Reflectors, methods for manufacturing reflective devices, and vehicles

Abstract

A reflective device comprising a first transparent substrate, a transparent conductive layer, a second transparent substrate, a reflective layer, a sealant, and a light-adjusting composition. The reflective layer faces the transparent conductive layer, the light-adjusting composition is provided between the reflective layer and the transparent conductive layer, the sealant is connected between the first transparent substrate and the second transparent substrate, a cavity is defined by the sealant, the transparent conductive layer and the reflective layer, the light-adjusting composition is provided within the cavity, and the sealant contains filler particles with a dielectric constant of 20 or more.

Description

[Technical Field]

[0001] This application relates to the following: Chinese Patent Application No. 202311075764.2, titled "REFLECTING DEVICE, MANUFACTURING METHOD FOR REFLECTING DEVICE, AND VEHICLE," filed with the China National Intellectual Property Administration on August 24, 2023; Chinese Patent Application No. 202311270928.7, titled "COLOR-CHANGING GLASS AND VEHICLE," filed with the China National Intellectual Property Administration on September 27, 2023; Chinese Patent Application No. 202311218509.9, titled "ANODE ELECTROCHROMIC MATERIAL, ELECTROCHROMIC COMPOSITION, AND ELECTROCHROMIC DEVICE," filed with the China National Intellectual Property Administration on September 19, 2023; and "ANODE Chinese Patent Application No. 202311216097.5, titled "ELECTROCHROMIC MATERIAL, ELECTROCHROMIC COMPOSITION, AND ELECTROCHROMIC DEVICE," filed with the China National Intellectual Property Administration on July 11, 2023; Chinese Patent Application No. 202310851114.6, titled "PHENAZINE COMPOUND INCLUDING BRIDGE RING STRUCTURE AND APPLICATION THEREOF, AND ELECTROCHROMIC DEVICE AND APPLICATION THEREOF," filed with the China National Intellectual Property Administration on September 27, 2023; "CARBAZOLE COMPOUND AND COMPOSITION, PREPARATION METHOD THEREFORE AND APPLICATION THEREFOF, AND ELECTROCHROMIC Chinese Patent Application No. 202311267781.6, titled "DEVICE," and Chinese Patent Application No. 202311136253, filed with the China National Intellectual Property Administration on August 31, 2023, titled "LIGHT INTENSITY ADJUSTMENT DEVICE AND APPLICATION THEREOF."This asserts the priority of Article 7, which is incorporated herein by reference in its entirety.

[0002] Technical field This application relates to the field of reflector technology, and more particularly to reflectors, methods for manufacturing reflectors, and vehicles.

[0003] background A reflector is an optical element with a smooth surface and the ability to reflect light. Some reflectors have adjustable reflectivity to suit a wider range of application scenarios.

[0004] Reflectors that automatically adjust reflectivity are primarily realized using organic small molecule compositions. Under applied voltage, the organic small molecules between the transparent conductive layer and the reflective layer undergo an electrochemical oxidation-reduction reaction, changing their molecular structure and absorbing visible light to adjust the reflectivity of the device. Currently, the dielectric breakdown voltage between the transparent conductive layer and the reflective layer is low. As a result, the light adjustment performance of the reflector tends to be unstable.

[0005] overview The technical problem to be solved in the embodiments of the present application is to provide a reflector having controllable reflectivity and high stability, a method for manufacturing a reflector, and a vehicle.

[0006] According to the first aspect, the present application is a reflecting device, A first transparent substrate sheet including a first surface and a second surface that are opposite to each other, A transparent conductive layer is placed on the second surface, A second transparent substrate sheet including a third surface and a fourth surface that are opposite to each other, A reflective layer is located on the third surface and faces the transparent conductive layer, A sealant, connected between a first transparent substrate sheet and a second transparent substrate sheet, wherein the sealant, a transparent conductive layer, and a reflective layer define a cavity, and the sealant contains filler particles having a dielectric constant of 20 or more. A light-adjusting composition placed within the cavity and A reflective device is provided that includes the following features.

[0007] In relation to the first aspect, in possible configurations, the dielectric constant of the filler particles is in the range of 25 to 150.

[0008] In relation to the first embodiment, in a possible configuration, the filler particles include at least one of lead titanate, barium titanate, lanthanum titanate, titanium oxide, and zirconium oxide.

[0009] In relation to the first aspect, in a possible configuration, the sealant is configured to be hollow in the thickness direction, and the two end faces of the sealant in the thickness direction are connected to a transparent conductive layer and a reflective layer, respectively.

[0010] In relation to the first aspect, in a possible configuration, the sealant comprises a first sealant and a second sealant, the first sealant and the second sealant defining and forming the sealant.

[0011] In relation to the first aspect, in possible configurations, the shape of the filler particle is one of a rectangular prism, a cube, a sphere, and a cylinder.

[0012] In relation to the first embodiment, in a possible configuration, the first transparent substrate sheet comprises one of glass, acrylic, and polyvinyl chloride, and the second transparent substrate sheet comprises one of glass, acrylic, and polyvinyl chloride, and the visible light transmittance of the first transparent substrate sheet and the visible light transmittance of the second transparent substrate sheet are both 80% or more.

[0013] In relation to the first embodiment, in a possible configuration, the transparent conductive layer satisfies at least one of the following conditions: the transparent conductive layer comprises at least one of ITO, CTO, ZnO, and InO; the thickness of the transparent conductive layer is in the range of 50 nm to 500 nm; and the visible light transmittance of the transparent conductive layer is 80% or more.

[0014] In relation to the first aspect, in a possible configuration, the reflective layer satisfies at least one of the following conditions: the reflective layer comprises one of silver, silver alloy, aluminum, aluminum alloy, chromium, and chromium alloy; the thickness of the reflective layer is in the range of 10 nm to 500 nm; and the reflectance of the reflective layer is 70% or more.

[0015] In relation to the first embodiment, in a possible configuration, the reflector further comprises a transition layer, which is located between the reflector and a third surface, and the transition layer comprises at least one of SiO, TiO, Nb2O5, and Al2O3.

[0016] In relation to the first aspect, in a possible configuration, the reflector further includes a first electrode plate and a second electrode plate, the first electrode plate being electrically connected to a transparent conductive layer and the second electrode plate being electrically connected to a reflective layer.

[0017] In relation to the first embodiment, in a possible configuration, the surface of the transparent conductive layer facing the first transparent substrate sheet includes a contact region that contacts the second surface and a concave region that is recessed away from the second surface. The concave region surrounds the contact region and is spaced apart from the second surface. A decorative layer is placed between the concave region and the second surface, and the reflectivity of the decorative layer is 50% or more.

[0018] According to a second aspect, the present invention relates to a method for manufacturing a reflector, The steps include preparing a first transparent substrate sheet including a first surface and a second surface arranged on opposite sides of each other, and placing a transparent conductive layer on the second surface, The steps include preparing a second transparent substrate sheet including a third surface and a fourth surface arranged on opposite sides of each other, and placing a reflective layer on the third surface, The steps include: bringing the transparent conductive layer facing the reflective layer and separating the transparent conductive layer from the reflective layer, The steps include forming a sealant between a first transparent substrate sheet and a second transparent substrate sheet, defining a cavity with the sealant, a transparent conductive layer, and a reflective layer, and injecting a light-adjusting composition into the cavity. Includes, The sealant contains filler particles with a dielectric constant of 20 or more. The present invention provides a method for manufacturing a reflective device.

[0019] In relation to the second aspect, in possible configurations, the step of placing a reflective layer on the third surface is: The steps include placing a transition layer on the third surface, The steps include: Placing a reflective layer on the surface of the transition layer that is away from the second transparent substrate sheet; Includes.

[0020] In relation to a second aspect, in a possible configuration, the sealant comprises a first sealant and a second sealant. The steps of forming a sealant between a first transparent substrate sheet and a second transparent substrate sheet, defining a cavity with the sealant, a transparent conductive layer, and a reflective layer, and injecting a light-modulating composition into the cavity are as follows: The first step is to place a first sealant connecting the first transparent substrate sheet and the second transparent substrate sheet between the first transparent substrate sheet and the second transparent substrate sheet, and to define a cavity having an opening with the first sealant, a transparent conductive layer, and a reflective layer. The steps include injecting a light-tuning composition into the cavity through an opening, The steps include: placing a second sealant between a first transparent substrate sheet and a second transparent substrate sheet to connect the first transparent substrate sheet and the second transparent substrate sheet; Includes.

[0021] In a third aspect, the present application discloses a vehicle, which includes a reflector according to the first aspect.

[0022] In this application, a sealant connects a first transparent substrate sheet and a second transparent substrate sheet. The sealant contains filler particles, the dielectric constant of which is 20 or more. This increases the dielectric breakdown voltage of the electric field formed by the reflective layer and the transparent conductive layer, improves the electrochemical stability of the filler particles under the electric field, improves the reflective reliability of the reflective device, and extends the service life of the reflective device.

