conductor layer 500 and the ion vacancy layer 600 are stacked adjacent to each other. The ion conductor layer 500 is used to provide mobile ions, and the ion vacancy layer 600 is used for the embedding or de-embedding of the mobile ions.

[0043] It can be understood that electrochromic glass generally includes two glass substrates and five thin films sandwiched between the two glass substrates. The five film layers are a transparent conductive layer (TC), an ion storage layer (CE), an ion conductor layer (IC), an electrochromic layer (EC), and a transparent conductive layer (TC). One glass substrate and an adjacent transparent conductive layer constitute a first conductive glass 100, and the other glass substrate and an adjacent transparent conductive layer constitute a second conductive glass 200. In this embodiment, both transparent conductive layers are indium tin oxide (ITO) conductive film layers, that is, both conductive glasses are ITO conductive glasses. Specifically, ITO conductive glass is made by coating a layer of ITO conductive film layer on a soda-lime-based or borosilicate-based glass substrate using a magnetron sputtering method. It should be noted that both 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 display of the color of the color-changing layer.

[0044] The electrochromic layer 400 controls the overall color of the electrochromic glass, the ion storage layer stores ions and balances charge, and the ion conductor layer 500 provides channels for mobile ions and ion transport. In this embodiment, an ion vacancy layer 600 is further provided between the ion storage layer 300 and the electrochromic layer 400. Optionally, the ion vacancy layer 600 has a layered structure with numerous defects and vacancies to facilitate the insertion and removal of mobile ions.

[0045] In addition, the number of ion conductor layers 500 can be set to one or more layers. Similarly, the number of ion vacancy layers 600 can also be set to one or more layers. The present invention does not limit the specific number of ion conductor layers 500 and ion vacancy layers 600; the ion vacancy layer 600 can be set between the ion storage layer 300 and the ion conductor layer 500, or between the electrochromic layer 400 and the ion conductor layer 500, or between two ion conductor layers 500. The present invention does not limit the specific positions of the ion conductor layer 500 and the ion vacancy layer 600, as long as the ion conductor layer 500 and the ion vacancy layer 600 are set between the ion storage layer 300 and the electrochromic layer 400.

[0046] The technical solution of this embodiment adds an ion vacancy layer 600 between the ion storage layer 300 and the ion vacancy layer 600. Since the ion vacancy layer 600 has more defects and vacancies, it is convenient for the migrating ions to be quickly embedded and de-embedded, so that the migrating ions only need to migrate between the ion storage layer 300 and the ion vacancy layer 600, or migrate between the electrochromic layer 400 and the ion vacancy layer 600, reducing the movement path of the migrating ions, so that the concentration of the migrating ions in the ion storage layer 300 and the electrochromic layer 400 can be maintained at a high concentration to complete electrochromism, thereby increasing the number of cycles of the electrochromic glass.

[0047] In one embodiment, the electrochromic glass includes an ion conductor layer 500 and an ion vacancy layer 600. The ion vacancy layer 600 is sandwiched between the ion storage layer 300 and the ion conductor layer 500. Specifically, the structure of the electrochromic glass is as follows: first conductive glass 100 / ion storage layer 300 / ion vacancy layer 600 / ion conductor layer 500 / electrochromic layer 400 / second conductive glass 200.

[0048] Alternatively, the ion vacancy layer 600 is sandwiched between the ion conductor layer 500 and the electrochromic layer 400. Specifically, Figure 1 As shown, the structure of the electrochromic glass is as follows: first conductive glass 100 / ion storage layer 300 / ion conductor layer 500 / ion vacancy layer 600 / electrochromic layer 400 / second conductive glass 200 .

[0049] It can be understood that the introduction of the ion vacancy layer 600 can effectively change the movement path of the migrating ions. Specifically, during the color change process of the electrochromic glass, the migrating ions enter the electrochromic layer 400 from the ion vacancy layer 600, causing the electrochromic layer 400 to change color. During the fading process, the migrating ions are directly deintercalated from the electrochromic layer 400 and enter the ion vacancy layer 600, reducing the movement path of the migrating ions and always maintaining the concentration of the migrating ions in the electrochromic layer 400, so that the color change and fading reactions are fully carried out. Similarly, the migrating ions enter the ion storage layer 300 from the ion vacancy layer 600, causing the ion storage layer 300 to fade. When the migrating ions enter the ion vacancy layer 600 from the ion storage layer 300, it will cause the ion storage layer 300 to color, completing the electrochromic reaction.