[0023] To more clearly explain the technical solutions or background art of the embodiments of this application, the accompanying drawings used to describe the embodiments or background art of this application are described below. [Brief explanation of the drawing]

[0024] [Figure 1] This is a cross-sectional view of a light-emitting mirror device according to several embodiments of the present application. [Figure 2] This is a top view of a light-emitting mirror device according to several embodiments of the present application, with the first transparent substrate sheet and transparent conductive layer removed. [Figure 3] This is a cross-sectional view of a transparent conductive layer according to several embodiments of the present application. [Figure 4] This is a schematic flowchart of a method for manufacturing a light-emitting mirror device according to several embodiments of the present invention. [Figure 5] This is a block diagram of a simplified vehicle structure according to several embodiments of the present invention. [Figure 6] This figure shows the structure of discoloration glass according to several embodiments of the present application. [Figure 7] This is a cross-sectional top view of discoloration glass according to several embodiments of the present application. [Figure 8] This figure shows another structure of discoloration glass according to some embodiments of the present application. [Figure 9] This figure shows yet another structure of discoloration glass according to some embodiments of the present application. [Figure 10] This figure shows the cross-sectional structure of discoloration glass according to several embodiments of the present application. [Figure 11] This figure shows another cross-sectional structure of discoloration glass according to several embodiments of the present application. [Figure 12] This figure shows yet another cross-sectional structure of discoloration glass according to some embodiments of the present application. [Figure 13] This figure shows the structure of an electrochromic device with several configurations according to the present invention. [Figure 14] This figure shows the structure of an electrochromic device with several configurations according to the present invention. [Figure 15] This figure shows the structure of an electrochromic device according to several embodiments. [Figure 16] This is a cross-sectional view of a light intensity adjustment device according to the configuration of the present invention. [Figure 17] Figure 17 is a bottom view of a light intensity adjustment device according to the configuration of the present invention, showing that at least one of the first electrical conductor 5d and the second electrical conductor 8d is formed in the device in an L-shape and structure. [Figure 18] Figure 18 is a bottom view of a light intensity adjustment device according to another configuration of the present invention, showing that the first electrical conductor 5d and the second electrical conductor 8d are formed within the device in an L-shape and structure. [Figure 19] This is a top view of a conventional I-shaped device, showing that a first I-shaped conductive layer 5d and a second I-shaped conductive layer 8d are formed within the device in an I-shape and structure. [Figure 20] This is a cross-sectional view of a conventional I-type device along the EE direction. [Figure 21] This is a cross-sectional view of a conventional I-type device along the FF direction.

[0025] Explanation of reference number 1:Reflector; 10: First transparent substrate sheet; 11: First surface; 12: Second surface; 20: transparent conductive layer; 21: contact area; 22: concave area; 30: Second transparent substrate sheet; 31: Third surface; 32: Fourth surface; 40: Reflective layer; 50: Light regulating composition; 60:Transition layer; 70: sealant; 71: first sealant; 72: second sealant; 80: Decorative layer; 90: First electrode plate; 100: Second electrode plate; 2: Vehicles; S101~S106: Step; 100a: Discoloration glass; 11a: First glass substrate board; 12a: Second glass substrate board; 20a: Discoloration assembly; 21a: Discoloration layer; 221a: First conductive layer; 222a: Second conductive layer; 231a: Diffusion ring; 241a: First protective layer; 242a: Second protective layer; 232a: Second diffusion ring; 31a: First substrate layer; 32a: Second substrate layer; 100a': Discoloration glass; 11a': First glass substrate board; 12a': Second glass substrate board; 20a': Discoloration assembly; 100b: Electrochromic device; 10b: First base board; 20b: First electrode; 11b: Second base board; 21b: Second electrode; 30b: Electrochromic layer; 40b: Sealing member; 100c: Electrochromic device; 10c: First base board; 20c: First electrode; 11c: Second base board; 21c: Second electrode; 30c: Electrochromic layer; 40c: Sealing member; 1d: First base layer; Ad: First conductive layer; 13d: Functional layer; Bd: Second conductive layer; 12d: Second base layer; 5d: First electrical conductor; 2d: First bottom layer; 3d: First conductive layer; 10d: Third conductive layer; 11d: Second bottom layer; 8d: Second electrical conductor; 7d: Frame sealant layer; 6d: Insulating layer; 4d: First protective layer; 9d: Second protective layer; 10d: Third conductive layer; 1n: First base material; 2n: First conductive surface; 3n: Cavity; 4n: Second conductive surface; 5n: Second base material; 6n: Frame sealant; 7n: Frame sealant.

[0026] Description of the Embodiment Reflectors are optical elements with smooth surfaces and the ability to reflect light, and are extremely important items in both life and science. The most common mirrors used for grooming, rearview mirrors used to observe the driving conditions of vehicles behind, and reflective telescopes are all reflectors.

[0027] To adapt reflectors to a wider range of application scenarios, some reflectors have adjustable reflectivity. Reflectors with automatically adjustable reflectivity are primarily realized using small organic molecule compositions. Under applied voltage, the small organic molecules between the transparent conductive layer and the reflective layer undergo an electrochemical redox reaction, changing their molecular structure and absorbing visible light, thereby adjusting the reflectivity of the device. Currently, the dielectric breakdown voltage between the transparent conductive layer and the reflective layer is low. As a result, the optical tuning performance of reflectors tends to be unstable.

[0028] To further clarify the purpose, technical solution, and advantages of this application, the application will be described in detail below with reference to the attached drawings.

[0029] This application discloses a reflector, a method for manufacturing a reflector, and a vehicle. The vehicle includes a reflector that can reflect incident light. For example, the reflector may be a reflector that can be used as a rearview mirror for a vehicle, thereby allowing the driver to observe the situation behind the vehicle by rearview mirror while driving the vehicle. The vehicle may be, but is not limited to, a fuel vehicle, an electric vehicle, a motorcycle, and an electric moped.

[0030] Please refer to Figures 1 and 2. The reflective device 1 includes a first transparent substrate sheet 10, a second transparent substrate sheet 30, a transparent conductive layer 20, a reflective layer 40, a sealant 70, and a light-adjusting composition 50.

[0031] The first transparent substrate sheet 10 includes a first surface 11 and a second surface 12 that are arranged on opposite sides in the thickness direction. The first transparent substrate sheet 10 includes at least one of glass, acrylic, and polyvinyl chloride, and the visible light transmittance of the first transparent substrate sheet 10 is 80% or more. Note that the visible light transmittance of the first transparent substrate sheet 10 may have an error. The visible light transmittance of the first transparent substrate sheet 10 may have an error of 10%. For example, in actual application, the visible light transmittance of the first transparent substrate sheet 10 may be set to 72% or more. The specific thickness of the first transparent substrate sheet 10 is not limited in this application. The first transparent substrate sheet 10 has a high visible light transmittance, which allows most of the incident light to pass through the first transparent substrate sheet 10.

[0032] The second transparent substrate sheet 30 includes a third surface 31 and a fourth surface 32 that are arranged on opposite sides in the thickness direction. The second transparent substrate sheet 30 includes at least one of glass, acrylic, and polyvinyl chloride, and the visible light transmittance of the second transparent substrate sheet 30 is 80% or more. Note that the visible light transmittance of the second transparent substrate sheet 30 may have an error. The visible light transmittance of the second transparent substrate sheet 30 may have an error of 10%. For example, in actual application, the visible light transmittance of the second transparent substrate sheet 30 may be set to 72% or more. The specific thickness of the second transparent substrate sheet 30 is not limited in this application.

[0033] The transparent conductive layer 20 is located on the second surface 12 and contains at least one of ITO (indium tin oxide), CTO (cadmium tin oxide), ZnO (zinc oxide), and InO (indium oxide). Note that the material of the transparent conductive layer 20 may be any one of ITO, CTO, ZnO, and InO, or it may be a composition of multiple materials from ITO, CTO, ZnO, and InO. The thickness of the transparent conductive layer 20 is in the range of 50 nm to 500 nm, and the thickness of the transparent conductive layer 20 may have an error of 10%. For example, the actual thickness of the transparent conductive layer 20 may be set to 45 nm to 550 nm. The visible light transmittance of the transparent conductive layer 20 is 80% or more, which allows incident light to pass through the transparent conductive layer 20. The visible light transmittance of the transparent conductive layer 20 may have an error of 10%. For example, during actual application, the visible light transmittance of the transparent conductive layer 20 is set to 72% or higher. The sheet resistance of the transparent conductive layer 20 is 30Ω or less, and the sheet resistance of the transparent conductive layer 20 may have an error of 10%. During actual application, the sheet resistance of the transparent conductive layer 20 may be 33Ω or less.

[0034] The reflective layer 40 is located on the third surface 31. Note that "located on the third surface 31" means that the reflective layer 40 is directly located on the third surface 31, or it is located indirectly on the third surface 31. The reflective layer 40 includes one of silver, silver alloy, aluminum, aluminum alloy, chromium, and chromium alloy. The thickness of the reflective layer 40 may be set to 10 nm to 500 nm, and the thickness of the reflective layer 40 may be 10%. For example, the actual thickness of the reflective layer 40 may be set to 9 nm to 550 nm. The reflectance of the reflective layer 40 is 70% or more. Specifically, the reflectance of the reflective layer 40 may have an error of 10%. For example, the actual reflectance of the reflective layer 40 may be greater than 63%, and the reflective layer 40 may be configured to reflect incident light. Due to its high reflectance, the reflective layer 40 can reflect most of the incident light that irradiates it. The sheet resistance of the reflective layer 40 is 10Ω or less, and the sheet resistance of the reflective layer 40 may have an error of 10%. In actual application, the sheet resistance of the reflective layer 40 may be 11Ω or less.

[0035] In the embodiments provided herein, the reflective layer 40 faces the transparent conductive layer 20. The reflective layer 40 is spaced apart from the transparent conductive layer 20. The transparent conductive layer 20 can be connected to the positive terminal of a power supply, and the reflective layer 40 can be electrically connected to the negative terminal of a power supply. The transparent conductive layer 20 is connected to the positive terminal of a power supply, and the reflective layer 40 is connected to the negative terminal of a power supply, thereby enabling the formation of an electric field.

[0036] The sealant 70 is connected between the first transparent substrate sheet 10 and the second transparent substrate sheet 30, and the sealant 70, the transparent conductive layer 20, and the reflective layer 40 define a cavity. The cavity is configured to house a light-modulating composition 50, which is used to adjust the reflectance of incident light.

[0037] The sealant 70 comprises an adhesive and filler particles. The adhesive may be a thermosetting adhesive. Alternatively, the sealant 70 may be a photocurable adhesive or a thermosetting adhesive. Specifically, the adhesive includes, but is not limited to, phenolic resins, epoxy resins, polyaminophens, unsaturated polyesters, heterocyclic polymers, unsaturated polyacetic acids, polyacrylic acids, epoxyacrylic acids, and polyurethane acrylic acids. The dielectric constant of the adhesive may be in the range of 2 to 4.

[0038] The dielectric constant of the filler particles is 20 or higher, which increases the dielectric breakdown voltage of the electric field formed by the reflective layer 40 and the transparent conductive layer 20, thereby improving the electrochemical stability of the photo-tuning composition under the electric field, improving the reflective reliability of the reflective device, and extending the service life of the reflective device. Note that the dielectric constant of the filler particles may have an error of 10%, and the actual dielectric constant of the filler particles may be 18 or higher.

[0039] The dielectric constant of the filler particles may be in the range of 25 to 150. The material of the filler particles may be one of lead titanate, barium titanate, lanthanum titanate, titanium oxide, and zirconium oxide, or the material of the filler particles may be a combination of several materials from lead titanate, barium titanate, lanthanum titanate, titanium oxide, and zirconium oxide.

[0040] In some embodiments, when filler particles with different dielectric constants are doped into the sealant, the dielectric strength between the transparent conductive layer and the reflective layer in the reflective device differs. See the table below for details. In the table, when filler particles with a dielectric constant of 26 are doped into the sealant, a voltage of 7V is required for dielectric breakdown between the transparent conductive layer and the reflective layer. When filler particles with a dielectric constant of 50 are doped into the sealant, a voltage of 12V is required for dielectric breakdown between the transparent conductive layer and the reflective layer. However, when filler particles with a dielectric constant of 1.56 are doped into the sealant, only a voltage of 3V is required for dielectric breakdown between the transparent conductive layer and the reflective layer.

[0041] [Table 1]

[0042] The shape of the filler particles may be any one of the following: a rectangular prism, a cube, a sphere, or a cylinder. In the sealant 70, all filler particles may have the same shape. Alternatively, different shapes of filler particles may be present simultaneously in the sealant 70. By using a filler with a regular shape and uniform size as a support, it is possible to effectively ensure that the thickness of the sealant is uniform, thereby ensuring that the gap between the first transparent substrate material and the second transparent substrate material is uniform, that the electric fields of the positive and negative electrode plates of the apparatus are stable and uniform, and that the reflectivity is uniform and stable.

[0043] In the embodiments provided in this application, when the filler particles are spherical, the size of the filler particles is in the range of 30 μm to 300 μm, and the filler particles placed in the adhesive are uniform in size, which tends to make the entire sealant 70 flatter, thereby improving the stability of the sealant 70 when connecting the first transparent substrate sheet 10 and the second transparent substrate sheet 30.

[0044] In the embodiments provided herein, in possible configurations, the transparent conductive layer 20 completely covers the second surface 12, the transition layer 60 completely covers the third surface 31, and the reflective layer 40 completely covers the transition layer 60. The sealant 70 is connected between the transparent conductive layer 20 and the reflective layer 40, and together with them defines a cavity.

[0045] Refer to Figure 3 for the embodiment provided in this application. The surface of the transparent conductive layer 20 facing the first transparent substrate sheet includes a contact area 21 that contacts the second surface and a concave area 22 that is recessed away from the second surface 12. The concave area 22 surrounds the contact area 21 and is spaced apart from the second surface 12. A decorative layer 80 is placed between the concave area 22 and the second surface 12, and the reflectivity of the decorative layer 80 is 50% or more. The reflectivity of the decorative layer 80 may have an error of 10%. In actual application, the reflectivity of the decorative layer 80 may be 45% or more. The decorative layer 80 can improve the overall aesthetic appearance of the reflective device. In addition, the decorative layer 80 can reduce the leakage of light incident on the light-adjusting composition 50 from the sealant 70.

[0046] In the embodiments provided herein, the sealant 70 comprises a first sealant 71 and a second sealant 72, the first sealant 71 and the second sealant 72 defining the sealant 70.

[0047] In the embodiments provided herein, the light-modulating composition 50 is in contact with the transparent conductive layer 20 and the reflective layer 40. In other words, if the first transparent substrate sheet 10 and the second transparent substrate sheet 30 are arranged vertically and the light-modulating composition 50 is placed on the third surface 31 of the second transparent substrate sheet 30, the light-modulating composition 50 can support the first transparent substrate sheet 10, thereby improving the overall structural stability of the reflective device.

[0048] The light-tuning composition 50 comprises a cathode active material and an anode active material. Under an electric field, the light-tuning composition 50 can undergo an electrochemical redox reaction, thereby changing the molecular mechanism within the light-tuning composition 50. In this way, the absorption of incident light by the light-tuning composition 50 can be improved, and the reflectance of the reflector can be reduced. For example, under an electric field, the light-tuning composition 50 can change the absorption of incident light. When the light-tuning composition 50 improves its light absorption ability under an electric field, the reflectance of the reflector can be reduced from over 60% to less than 15%. Note that when specifically adjusting the reflectance of the reflector, the reflectance of the reflector can be controlled by adjusting the electric field strength.

[0049] In the embodiments provided herein, the reflective device further includes a transition layer 60. The transition layer 60 is located between the reflective layer 40 and the third surface 31. The transition layer 60 includes at least one of SiO (silicon monoxide), TiO (indium tin oxide), Nb2O5 (niobium pentoxide), and Al2O3 (aluminum oxide). Note that the second transparent substrate sheet 30 includes one of glass, acrylic, and polyvinyl chloride, and the reflective layer 40 includes one of silver, silver alloy, aluminum, aluminum alloy, chromium, and chromium alloy. If the reflective layer 40 is located directly on the second transparent substrate sheet 30, the connection between the reflective layer 40 and the second transparent substrate sheet 30 is prone to instability. The transition layer 60 includes at least one of SiO, TiO, Nb2O5, and Al2O3. The transition layer 60 can adhere well to the second transparent substrate sheet 30, and the reflective layer 40 can adhere even better to the transition layer 60. The transition layer 60 is placed on the third surface 31 of the second transparent substrate sheet 30, and then the reflective layer 40 is placed on the transition layer 60, thereby allowing the reflective layer 40 to be placed on the second transparent substrate sheet 30 more stably. The thickness of the transition layer 60 may be in the range of 1 nm to 300 nm, and a 10% error is allowed in the process of forming the transition layer 60, and the thickness of the transition layer 60 may be in the range of 0.9 nm to 330 nm.