[0050] In another embodiment, the electrochromic glass includes two ion conductor layers 500 and an ion vacancy layer 600, wherein the ion vacancy layer 600 is sandwiched between the two ion conductor layers 500. Figure 2 As shown, the structure of the electrochromic glass is as follows: first conductive glass 100 / ion storage layer 300 / ion conductor layer 500 / ion vacancy layer 600 / ion conductor layer 500 / electrochromic layer 400 / second conductive glass 200. Compared to the previous embodiment, this embodiment adds an ion conductor layer 500, allowing the ion storage layer and electrochromic layer 400 to be positioned adjacent to the ion conductor layer 500. This helps increase the concentration of mobile ions in both the ion storage layer and the electrochromic layer 400, thereby promoting electrochromism.

[0051] In another embodiment, the electrochromic glass includes an ion conductor layer 500 and two ion vacancy layers 600, wherein the ion conductor layer 500 is sandwiched between the two ion vacancy layers 600. Figure 3As shown, the structure of the electrochromic glass is as follows: first conductive glass 100 / ion storage layer 300 / ion vacancy layer 600 / ion conductor layer 500 / ion vacancy layer 600 / electrochromic layer 400 / second conductive glass 200. Compared to the above two embodiments, the technical solution of this embodiment adds an ion vacancy layer 600, so that ion vacancy layers 600 are provided near both the ion storage layer and the electrochromic layer 400. This reduces the movement path of migrating ions between the ion storage layer and the ion vacancy layer 600, and also reduces the movement path of migrating ions between the electrochromic layer 400 and the ion vacancy layer 600. This allows the concentration of migrating ions in the ion storage layer 300 and the electrochromic layer 400 to maintain a high concentration for a long time, thereby improving the cycle life of the electrochromic glass.

[0052] Optionally, the ion vacancy layer 600 is a carbon-based material layer, a silicon-based material layer, a tin-based material layer, etc. It is understood that the ion vacancy layer 600 should be a material layer with more defects and vacancies to facilitate the embedding or de-embedding of mobile ions.

[0053] The carbon-based material layer may be made of one or more materials selected from graphene, amorphous carbon, mesocarbon microbeads, natural graphite, and artificial graphite. It is understood that the carbon-based material layer is generally a layered structure with a large number of defects and vacancies, which facilitates the rapid embedding and de-embedding of mobile ions. Furthermore, the carbon-based material also has excellent electrical conductivity, thereby facilitating enhanced ion transport between the ion storage layer 300 and the electrochromic layer 400.

[0054] Optionally, the material of the ion storage layer 300 is selected from any one or more of NiO, IrO2, Cr2O5, V2O5, Co2O3, and Rh2O3; the material of the electrochromic layer 400 is selected from any one or more of WO3, MoO3, TiO2, Nb2O5, MnO2, Ta2O5, viologens, polyaniline, viologens, pyrazoline, and polypyrrole; the material of the ion conductor layer 500 is selected from any one or more of LiPON, LiTaO3, LiNbO3, LiMn2O4, LiFePO4, LiCoO2, sodium manganate, sodium cobaltate, sodium vanadate, aluminum ion-doped LiTaO3, aluminum ion-doped LiNbO3, and an acidified polymer electrolyte; and the mobile ions are any one or more of lithium ions, sodium ions, aluminum ions, and hydrogen ions. It will be appreciated that the type of mobile ions depends on the material of the ion conductor layer 500. If the material of the ion conductor layer 500 is a lithium-containing electrolyte such as LiPON, LiTaO3, LiNbO3, LiMn2O4, LiFePO4, LiCoO2, then the migrating ions are lithium ions; if the material of the ion conductor layer 500 is a sodium-containing electrolyte such as sodium manganate, sodium cobaltate, sodium vanadate, then the migrating ions are sodium ions; if the material of the ion conductor layer 500 is an aluminum- and lithium-containing electrolyte such as aluminum ion-doped LiTaO3 or aluminum ion-doped LiNbO3, then the migrating ions are aluminum ions and lithium ions; if the material of the ion conductor layer 500 is an acidified polymer electrolyte, such as a polymer electrolyte acidified by nitric acid, sulfuric acid or phosphoric acid, then the migrating ions are hydrogen ions.