[0050] In the embodiments provided herein, the reflector further includes a first electrode plate 90 and a second electrode plate 100. The first electrode plate 90 is electrically connected to the transparent conductive layer 20, and the second electrode plate 100 is electrically connected to the reflective layer 40. The first electrode plate 90 and the second electrode plate 100 are arranged in the reflector so that the reflector can be electrically connected to an external power supply. Specifically, the first electrode plate 90 is connected to the positive electrode of the external power supply, and the second electrode plate 100 is connected to the negative electrode of the external power supply, so that the transparent conductive layer 20 and the reflective layer 40 form an electric field.

[0051] Please refer to Figure 4. Embodiments of the present application further provide a method for manufacturing a reflective device. For the specific structure of the reflective device, please refer to the description in Example 1. This method includes the following steps:

[0052] S101: A step of preparing a first transparent substrate sheet including a first surface and a second surface arranged on opposite sides of each other, and placing a transparent conductive layer on the second surface.

[0053] The transparent conductive layer is plated onto the second surface by vacuum plating.

[0054] S102: A second transparent substrate sheet is prepared, which includes a third surface and a fourth surface arranged on opposite sides of each other, and a reflective layer is placed on the third surface.

[0055] In some embodiments, the step of placing a reflective layer on a third surface includes the step of placing a transition layer on the third surface and the step of placing a reflective layer on the surface of the transition layer that is away from the second transparent substrate sheet.

[0056] Specifically, in order to ensure that the reflective layer can be stably positioned on the second transparent substrate sheet, the transition layer is vacuum-plated onto the third surface, and then the reflective layer is vacuum-plated onto the transition layer.

[0057] S103: A step of bringing the transparent conductive layer facing the reflective layer and separating the transparent conductive layer from the reflective layer.

[0058] S104: A step of placing a sealant connecting the first transparent substrate sheet and the second transparent substrate sheet between the first transparent substrate sheet and the second transparent substrate sheet, thereby defining a cavity having an opening with the sealant, a transparent conductive layer, and a reflective layer. The sealant contains filler particles having a dielectric constant of 20 or more.

[0059] The sealant can connect the first transparent substrate sheet and the second transparent substrate sheet, thereby improving the connection stability between the first transparent substrate sheet and the second transparent substrate sheet.

[0060] When applying the sealant, the sealant may be distributed to the third surface or reflective layer of the second transparent substrate sheet to form a cavity with an opening, and pressure is applied to the first transparent substrate sheet and the second transparent substrate sheet to cure the first sealant.

[0061] S105: Step of injecting a light-tuning composition into the cavity through an opening.

[0062] By connecting the first transparent substrate sheet and the second transparent substrate sheet with a sealant, a cavity for housing the adjustment layer can be further formed. Specifically, the cavity has an opening, and the light adjustment composition is injected into the cavity through the opening using a vacuum injection method.

[0063] In some embodiments, the sealant comprises a first sealant and a second sealant. The steps include forming a sealant between a first transparent substrate sheet and a second transparent substrate sheet, defining a cavity with the sealant, a transparent conductive layer, and a reflective layer, and injecting a light-modulating composition into the cavity. The first step is to place a first sealant connecting the first transparent substrate sheet and the second transparent substrate sheet between the first transparent substrate sheet and the second transparent substrate sheet, and to define a cavity having an opening with the first sealant, a transparent conductive layer, and a reflective layer. The steps include injecting a light-tuning composition into the cavity through an opening and Includes.

[0064] In some embodiments, a method for manufacturing a reflector further includes the following steps:

[0065] S106: A step of sealing the opening by placing a second sealant connecting the first transparent substrate sheet and the second transparent substrate sheet between the first transparent substrate sheet and the second transparent substrate sheet.

[0066] The second sealant can seal the opening and confine the light-tuning composition within the cavity. In addition, the second sealant connects the first transparent substrate sheet and the second transparent substrate sheet, improving the connection stability between the two sheets.

[0067] Please refer to Figure 5. Embodiments of the present invention further provide a vehicle 2, which includes a reflector 1 according to one of the embodiments described above. As described above, the reflector 1 can reflect incident light. For example, the reflector 1 may be a reflector, which can be used as a rearview mirror for the vehicle, thereby allowing the driver to observe the situation behind the vehicle by the rearview mirror while driving the vehicle 2. The vehicle may be, but is not limited to, a fuel cell vehicle, an electric vehicle, a motorcycle, and an electric moped.

[0068] In some embodiments, the present application further provides discoloration glass and a vehicle.

[0069] In some embodiments, the color-changing glass comprises two glass substrate boards and a color-changing assembly sandwiched between these two glass substrate boards, the color-changing assembly comprising a color-changing layer, a diffusion ring, a first conductive layer, and a second conductive layer. The diffusion ring and the color-changing layer are located on the first conductive layer. The second conductive layer is located on the surface of the color-changing layer away from the first conductive layer. The diffusion ring is separately insulated from the color-changing layer and the second conductive layer. The diffusion ring and the second conductive layer are separately connected to an external circuit to form a potential difference between the first and second conductive layers and to change the color of the color-changing layer. The diffusion ring is located around the color-changing layer. The conductive sheet resistance of the diffusion ring material is smaller than the conductive sheet resistance of the first conductive layer material.

[0070] In some embodiments, the conductive sheet resistance of the diffusion ring material is in the range of 5 mΩ / □ to 30 mΩ / □, and / or the conductive sheet resistance of the first conductive layer material is in the range of 5 Ω / □ to 100 Ω / □.

[0071] In some embodiments, the diffusion ring is prepared using one of metallic silver, copper, silver paste, an optically transparent adhesive, and a conductive ink; and / or the first conductive layer is prepared using one of indium tin oxide, tin oxide, antimond-doped tin oxide, fluorine-doped tin oxide, antimond-doped zinc oxide, and aluminum-doped zinc oxide.

[0072] In some embodiments, the discoloration assembly further includes a first protective layer, the first protective layer being conductive and located between the first conductive layer and the discoloration layer, and the first protective layer being configured to prevent corrosion of the first conductive layer; and / or the discoloration assembly further includes a second protective layer, the second protective layer being conductive and located between the second conductive layer and the discoloration layer, and the second protective layer being configured to prevent corrosion of the second conductive layer.

[0073] In some embodiments, the first protective layer and / or the second protective layer are prepared using at least one of titanium, silver, aluminum, platinum, iridium, rhodium, ruthenium, and copper.

[0074] In some embodiments, the thickness of the first protective layer is less than the thickness of the first conductive layer, and the thickness of the first protective layer is in the range of 5 nm to 50 nm; and / or the thickness of the second protective layer is less than the thickness of the second conductive layer, and the thickness of the second protective layer is in the range of 5 nm to 50 nm.

[0075] In some embodiments, the discoloration assembly further includes a second diffusion ring. The second diffusion ring is positioned in a second conductive layer surrounding the discoloration layer, and the second diffusion ring is separately insulated from the discoloration layer and the diffusion ring. The second conductive layer is connected to an external circuit via the second diffusion ring.

[0076] In some embodiments, the second diffusion ring and the first diffusion ring are prepared using the same material; and / or the second conductive layer and the first conductive layer are prepared using the same material.

[0077] In some embodiments, the discoloration assembly further includes an insulating layer. The insulating layer is located between a diffusion ring and a second diffusion ring and is configured to provide insulation between the diffusion ring and the second diffusion ring.

[0078] In some embodiments, the insulating layer extends toward the first conductive layer and fills the space between the diffusion ring and the discoloration layer; and / or the insulating layer extends toward the second conductive layer and fills the space between the second diffusion ring and the discoloration layer.

[0079] In some embodiments, a vehicle is further provided that includes a vehicle body and a color-changing glass according to any one of the embodiments described above, wherein the color-changing glass is embedded in the vehicle body.

[0080] Furthermore, in the color-changing glass of this application, the diffusion ring is positioned around the color-changing layer, so that the current from the external circuit is first diffused by the diffusion ring, then flows into the first conductive layer, and diffuses from the edge of the first conductive layer to the center of the first conductive layer. Because the conductive sheet resistance of the diffusion ring material is lower, the diffusion ring can diffuse the current around the color-changing layer faster than the first conductive layer, thereby diffusing the current into the color-changing layer more quickly and changing the color of the color-changing layer, thereby improving the response speed of the color-changing glass of this application.

[0081] Since the vehicle provided in this application uses the color-changing glass provided in this application, it can be understood that the vehicle also has the beneficial effect of improving response speed.

[0082] The specific configuration of the discoloration glass and the vehicle is as follows:

[0083] Specifically, this application provides a vehicle including a body and color-changing glass. The color-changing glass is fixed to the body. The color-changing glass can change color under an external electric current. Therefore, it can be understood that the color-changing glass can absorb some of the light based on its own color to achieve lighting adjustment inside the vehicle. This improves the user experience. For example, the color-changing glass may be used in structures such as sunroofs, rearview mirrors, windshields, or windows in a vehicle.

[0084] In some other embodiments, it may be understood that the color-changing glass may be further used in other scenarios requiring light adjustment, such as eyeglass lenses, mobile phone screens, or mobile phone films. This is not particularly limited in this application.