[0055] In one embodiment, the conductive glass is ITO conductive glass, the ion storage layer 300 is a NiO layer, the electrochromic layer 400 is a WO3 layer, and the ion conductor layer 500 is a LiNbO3 layer, that is, the migration ions are lithium ions. Thus, the structure of the electrochromic glass is as follows: ITO conductive glass / NiO layer / LiNbO3 layer / carbon-based material layer / WO3 layer / ITO conductive glass; the color change and fading process of the electrochromic glass is as follows: During the color change process, lithium ions enter the WO3 layer from the carbon-based material layer, causing W 6+ To W 5+ During the fading process, lithium ions are directly deintercalated from the WO3 layer and enter the carbon-based material layer, reducing the movement path of lithium ions and always maintaining the concentration of lithium ions in the WO3 layer, allowing the color change and fading reactions to proceed fully. Similarly, lithium ions enter the NiO layer from the carbon-based material layer, causing the NiO layer to fade. When lithium ions enter the carbon-based material layer from NiO, they will cause the NiO layer to color, completing the electrochromic reaction.

[0056] Furthermore, the thickness of the ion storage layer 300 ranges from 70 to 150 nm. Optionally, the thickness of the ion storage layer 300 is 70 nm, 110 nm, or 150 nm. The thickness of the electrochromic layer 400 ranges from 70 to 150 nm. Optionally, the thickness of the electrochromic layer 400 is 70 nm, 110 nm, or 150 nm. It is understood that the thickness of the ion storage layer 300 and the electrochromic layer 400 should not be too thin or too thick. Specifically, the ion intercalation and deintercalation process that determines the reaction rate in the electrochromic reaction is diffusion-controlled. Therefore, the color change effect depends on the diffusion coefficient of ions in the film and the specific surface area of ​​the film. If the film is too thin, the process is difficult to control and there are fewer sites for the migrating ions to embed, resulting in a poor application effect of the electrochromic layer 400. On the other hand, if the film is too thick, repeated coating is required, which is costly. The thicker the film, the longer the migration path of the migrating ions, resulting in a slower reaction.

[0057] The thickness of the ion conductor layer 500 ranges from 50 to 150 nm. Optionally, the thickness of the ion conductor layer 500 is 50 nm, 100 nm, or 150 nm. It is understood that the thickness of the ion conductor layer 500 should be neither too thin nor too thick. If the ion conductor layer 500 is too thin, process control will be difficult, and the supply of mobile ions will be insufficient, making it difficult to fully induce color change. If the ion conductor layer 500 is too thick, the application range of the electrochromic glass will be affected, as electronic devices now tend to be thin and lightweight.

[0058] The thickness of the ion vacancy layer 600 ranges from 10 to 50 nm. Optionally, the thickness of the ion vacancy layer 600 is 10 nm, 30 nm, or 50 nm. The ion vacancy layer 600 is selected to store some of the migrating ions. If the ion vacancy layer 600 is too thin, there will be fewer vacancies and the storage function will not be well performed. If the ion vacancy layer 600 is too thick, the cost will increase and the optical density (light-shielding ability) of the electrochromic glass will be increased, affecting the transmittance of the electrochromic glass.

[0059] An embodiment of the present invention also provides a method for preparing electrochromic glass, comprising the following steps:

[0060] coating an electrochromic layer on the first conductive glass or the second conductive glass by magnetron sputtering;

[0061] coating an ion storage layer on the first conductive glass or the second conductive glass by magnetron sputtering;

[0062] coating an ion conductor layer on the first conductive glass and / or the second conductive glass by magnetron sputtering;

[0063] coating an ion vacancy layer on the first conductive glass and / or the first conductive glass by magnetron sputtering or spin coating;

[0064] The first conductive glass and the second conductive glass are assembled to obtain electrochromic glass.

[0065] Specifically, the electrochromic layer and the ion storage layer can be plated on the same conductive glass, and finally the conductive glass can be assembled with another conductive glass; the electrochromic layer and the ion storage layer can also be plated on different conductive glasses respectively, and finally the two conductive glasses can be assembled. If the ion conductor layer has only one layer, it can be plated on any conductive glass. If there are multiple layers, it can be plated on the same conductive glass or on different conductive glasses. Similarly, if the ion vacancy layer has only one layer, it can be plated on any conductive glass. If there are multiple layers, it can be plated on the same conductive glass or on different conductive glasses. It is worth noting that the plating order of the electrochromic layer, the ion storage layer, the ion conductor layer and the ion vacancy layer depends on the specific structure of the electrochromic glass.

[0066] Furthermore, before depositing the ion storage layer on the first conductive glass by magnetron sputtering and depositing the electrochromic layer on the second conductive glass by magnetron sputtering, the steps of: cleaning the surfaces of the first and second conductive glasses are also included. Specifically, the ITO conductive glass is sequentially passed through polyacrylamide and silicone oil to remove oil stains on the surface of the ITO conductive glass. The surface is then passed through solutions such as acetone and ethanol to remove any remaining oil stains and impurities. Finally, the surface is cleaned using an ultrasonic cleaner and then wiped dry with acetone and ethanol to complete the cleaning of the conductive glass surfaces.

[0067] Furthermore, in the step of coating the electrochromic layer on the first conductive glass or the second conductive glass by magnetron sputtering, the sputtering power is 20 to 150 kW, the coating rate is 0.1 to 3 m / min, the argon flow rate is 300 to 1000 ml / min, and the oxygen flow rate is 500 to 700 ml / min;

[0068] In the step of plating the ion storage layer on the first conductive glass or the second conductive glass by magnetron sputtering, the sputtering power is 20-150 kW, the plating rate is 0.1-3 m / min, the argon flow rate is 300-1000 ml / min, and the oxygen flow rate is 500-700 ml / min;

[0069] In the step of plating the ion conductor layer on the first conductive glass and / or the second conductive glass by magnetron sputtering, the sputtering power is 50 to 130 kW, the plating rate is 0.15 to 3 m / min, and the argon flow rate is 300 to 1000 ml / min;

[0070] In the step of plating an ion vacancy layer on the first conductive glass and / or the second conductive glass by magnetron sputtering or spin coating, the sputtering power is 10-50 KW, the plating rate is 0.15-1 m / min, and the argon flow rate is 100-500 ml / min.

[0071] Furthermore, the steps for assembling the first conductive glass and the second conductive glass are as follows: leaving a controller circuit contact point on the cleaned ITO conductive glass surface, bonding the two conductive glasses that have completed magnetron sputtering relative to each other, and finally evenly injecting UV-proof sealant into the glass joint to complete the assembly of the electrochromic glass.

[0072] The following describes the structure of each film layer of the electrochromic glass, the thickness of each film layer, the preparation method, and the corresponding effects with reference to specific embodiments.

[0073] Example 1 to Example 4

[0074] The structure of the electrochromic glass is as follows: ITO conductive glass / NiO layer / LiNbO3 layer / carbon-based material layer / WO3 layer / ITO conductive glass (first conductive glass / ion storage layer / ion conductor layer / ion vacancy layer / electrochromic layer / second conductive glass). In Examples 1 to 4, the electrochromic glass structures are identical, but the thicknesses of the various layers vary. Specific layer thicknesses are shown in Table 1.

[0075] (1) Clean the surface of ITO conductive glass

[0076] A 20cm*20cm glass sample was passed through polyacrylamide and silicone oil in turn to remove the oil stains on the surface of the ITO conductive glass. Then, it was passed through acetone, ethanol and other solutions to remove the oil stains and impurities that were not cleaned thoroughly. Finally, it was cleaned in an ultrasonic cleaner for 3 hours. The sample was taken out and wiped dry with acetone and ethanol before the next step.