[0085] Figure 6 shows the structure of the discoloration glass 100a according to an embodiment of the present invention, and Figure 7 is a cross-sectional top view of the discoloration glass 100a according to an embodiment of the present invention. For the sake of clarity, the thickness direction of the discoloration glass 100a in the present invention is designated as the first direction 001, and the mutually orthogonal second direction 002 and third direction 003 are both orthogonal to the first direction 001.

[0086] As shown in Figures 6 and 7, the color-changing glass 100a in this application includes a first glass substrate board 11a, a second glass substrate board 12a, and a color-changing assembly 20a. The first glass substrate board 11a, the color-changing assembly 20a, and the second glass substrate board 12a are laminated in a first direction 001. Light emitted from the first glass substrate board 11a or the second glass substrate board 12a can be directed to the color-changing assembly 20a, and the color-changing assembly 20a can absorb a portion of the light based on its own color to achieve adjustment of the light emitted from the second glass substrate board 12a or the first glass substrate board 11a.

[0087] In addition, the color-changing assembly 20a can change its own color under external circuitry, thereby allowing external light to adjust the color and intensity of the light passing through the color-changing assembly 20a under external circuitry, and expanding the light adjustment range of the color-changing glass 100a in this application.

[0088] Specifically, as shown in Figure 6, the discoloration assembly 20a includes a discoloration layer 21a, a first conductive layer 221a, a second conductive layer 222a, and a diffusion ring 231a. In the first direction 001, the first conductive layer 221a is located between the discoloration layer 21a and the first glass substrate board 11a, the second conductive layer 222a is located between the discoloration layer 21a and the second glass substrate board 12a, and the diffusion ring 231a is located on the first conductive layer 221a. The diffusion ring 231a is electrically connected to the positive electrode of the external circuit, and the second conductive layer 222a is electrically connected to the negative electrode of the external circuit.

[0089] It can be understood that the current from the external circuit enters the first conductive layer 221a via the diffusion ring 231a, enters the second conductive layer 222a via the discoloration layer 21a, and flows back into the external circuit from the negative electrode, forming a closed loop.

[0090] In the first direction 001, if a potential difference exists between two opposing sides of the color-changing layer 21a, current from the external circuit can flow into the color-changing layer 21a. This causes the color-changing layer 21a to adjust its own color under current, thereby achieving the color-changing effect of the color-changing assembly 20a, and thus realizing the color-changing function of the color-changing glass 100a in this application, and the light-adjusting function of the color-changing glass 100a in this application.

[0091] As shown in Figure 7, the diffusion ring 231a is positioned on the surface of the first conductive layer 221a facing the second conductive layer 222a, and the diffusion ring 231a is positioned around the discoloration layer 21a. The diffusion ring 231a has an annular shape. In view of this, it can be understood that the current flowing in from the diffusion ring 231a diffuses from the edge region to the central region in the second direction 002 and the third direction 003, thereby shortening the diffusion time of the current in the first conductive layer 221a.

[0092] Under the action of different voltages, the color-changing layer 21a changes to a different color. It can be understood that shortening the current diffusion time in the first conductive layer 221a can shorten the time required for the current density to be uniform across the entire area of ​​the first conductive layer 221a. In view of this, if the current density is constant, the magnitude of the current acting across the entire area of ​​the color-changing layer 21a will also be relatively constant, thereby improving the color uniformity of the color-changing layer 21a and enhancing the color uniformity of the color-changing glass 100a in this application.

[0093] In addition, shortening the current diffusion time in the first conductive layer 221a also shortens the time it takes for the current to pass through the first conductive layer 221a and act on the discoloration layer 21a. This improves the discoloration speed of the discoloration layer 21a, thereby improving the response speed of the discoloration glass 100a in this application and enhancing the user experience.

[0094] As shown in Figures 6 and 7, the diffusion ring 231a is spaced apart from the second conductive layer 222a in the first direction 001, thereby insulating the second conductive layer 222a and the diffusion ring 231a from each other and avoiding a short circuit caused by mutual contact between the diffusion ring 231a and the second conductive layer 222a.

[0095] The diffusion ring 231a is separated from the discoloration layer 21a in the second direction 002 and the third direction 003, thereby preventing the color of the edge region of the discoloration layer 21a from not matching the color of the remaining region due to current from an external circuit flowing directly into the discoloration layer 21a via the diffusion ring 231a, and thus preventing the uniformity of the color of the discoloration glass 100a in this application from being compromised. On the other hand, the diffusion ring 231a is located between the first conductive layer 221a and the second conductive layer 222a, and the discoloration layer 21a is conductive. In view of this, it can be understood that separating the diffusion ring 231a from the discoloration layer 21a can further prevent short-circuit phenomena that occur between the diffusion ring 231a and the second conductive layer 222a due to the discoloration layer 21a.

[0096] Therefore, unlike conventional solutions in which the conductive layer is directly connected to an external circuit, the present invention has a diffusion ring 231a positioned around the color-changing layer 21a on the color-changing glass 100a, which allows the current from the external circuit to first act upon the diffusion ring 231a and then flow into the first conductive layer 221a. The method of diffusing the current from the edge region to the center region, implemented in cooperation with the diffusion ring 231a, shortens the current diffusion time in the first conductive layer 221a, thereby conducting the current to the color-changing layer 21a more quickly and uniformly, improving the response speed and color uniformity of the color-changing glass 100a in the present invention.

[0097] In this embodiment, the conductive sheet resistance of the material of the diffusion ring 231a is smaller than that of the material of the first conductive layer 221a. For materials of the same thickness, it has been shown that the greater the sheet resistance of the material, the greater the resistance of the material, and the worse the conductivity of the material. By preparing the diffusion ring 231a using a material having a sheet resistance smaller than that of the material required to prepare the first conductive layer 221a, it is possible to shorten the diffusion time of the current of the external circuit in the diffusion ring 231a, and by shortening the diffusion time of the current in the diffusion ring 231a, the rate at which the current is conducted to the discoloration layer 21a is improved, thereby improving the response speed of the discoloration glass 100a in this application.

[0098] In this embodiment, the sheet resistance of the material of the diffusion ring 231a is in the range of 5 mΩ / □ to 30 mΩ / □. For example, the sheet resistance of the material of the diffusion ring 231a is in the range of 6 mΩ / □ to 10 mΩ / □. If the sheet resistance of the material of the diffusion ring 231a is less than 5 mΩ / □, it can be understood that the voltage between the first conductive layer 221a and the second conductive layer 222a of the external circuit will increase, and the voltage on the two opposing sides of the discoloration layer 21a will increase. This does not allow the user to adjust the voltage on the two sides of the discoloration layer 21a by adjusting the voltage of the external circuit.

[0099] If the sheet resistance of the diffusion ring 231a material is greater than 30 mΩ / □, the diffusion time of the external current in the diffusion ring 231a will be longer, and the external current may flow directly into the first conductive layer 221a without being diffused by the diffusion ring 231a. This will increase the diffusion time of the external current in the first conductive layer 221a, which will also affect the uniformity of discoloration and the response speed of the discoloration glass 100a in this application.

[0100] Therefore, in the color-changing glass 100a of this application, the diffusion ring 231a is prepared using a material with a sheet resistance in the range of 5 mΩ / □ to 30 mΩ / □, thereby allowing the user to adjust the color-changing effect of the color-changing layer 21a by adjusting the voltage of an external circuit, and further improving the uniformity of color-changing and the response speed of the color-changing glass 100a of this application. In this way, the user experience is improved.

[0101] In the embodiment, as shown in Figure 6, the diffusion ring 231a has a first thickness D1 in a first direction 001, and the first thickness D1 is in the range of 40 μm to 200 μm. For example, the first thickness D1 is 100 μm. If the first thickness D1 is less than 40 μm, it can be understood that this does not facilitate the connection between the diffusion ring 231a and the external circuit. In addition, this may lead to a disconnection between the diffusion ring 231a and the external circuit during transport, which will affect the color change function of the color-changing glass 100a in this application.

[0102] If the first thickness D1 is greater than 200 μm, the increase in the first thickness D1 reduces the gap between the diffusion ring 231a and the second conductive layer 222a due to the gap between the first conductive layer 221a and the second conductive layer 222a. This can lead to contact between the diffusion ring 231a and the second conductive layer 222a, resulting in a short circuit.

[0103] Therefore, in the color-changing glass 100a of this application, the first thickness D1 is set in the range of 40 μm to 200 μm, thereby ensuring the connection effect between the diffusion ring 231a and the external circuit, and further avoiding the short-circuit phenomenon caused between the diffusion ring 231a and the second conductive layer 222a, thereby ensuring the color-changing function of the color-changing glass 100a of this application.

[0104] In the embodiment, as shown in Figure 6, the diffusion ring 231a has a first width W1 in a second direction 002, and the first width W1 is in the range of 1 mm to 3 mm. For example, the first width W1 of the diffusion ring 231a is 2 mm. If the first width W1 is less than 1 mm, it can be understood that this does not facilitate the connection between the diffusion ring 231a and the external circuit. In addition, this may lead to a disconnection between the diffusion ring 231a and the external circuit during transport, which will affect the color-changing function of the color-changing glass 100a in this application.

[0105] In addition, when the first width W1 is less than 1 mm, the contact area between the diffusion ring 231a and the first conductive layer 221a also decreases, which increases the current diffusion time in the first conductive layer 221a and reduces the response speed of the discoloration glass 100a in this invention.

[0106] If the first width W1 is greater than 3 mm, the diffusion ring 231a extends toward the discoloration layer 21a in the second direction 002, reducing the size of the discoloration layer 21a in the second direction 002, which affects the discoloration effect of the discoloration glass 100a in this application. At the same time, if the diffusion ring 231a extends away from the discoloration layer 21a in the second direction 002, the overall size of the discoloration glass 100a in the second direction 002 also increases, reducing the proportion of the discoloration layer 21a in the discoloration glass 100a in this application, which affects the discoloration effect of the discoloration glass 100a in this application.

[0107] Therefore, in the color-changing glass 100a of this application, the first width W1 is set in the range of 1 mm to 3 mm, thereby ensuring the connection effect between the diffusion ring 231a and the external circuit, and further avoiding the influence of the diffusion ring 231a on the proportion of the color-changing layer 21a. In addition, the effect of the diffusion ring 231a in shortening the diffusion time of the first conductive layer 221a is further ensured. In this way, the color-changing function and color-changing effect of the color-changing glass 100a of this application are ensured, and the response speed of the color-changing glass 100a of this application is improved.

[0108] In one embodiment, the diffusion ring 231a is prepared using one of metallic silver, copper, silver paste, an optically transparent adhesive, and a conductive ink. For example, the diffusion ring 231a is prepared using silver paste.

[0109] In the embodiment, as shown in Figure 6, the sheet resistance of the material of the first conductive layer 221a is in the range of 5Ω / □ to 100Ω / □. For example, the sheet resistance of the material of the first conductive layer 221a is in the range of 8Ω / □ to 15Ω / □. If the sheet resistance of the material of the first conductive layer 221a is less than 5Ω / □, it can be understood that the voltage across the two opposing sides of the discoloration layer 21a will increase. This does not allow the user to adjust the voltage across the two sides of the discoloration layer 21a by adjusting the voltage of an external circuit.

[0110] If the sheet resistance of the material of the first conductive layer 221a is greater than 100Ω / □, the diffusion time of the external current in the first conductive layer 221a becomes longer, which affects the uniformity of discoloration and the response speed of the discoloration glass 100a in this application.

[0111] Therefore, in the color-changing glass 100a of this application, the first conductive layer 221a is prepared using a material with a sheet resistance in the range of 5Ω / □ to 100Ω / □, thereby allowing the user to adjust the color-changing effect of the color-changing layer 21a by adjusting the voltage of an external circuit, and further improving the uniformity of color-changing and the response speed of the color-changing glass 100a of this application. In this way, the user experience is improved.

[0112] In an embodiment, as shown in Figure 6, the first conductive layer 221a has a second thickness D2 in the first direction 001, and the second thickness D2 is in the range of 50 nm to 500 nm. For example, the second thickness D2 is in the range of 80 nm to 150 nm. The first conductive layer 221a can reduce electromagnetic radiation, ultraviolet rays, and infrared rays. In view of this, it can be understood that if the second thickness D2 is less than 50 nm, the absorption capacity of the first conductive layer 221a for electromagnetic radiation, ultraviolet rays, and infrared rays decreases, which affects the absorption efficiency of the discoloration glass 100a in this application for electromagnetic radiation, ultraviolet rays, and infrared rays.

[0113] The thickness of the first conductive layer 221a is further related to its conductivity and transparency. In view of this, it can be understood that if the second thickness D2 is greater than 500 nm, the first conductive layer 221a may have a specific color, which affects the uniformity of the color of the color-changing glass 100a in this application. In addition, an increase in the second thickness D2 further affects the conductivity of the first conductive layer 221a. As a result, the potential difference between two opposing sides of the color-changing layer 21a is affected, which affects the color-changing function of the color-changing glass 100a in this application.

[0114] Therefore, by arranging a first conductive layer 221a having a second thickness D2 in the range of 50 nm to 500 nm, the absorption efficiency of the first conductive layer 221a against electromagnetic radiation, ultraviolet rays, and infrared rays can be guaranteed. Furthermore, the conductivity and transparency of the first conductive layer 221a can be guaranteed, thereby ensuring the uniformity of color and the color-changing function of the color-changing glass 100a in this application.

[0115] In the embodiment, the first conductive layer 221a is prepared using one of indium tin oxide, tin oxide, antimond-doped tin oxide, fluorine-doped tin oxide, antimond-doped zinc oxide, and aluminum-doped zinc oxide, thereby ensuring the light transmittance of the first conductive layer 221a and further ensuring the conductivity of the first conductive layer 221a. For example, the first conductive layer 221a is prepared using indium tin oxide.

[0116] Figure 8 shows another structure of the discoloration glass 100a according to an embodiment of the present invention.

[0117] As shown in Figure 8, the discoloration assembly 20a further includes a first protective layer 241a. The first protective layer 241a is prepared using a conductive material and is positioned between the first conductive layer 221a and the discoloration layer 21a, thereby separating the first conductive layer 221a and the discoloration layer 21a. The material for preparing the discoloration layer 21a may contain acids and bases. In view of this, it can be understood that by placing the first protective layer 241a, the acids and bases of the discoloration layer 21a will not act on the first conductive layer 221a, preventing corrosion of the first conductive layer 221a, ensuring the integrity of the first conductive layer 221a, and ensuring the discoloration efficiency of the discoloration glass 100a in this application.

[0118] As shown in Figure 8, the discoloration assembly 20a further includes a second protective layer 242a. The second protective layer 242a is prepared using a conductive material and is positioned between the second conductive layer 222a and the discoloration layer 21a, thereby separating the two layers. The material for preparing the discoloration layer 21a may contain acids and bases. In view of this, it can be understood that by placing the second protective layer 242a, the acids and bases of the discoloration layer 21a will not act on the second conductive layer 222a, preventing corrosion of the second conductive layer 222a, ensuring the integrity of the second conductive layer 222a, and ensuring the discoloration efficiency of the discoloration glass 100a in this application.

[0119] Alternatively, in some other embodiments, the color-changing glass 100a in the present application may have only a first protective layer 241a disposed between the first conductive layer 221a and the color-changing layer 21a, or only a second protective layer 242a disposed between the second conductive layer 222a and the color-changing layer 21a. This is not particularly limited in the present application.

[0120] In one embodiment, the first protective layer 241a is prepared using at least one of titanium, silver, aluminum, platinum, iridium, rhodium, ruthenium, and copper.

[0121] In the embodiment, as shown in Figures 6 and 8, the first protective layer 241a has a third thickness D3, and the third thickness D3 is smaller than the second thickness D2. The light transmittance of the material used to prepare the first protective layer 241a is insufficient. In view of this, it can be understood that by arranging the first protective layer 241a having a third thickness D3 smaller than the second thickness D2 of the first conductive layer 221a, the conductivity of the first protective layer 241a can be guaranteed, the light absorption effect of the first protective layer 241a can be reduced, the influence of the first protective layer 241a on the color of the discoloration glass 100a in this application can be reduced, and the uniformity of the color of the discoloration glass 100a in this application can be guaranteed.

[0122] The third thickness D3 is in the range of 5 nm to 50 nm. For example, the third thickness D3 is in the range of 8 nm to 20 nm. The corrosion resistance of the first protective layer 241a has limitations. In view of this, it can be understood that if the third thickness D3 is less than 5 nm, the protective effect of the first protective layer 241a on the first conductive layer 221a will be reduced. As a result, acidic and basic substances in the discoloration layer 21a may pass through the first protective layer 241a and corrode the first conductive layer 221a, which may affect the discoloration function of the discoloration glass 100a in this application.

[0123] The light transmittance of the material used to prepare the first protective layer 241a is insufficient. In view of this, it can be understood that if the third thickness D3 is greater than 50 nm, the light emitted by the first protective layer 241a will be absorbed to a greater extent, and furthermore, the light may be blocked by the first protective layer 241a, which will affect the light transmittance effect of the discoloration glass 100a in this application.

[0124] Therefore, the third thickness D3 is set in the range of 5 nm to 50 nm, thereby ensuring the protective effect of the first protective layer 241a over the first conductive layer 221a, and further reducing the light blocking by the first protective layer 241a, thereby ensuring the light transmission effect of the color-changing glass 100a in this application.