[0077] (2) Preparation of electrochromic layer

[0078] Take a piece of cleaned ITO conductive glass and use magnetron sputtering to coat a WO3 layer on the ITO conductive glass. The sputtering power is controlled to be 100KW, the coating rate is 0.15m / min, the Ar flow rate is 700ml / min, and the O2 flow rate is 500ml / min.

[0079] (3) Preparation of carbon-based material layer

[0080] A carbon-based material layer was deposited on the WO3 layer by magnetron sputtering, with the sputtering power controlled at 30 kW, the coating rate at 0.15 m / min, and the Ar flow rate at 300 ml / min.

[0081] (4) Preparation of ion conductor layer

[0082] A LiNbO3 layer was deposited on the carbon-based material layer by magnetron sputtering, with the sputtering power controlled to be 130 KW, the coating rate to be 0.15 m / min, and the Ar flow rate to be 1000 ml / min.

[0083] (5) Preparation of ion storage layer

[0084] Take another piece of ITO conductive glass that has been cleaned, and use magnetron sputtering to plate a NiO layer on the ITO conductive glass. Control the sputtering power to 130KW, the coating rate to 2m / min, the Ar flow rate to 700ml / min, and the O2 flow rate to 500ml / min.

[0085] (6) Assembling electrochromic glass

[0086] The controller circuit contact point is left on the cleaned surface of the ITO conductive glass, and the two conductive glasses that have completed magnetron sputtering are bonded relative to each other. Finally, UV-proof sealant is evenly injected into the glass joint to complete the assembly of the electrochromic glass.

[0087] Example 5 to Example 8

[0088] The structure of the electrochromic glass is as follows: ITO conductive glass / NiO layer / LiNbO3 layer / carbon-based material layer / LiNbO3 layer / WO3 layer / ITO conductive glass (first conductive glass / ion storage layer / ion conductor layer / ion vacancy layer / ion conductor layer / electrochromic layer / second conductive glass). In Examples 5 to 8, the electrochromic glass structures are identical, but the thicknesses of the various layers vary. Specific layer thicknesses are shown in Table 2.

[0089] (1) Clean the surface of ITO conductive glass

[0090] A 20cm*20cm glass sample was passed through polyacrylamide and silicone oil in turn to remove the oil stains on the surface of the ITO conductive glass. Then, it was passed through acetone, ethanol and other solutions to remove the oil stains and impurities that were not cleaned thoroughly. Finally, it was cleaned in an ultrasonic cleaner for 3 hours. The sample was taken out and wiped dry with acetone and ethanol before the next step.

[0091] (2) Preparation of electrochromic layer

[0092] Take a piece of cleaned ITO conductive glass and use magnetron sputtering to coat a WO3 layer on the ITO conductive glass. The sputtering power is controlled to be 100KW, the coating rate is 0.15m / min, the Ar flow rate is 700ml / min, and the O2 flow rate is 500ml / min.

[0093] (3) Preparation of ion conductor layer

[0094] A LiNbO3 layer was deposited on the WO3 layer by magnetron sputtering, with the sputtering power controlled at 130KW, the coating rate at 0.15m / min, and the Ar flow rate at 1000ml / min.

[0095] (4) Preparation of carbon-based material layer

[0096] A carbon-based material layer was deposited on the LiNbO3 layer by magnetron sputtering, with the sputtering power controlled at 30 KW, the coating rate at 0.15 m / min, and the Ar flow rate at 300 ml / min.

[0097] (5) Preparation of ion conductor layer

[0098] A LiNbO3 layer was deposited on the carbon-based material layer by magnetron sputtering, with the sputtering power controlled to be 130 KW, the coating rate to be 0.15 m / min, and the Ar flow rate to be 1000 ml / min.

[0099] (6) Preparation of ion storage layer

[0100] Take another piece of ITO conductive glass that has been cleaned, and use magnetron sputtering to plate a NiO layer on the ITO conductive glass. Control the sputtering power to 130KW, the coating rate to 2m / min, the Ar flow rate to 700ml / min, and the O2 flow rate to 500ml / min.