[0125] In the embodiment, as shown in Figures 6 and 8, the second protective layer 242a has a fourth thickness D4, and the fourth thickness D4 is smaller than the thickness of the second conductive layer 222a. In this way, the conductivity of the second protective layer 242a is guaranteed, the light absorption effect of the second protective layer 242a is reduced, the influence of the second protective layer 242a on the color of the discoloration glass 100a in the present invention is reduced, and the uniformity of the color of the discoloration glass 100a in the present invention is guaranteed.

[0126] The fourth thickness D4 is in the range of 5 nm to 50 nm. For example, the fourth thickness D4 is in the range of 8 nm to 20 nm. In this way, the protective effect of the second protective layer 242a on the second conductive layer 222a can be guaranteed, and the light transmission effect of the color-changing glass 100a in this application can be guaranteed by further reducing the light blocking by the second protective layer 242a.

[0127] In one embodiment, the second protective layer 242a is prepared using at least one of titanium, silver, aluminum, platinum, iridium, rhodium, ruthenium, and copper.

[0128] In this embodiment, the first protective layer 241a and the second protective layer 242a are prepared using the same material.

[0129] In the embodiment, the thickness of the second protective layer 242a is in the range of 5 nm to 50 nm, for example, the thickness of the second protective layer 242a is in the range of 8 nm to 20 nm.

[0130] In some embodiments, the second conductive layer 222a is prepared using one of indium tin oxide, tin oxide, antimond-doped tin oxide, fluorine-doped tin oxide, antimond-doped zinc oxide, and aluminum-doped zinc oxide, thereby ensuring the light transmittance of the second conductive layer 222a and further ensuring its conductivity. For example, the second conductive layer 222a is prepared using indium tin oxide.

[0131] In this embodiment, the first conductive layer 221a and the second conductive layer 222a are prepared using the same material.

[0132] In this embodiment, the sheet resistance of the material of the second conductive layer 222a is in the range of 5Ω / □ to 100Ω / □. For example, the sheet resistance of the material of the second conductive layer 222a is in the range of 8Ω / □ to 15Ω / □.

[0133] In the embodiment, the thickness of the second conductive layer 222a is also in the range of 50 nm to 500 nm. For example, the thickness of the second conductive layer 222a is in the range of 80 nm to 150 nm.

[0134] Figure 9 shows yet another structure of the discoloration glass 100a according to an embodiment of the present invention.

[0135] As shown in Figure 9, the discoloration assembly 20a further includes a second diffusion ring 232a. The second diffusion ring 232a is located on the surface of the second conductive layer 222a facing the first conductive layer 221a, and the second diffusion ring 232a is located around the discoloration layer 21a.

[0136] The second diffusion ring 232a has an annular shape. In view of this, it can be understood that the current flowing through the discoloration layer 21a to the second conductive layer 222a is diffused from the central region to the edge region in the second direction 002 and the third direction 003, thereby shortening the diffusion time of the current in the second conductive layer 222a.

[0137] The diffusion ring 231a can shorten the current diffusion time in the first conductive layer 221a. In view of this, it can be understood that the cooperation between the diffusion ring 231a and the second diffusion ring 232a shortens the current diffusion time in the first conductive layer 221a and the second conductive layer 222a, thereby shortening the time required for the current on the two opposing sides of the discoloration layer 21a to become uniform. In this way, the discoloration speed of the discoloration layer 21a is improved, the response speed of the discoloration glass 100a in this application is improved, and the user experience is improved.

[0138] As shown in Figure 9, the second diffusion ring 232a is separated from the diffusion ring 231a in the first direction 001, thereby insulating the second diffusion ring 232a and the diffusion ring 231a from each other and avoiding a short circuit caused by mutual contact between the diffusion ring 231a and the second diffusion ring 232a. In addition, the influence of the current flowing directly from the discoloration layer 21a to the second diffusion ring 232a on the color of the discoloration layer 21a is further avoided, and the uniformity of the color of the discoloration glass 100a is guaranteed.

[0139] The second diffusion ring 232a is separated from the discoloration layer 21a in the second direction 002 and the third direction 003, thereby preventing the diffusion ring 231a and the second diffusion ring 232a from connecting due to the formation of an electric field between them under the external circuit, and thus avoiding a short circuit between the diffusion ring 231a and the second diffusion ring 232a.

[0140] In one embodiment, the second diffusion ring 232a is prepared using one of metallic silver, copper, silver paste, an optically transparent adhesive, and a conductive ink. For example, the second diffusion ring 232a is prepared using silver paste.

[0141] In this embodiment, the second diffusion ring 232a and the diffusion ring 231a are prepared using the same material.

[0142] In this embodiment, the sheet resistance of the material for the second diffusion ring 232a is in the range of 5 mΩ / □ to 30 mΩ / □. For example, the sheet resistance of the material for the diffusion ring 231a is in the range of 6 mΩ / □ to 10 mΩ / □.

[0143] In this embodiment, the thickness of the second diffusion ring 232a is in the range of 40 μm to 200 μm. For example, the thickness of the second diffusion ring 232a is 100 μm.

[0144] In this embodiment, the width of the second diffusion ring 232a is in the range of 1 mm to 3 mm. For example, the width of the second diffusion ring 232a is 2 mm.

[0145] Figure 10 shows the cross-sectional structure of the discoloration glass 100a according to an embodiment of the present invention.

[0146] As shown in Figure 10, the discoloration assembly 20a further includes an insulating layer 25. The insulating layer 25 is located between the diffusion ring 231a and the second diffusion ring 232a in the first direction 001, thereby providing insulation between the diffusion ring 231a and the second diffusion ring 232a and reducing the possibility of the diffusion ring 231a and the second diffusion ring 232a being connected and short-circuiting, thereby ensuring the safety of use of the discoloration glass 100a in this application.

[0147] In another embodiment, two insulating layers 25 may be arranged alternately, and it can be understood that they are both located between the diffusion ring 231a and the second diffusion ring 232a in a first direction 001. One of the insulating layers 25 is coated on the surface of the diffusion ring 231a facing the second diffusion ring 232a, and the other insulating layer 25 is coated on the surface of the second diffusion ring 232a facing the diffusion ring 231a, and the two insulating layers 25 are spaced apart from each other to achieve insulation between the diffusion ring 231a and the second diffusion ring 232a.

[0148] In this embodiment, as shown in Figure 10, the insulating layer 25 extends toward the first conductive layer 221a and fills the space between the diffusion ring 231a and the discoloration layer 21a, thereby achieving insulation between the diffusion ring 231a and the discoloration layer 21a and reducing the possibility of current in the diffusion ring 231a being directly transmitted to the discoloration layer 21a. In addition, the situation in which the diffusion ring 231a and the second diffusion ring 232a are connected due to the discoloration layer 21a is further avoided. Furthermore, the formation of an electric field between the diffusion ring 231a and the second diffusion ring 232a under external current is further avoided, and the possibility of a short circuit between the diffusion ring 231a and the second diffusion ring 232a under an electric field is avoided, thereby achieving the safety of use of the discoloration glass 100a in this application.

[0149] In another embodiment, as shown in Figure 11, when the insulating layer 25 is filled between the diffusion ring 231a and the discoloration layer 21a, it can be understood that it extends further toward the second conductive layer 222a and fills the space between the second diffusion ring 232a and the discoloration layer 21a, thereby avoiding the influence of the diffusion ring 231a and the second diffusion ring 232a on the discoloration effect of the discoloration layer 21a, ensuring the insulating performance between the diffusion ring 231a and the second diffusion ring 232a, and improving the safety of use of the discoloration glass in this application.

[0150] In another embodiment, the insulating layer 25 may extend only toward the second conductive layer 222a and fill the space between the second diffusion ring 232a and the discoloration layer 21a. This is not particularly limited in this application.

[0151] In one embodiment, the insulating layer 25 is prepared using insulating ink.

[0152] In one embodiment, the resistance of the insulating layer 25 material is 10 5 It is greater than Ω. For example, the resistance of the insulating layer 25 material is 10 6 It is greater than Ω.

[0153] In the embodiment, the thickness of the insulating layer 25 is in the range of 5 μm to 80 μm. For example, the thickness of the insulating layer 25 is in the range of 8 μm to 20 μm. It can be understood that by limiting the thickness of the insulating layer 25 to 5 μm to 80 μm, it is possible to avoid the effect on the insulating effect due to the insulating layer 25 being too thin, and to further avoid the effect on the overall thickness of the discoloration glass 100a due to the insulating layer 25 being too thick, thereby ensuring the safety of use of the discoloration glass 100a in this application.