[0101] (7) Assembling electrochromic glass

[0102] The controller circuit contact point is left on the cleaned surface of the ITO conductive glass, and the two conductive glasses that have completed magnetron sputtering are bonded relative to each other. Finally, UV-proof sealant is evenly injected into the glass joint to complete the assembly of the electrochromic glass.

[0103] Example 9 to Example 12

[0104] The structure of the electrochromic glass is as follows: ITO conductive glass / NiO layer / carbon-based material layer / LiNbO3 layer / carbon-based material layer / WO3 layer / ITO conductive glass (first conductive glass / ion storage layer / ion vacancy layer / ion conductor layer / ion vacancy layer / electrochromic layer / second conductive glass). In Examples 9 to 12, the electrochromic glass structures are identical, but the thicknesses of the various layers vary. Specific layer thicknesses are shown in Table 3.

[0105] (1) Clean the surface of ITO conductive glass

[0106] A 20cm*20cm glass sample was passed through polyacrylamide and silicone oil in turn to remove the oil stains on the surface of the ITO conductive glass. Then, it was passed through acetone, ethanol and other solutions to remove the oil stains and impurities that were not cleaned thoroughly. Finally, it was cleaned in an ultrasonic cleaner for 3 hours. The sample was taken out and wiped dry with acetone and ethanol before the next step.

[0107] (2) Preparation of electrochromic layer

[0108] Take a piece of cleaned ITO conductive glass and use magnetron sputtering to coat a WO3 layer on the ITO conductive glass. The sputtering power is controlled to be 100KW, the coating rate is 0.15m / min, the Ar flow rate is 700ml / min, and the O2 flow rate is 500ml / min.

[0109] (3) Preparation of carbon-based material layer

[0110] A carbon-based material layer was deposited on the WO3 layer by magnetron sputtering, with the sputtering power controlled at 30 kW, the coating rate at 0.15 m / min, and the Ar flow rate at 300 ml / min.

[0111] (4) Preparation of ion conductor layer

[0112] A LiNbO3 layer was deposited on the carbon-based material layer by magnetron sputtering, with the sputtering power controlled to be 130 KW, the coating rate to be 0.15 m / min, and the Ar flow rate to be 1000 ml / min.

[0113] (5) Preparation of carbon-based material layer

[0114] A carbon-based material layer was deposited on the LiNbO3 layer by magnetron sputtering, with the sputtering power controlled at 30 kW, the coating rate at 0.15 m / min, and the Ar flow rate at 300 ml / min.

[0115] (6) Preparation of ion storage layer

[0116] Take another piece of ITO conductive glass that has been cleaned, and use magnetron sputtering to plate a NiO layer on the ITO conductive glass. Control the sputtering power to 130KW, the coating rate to 2m / min, the Ar flow rate to 700ml / min, and the O2 flow rate to 500ml / min.

[0117] (7) Assembling electrochromic glass

[0118] The controller circuit contact point is left on the cleaned surface of the ITO conductive glass, and the two conductive glasses that have completed magnetron sputtering are bonded relative to each other. Finally, UV-proof sealant is evenly injected into the glass joint to complete the assembly of the electrochromic glass.

[0119] Comparative Example 1 and Comparative Example 2

[0120] The electrochromic glass structure is as follows: ITO conductive glass / NiO layer / LiNbO3 layer / WO3 layer / ITO conductive glass (first conductive glass / ion storage layer / ion conductor layer / electrochromic layer / second conductive glass). The electrochromic glass in Comparative Examples 1 and 2 has the same structure, but the thickness of each layer varies. Specific film thicknesses are shown in Table 4.

[0121] (1) Clean the surface of ITO conductive glass

[0122] A 20cm*20cm glass sample was passed through polyacrylamide and silicone oil in turn to remove the oil stains on the surface of the ITO conductive glass. Then, it was passed through acetone, ethanol and other solutions to remove the oil stains and impurities that were not cleaned thoroughly. Finally, it was cleaned in an ultrasonic cleaner for 3 hours. The sample was taken out and wiped dry with acetone and ethanol before the next step.

[0123] (2) Preparation of electrochromic layer

[0124] Take a piece of cleaned ITO conductive glass and use magnetron sputtering to coat a WO3 layer on the ITO conductive glass. The sputtering power is controlled to be 100KW, the coating rate is 0.15m / min, the Ar flow rate is 700ml / min, and the O2 flow rate is 500ml / min.

[0125] (3) Preparation of ion conductor layer

[0126] A LiNbO3 layer was deposited on the WO3 layer by magnetron sputtering, with the sputtering power controlled at 130KW, the coating rate at 0.15m / min, and the Ar flow rate at 1000ml / min.

[0127] (4) Preparation of ion storage layer

[0128] Take another piece of ITO conductive glass that has been cleaned, and use magnetron sputtering to plate a NiO layer on the ITO conductive glass. Control the sputtering power to 130KW, the coating rate to 2m / min, the Ar flow rate to 700ml / min, and the O2 flow rate to 500ml / min.

[0129] (5) Assembling electrochromic glass

[0130] The controller circuit contact point is left on the cleaned surface of the ITO conductive glass, and the two conductive glasses that have completed magnetron sputtering are bonded relative to each other. Finally, UV-proof sealant is evenly injected into the glass joint to complete the assembly of the electrochromic glass.

[0131] Table 1. Response time and cycle counts for the electrochromic glasses with different film thicknesses prepared in Examples 1 to 4. (ITO conductive glass / NiO layer / LiNbO3 layer / carbon-based material layer / WO3 layer / ITO conductive glass)

[0132]

[0133]

[0134] Table 2. Response time and cycle counts for the electrochromic glasses of different film thicknesses prepared in Examples 5-8. (ITO conductive glass / NiO layer / LiNbO3 layer / carbon-based material layer / LiNbO3 layer / WO3 layer / ITO conductive glass)

[0135]

[0136] Table 3. Response time and cycle counts for the electrochromic glasses with different film thicknesses prepared in Examples 9-12. (ITO conductive glass / NiO layer / carbon-based material layer / LiNbO3 layer / carbon-based material layer / WO3 layer / ITO conductive glass)

[0137]

[0138]

[0139] Table 4. Response time and cycle counts for the electrochromic glasses with different film thicknesses prepared in Comparative Examples 1 and 2. (ITO conductive glass / NiO layer / LiNbO3 layer / WO3 layer / ITO conductive glass)

[0140]

[0141] It should be noted that the response time of electrochromic glass includes both tinting time and fading time. The tinting time refers to the time required for the electrochromic glass to transition from a faded state to a tinted state, while the fading time refers to the time required for the electrochromic glass to transition from a tinted state to a faded state. In the above embodiments and comparative examples, the response time is expressed in terms of tinting time.

[0142] The number of cycles of electrochromic glass refers to the number of times the electrochromic glass can cycle stably. If the electrochromic glass changes color slowly after multiple cycles, it will not be counted in the number of cycles.

[0143] By comparing the embodiment with the comparative example, it can be found that the number of cycles of the electrochromic glass of the embodiment is better than that of the electrochromic glass of the comparative example. This is because, compared with the comparative example, in the electrochromic glass of the embodiment, a carbon-based material layer (ion vacancy layer) is added between the WO3 layer (electrochromic layer) and the NiO layer (ion storage layer). Since the carbon-based material layer has more defects and vacancies, lithium ions can be quickly embedded and deintercalated, reducing the movement path of lithium ions, so that the concentrations of the WO3 layer and the NiO layer can be maintained at a high concentration for a long time, which is beneficial to improving the number of cycles of the electrochromic glass.

[0144] By comparing Examples 1 to 4, Examples 5 to 8, and Examples 9 to 12, it can be found that for electrochromic glass of the same structure, the thicker the thickness of the carbon-based material layer (ion vacancy layer), the faster the response time of the electrochromic glass and the better the number of cycles. This is because the thicker the carbon-based material layer, the more vacancies and defects it has, which is more conducive to the embedding and de-embedding of lithium ions, thereby improving the number of cycles of the electrochromic glass. However, if the carbon-based material layer is too thick, it will increase the cost and also affect the transmittance of the electrochromic glass. Therefore, it is necessary to comprehensively consider a variety of influencing factors to select the appropriate thickness of the carbon-based material layer.

[0145] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made by using the contents of the present invention description and drawings under the inventive concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. An electrochromic glass, characterized in that: include: a first conductive glass and a second conductive glass; The ion storage layer and the electrochromic layer are both sandwiched between the first conductive glass and the second conductive glass; as well as, At least one ion conductor layer and at least one ion vacancy layer are both sandwiched between the ion storage layer and the electrochromic layer, the ion conductor layer and the ion vacancy layer are stacked adjacent to each other, the ion conductor layer is used to provide mobile ions, and the ion vacancy layer is used for embedding or de-embedding the mobile ions; The ion vacancy layer is a carbon-based material layer; the first conductive glass and the second conductive glass are both ITO conductive glass; The electrochromic glass includes two ion conductor layers and an ion vacancy layer, wherein the ion vacancy layer is sandwiched between the two ion conductor layers; or the electrochromic glass includes an ion conductor layer and two ion vacancy layers, wherein the ion conductor layer is sandwiched between the two ion vacancy layers.

2. The electrochromic glass according to claim 1, wherein: The material of the carbon-based material layer is selected from any one or more of graphene, amorphous carbon, mesocarbon microbeads, natural graphite and artificial graphite.

3. The electrochromic glass according to claim 1, wherein: The material of the ion storage layer is selected from any one or more of NiO, IrO2, Cr2O5, V2O5, Co2O3, and Rh2O3; the material of the electrochromic layer is selected from any one or more of WO3, MoO3, TiO2, Nb2O5, MnO2, Ta2O5, violaceous acid, polyaniline, violaceous acid, pyrazoline, and polypyrrole; the material of the ion conductor layer is selected from any one or more of LiPON, LiTaO3, LiNbO3, LiMn2O4, LiFePO4, LiCoO2, sodium manganate, sodium cobaltate, sodium vanadate, aluminum ion-doped LiTaO3, aluminum ion-doped LiNbO3, and acidified polymer electrolyte; the migrating ions are any one or more of lithium ions, sodium ions, aluminum ions, and hydrogen ions.

4. The electrochromic glass according to claim 1, wherein: The thickness of the ion storage layer ranges from 70 to 150 nm; the thickness of the electrochromic layer ranges from 70 to 150 nm; the thickness of the ion conductor layer ranges from 50 to 150 nm; and the thickness of the ion vacancy layer ranges from 10 to 50 nm.

5. The method for preparing the electrochromic glass according to any one of claims 1 to 4, characterized in that: The preparation method comprises: coating an electrochromic layer on the first conductive glass or the second conductive glass by magnetron sputtering; coating an ion storage layer on the first conductive glass or the second conductive glass by magnetron sputtering; coating an ion conductor layer on the first conductive glass and / or the second conductive glass by magnetron sputtering; coating an ion vacancy layer on the first conductive glass and / or the first conductive glass by magnetron sputtering or spin coating; The first conductive glass and the second conductive glass are assembled to obtain electrochromic glass.

6. The method for preparing electrochromic glass according to claim 5, wherein: In the step of coating the electrochromic layer on the first conductive glass or the second conductive glass by magnetron sputtering, the sputtering power is 20-150 kW, the coating rate is 0.1-3 m / min, the argon flow rate is 300-1000 ml / min, and the oxygen flow rate is 500-700 ml / min; In the step of plating the ion storage layer on the first conductive glass or the second conductive glass by magnetron sputtering, the sputtering power is 20-150 kW, the plating rate is 0.1-3 m / min, the argon flow rate is 300-1000 ml / min, and the oxygen flow rate is 500-700 ml / min; In the step of plating the ion conductor layer on the first conductive glass and / or the second conductive glass by magnetron sputtering, the sputtering power is 50 to 130 kW, the plating rate is 0.15 to 3 m / min, and the argon flow rate is 300 to 1000 ml / min; In the step of plating an ion vacancy layer on the first conductive glass and / or the second conductive glass by magnetron sputtering or spin coating, the sputtering power is 10-50 KW, the plating rate is 0.15-1 m / min, and the argon flow rate is 100-500 ml / min.

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