[0154] In this embodiment, the width of the insulating layer 25 is in the range of 3 mm to 5 mm. For example, the width of the insulating layer 25 is in the range of 4 mm to 4.5 mm. It can be understood that by limiting the width of the insulating layer 25 to 3 mm to 5 mm, it is possible to avoid the effect on the insulating effect due to the width of the insulating layer 25 being too small, and to further avoid the effect on the spatial proportion due to the width of the discoloration layer 21a being too large, thereby ensuring the discoloration efficiency of the discoloration glass 100a in this application.

[0155] In the embodiment, as shown in Figures 6 to 11, the discoloration assembly 20a further includes a sealing layer 26. The sealing layer 26 is annular in shape and surrounds the discoloration layer 21a. The insulating layer 25, the diffusion ring 231a, and the second diffusion ring 232a are all separated from the discoloration layer 21a using the sealing layer 26.

[0156] The material used for the discoloration layer 21a is typically fluid. Therefore, it can be understood that by arranging the sealing layer 26 surrounding the discoloration layer 2a1, the insulating performance between the discoloration layer 21a and the diffusion ring 231a and the second diffusion ring 232a can be improved, and furthermore, the relative position of the discoloration layer 21a can be defined. In addition, by further isolating the discoloration layer 21a from the external environment and avoiding the phenomenon of water and oxygen flowing into the discoloration layer 21a and reacting with the material of the discoloration layer 2a1, the discoloration effect of the discoloration glass 100a in this application can be improved.

[0157] In some embodiments, the sealing layer 26 is prepared using at least one of a phenolic resin, an epoxy resin, and an organic silica gel adhesive. For example, the sealing layer 26 is prepared using an epoxy resin. In some other embodiments, it may be understood that the sealing layer 26 may instead be made of another material that has adhesive properties, good sealing performance, and low permeability to water, oxygen, and organic solvents, and does not react with the material of the discoloration layer 21a.

[0158] In the embodiment, as shown in Figure 11, the sealing layer 26 has a fifth thickness D5 in the first direction 001, and the fifth thickness D5 is in the range of 70 μm to 250 μm. For example, the fifth thickness D5 is in the range of 100 μm to 150 μm. The thickness of the discoloration layer 21a in the first direction 001 remains constant. In view of this, it can be understood that if the fifth thickness D5 is less than 70 μm, some areas of the discoloration layer 21a are connected to the external environment, and water and oxygen in the external environment react with the exposed portion of the discoloration layer 21a, which affects the discoloration effect of the discoloration glass 100a in this application.

[0159] If the fifth thickness D5 is greater than 250 μm, a gap exists between the discoloration layer 21a and the sealing layer 26. The discoloration layer 21a is fluid. In view of this, it can be understood that the discoloration layer 21a may separate from the first conductive layer 221a or the second conductive layer 222a, which affects the conductivity between the external current and the discoloration layer 21a, and further affects the discoloration function and discoloration effect of the discoloration glass 100a in this application.

[0160] Therefore, the fifth thickness D5 is set in the range of 70 μm to 250 μm, thereby ensuring the barrier effect of the sealing layer 26 against the discoloration layer 21a, and further ensuring the connection between the discoloration layer 21a and the first conductive layer 221a and the second conductive layer 222a, thereby ensuring the discoloration function and discoloration effect of the discoloration glass 100a in this application.

[0161] In the embodiment, as shown in Figure 11, the sealing layer 26 has a second width W2, which is in the range of 1.2 mm to 4 mm. For example, the second width W2 is in the range of 1.8 mm to 2.2 mm. By setting the second width W2 in the range of 1.2 mm to 4 mm, it is possible to avoid a situation where the water-oxygen barrier effect of the sealing layer 26 is insufficient due to the second width W2 being too small, and further avoid a situation where the spatial proportion of the discoloration layer 21a is reduced due to the second width W2 being too large, thereby ensuring the water-oxygen barrier effect of the sealing layer 26 and the discoloration effect of the discoloration glass 100a in this application.

[0162] In the embodiment, as shown in Figures 10 and 11, the color-changing glass 100a in the present application further includes a first substrate layer 31a and a second substrate layer 32a. In the first direction 001, the first substrate layer 31a is located between the first glass substrate board 11a and the first conductive layer 221a, and the second substrate layer 32a is located between the second glass substrate board 12a and the second conductive layer 222a.

[0163] In view of the process for arranging the first conductive layer 221a and the second conductive layer 222a in existing processes, it can be understood that by arranging the first substrate layer 31a and the second substrate layer 32a, the difficulty of arranging the first conductive layer 221a and the second conductive layer 222a on the first glass substrate board 11a and the second glass substrate board 12a can be reduced. This ensures a connection effect between the first conductive layer 221a and the second conductive layer 222a and the first glass substrate board 11a and the second glass substrate board 12a, and further reduces the difficulty of the process, making preparation easier.

[0164] In the embodiment, the first base layer 31a is prepared using one of titanium dioxide, tantalum pentoxide, niobium pentoxide, silicon dioxide, and magnesium fluoride. For example, the first base layer 31a is prepared using niobium pentoxide.

[0165] In the embodiment, the thickness of the first substrate layer 31a is in the range of 30 nm to 100 nm. For example, the thickness of the first substrate layer 31a is in the range of 30 nm to 50 nm. By arranging the first substrate layer 31a with a thickness in the range of 30 nm to 100 nm, it is possible to avoid the influence on the preparation effect of the first conductive layer 221a due to the thickness of the first substrate layer 31a being too small, and to further avoid the influence on the overall thickness of the discoloration glass 100a due to the thickness of the first substrate layer 31 being too large.

[0166] In the embodiment, the second base layer 32a is prepared using one of titanium dioxide, tantalum pentoxide, niobium pentoxide, silicon dioxide, and magnesium fluoride. For example, the second base layer 32a is prepared using niobium pentoxide.

[0167] In this embodiment, the thickness of the second substrate layer 32a is in the range of 30 nm to 100 nm. For example, the thickness of the second substrate layer 32a is in the range of 30 nm to 50 nm. It can be understood that by arranging the second substrate layer 32a with a thickness in the range of 30 nm to 100 nm, it is possible to avoid the influence on the preparation effect of the second conductive layer 222a due to the thickness of the second substrate layer 32a being too small, and to further avoid the influence on the overall thickness of the discoloration glass 100a due to the thickness of the second substrate layer 32a being too large.

[0168] Figure 12 shows yet another cross-sectional structure of the discoloration glass 100a according to an embodiment of the present invention.

[0169] As shown in Figure 12, the size of the second glass substrate board 12a is smaller than the size of the first glass substrate board 11a. Correspondingly, the second diffusion ring 232a may extend further in the first direction 001 and directly contact the side edge of the second conductive layer 222a. It can be understood that by setting the size of the second glass substrate board 12a to be different from the size of the first glass substrate board 11a, the color-changing glass 100a in this application can be adapted to different usage conditions.

[0170] In one embodiment, the discoloration layer 21a is a composition comprising a cathode discoloration material and an anode discoloration material. The cathode discoloration material is at least one of viologen, substituted viologen, anthraquinone, and substituted anthraquinone. For example, the cathode discoloration material is methyl viologen. The concentration of the cathode discoloration material is in the range of 10 mmol / L to 300 mmol / L. For example, the concentration of the cathode discoloration material is in the range of 50 mmol / L to 80 mmol / L.

[0171] The anode discoloration material is at least one of diphenylamine, substituted diphenylamine, N-substituted compounds of diphenylamine, triphenylamine, substituted triphenylamine, ferrocene, substituted ferrocene, ferrocene salts, substituted ferrocene salts, phenothiazine, substituted phenothiazine, thianthrene, substituted thianthrene, phenazine, substituted phenazine, 5,10-dihydrophenazine, and substituted 5,10-dihydrophenazine. For example, the anode discoloration material is an N-substituted compound of diphenylamine, substituted phenothiazine, and substituted 5,10-dihydrophenazine. The concentration of the anode discoloration material is in the range of 10 mmol / L to 300 mmol / L. For example, the concentration of the anode discoloration material is in the range of 60 mmol / L to 100 mmol / L.

[0172] It can be understood that the anode discoloration material and the cathode discoloration material can change their own colors under the potential difference between two opposite side surfaces of the discoloration layer 21a, so as to realize the discoloration function of the discoloration glass 100a in the present application.

[0173] In an embodiment, the discoloration layer 21a further contains a solvent, and the solvent is at least one of sulfone, amide, ether, alcohol, nitrile, ketone, and ester. Specifically, the solvent is at least one of 3-methylsulfolane, dimethyl sulfoxide, dimethylformamide, tetraethylene glycol dimethyl ether, ethoxyethanol, acetonitrile, glutaronitrile, 3-hydroxypropionitrile, 2-methylglutaronitrile, 2-acetylbutyrolactone, cyclopentanone, β-propiolactone, γ-butyrolactone, γ-valerolactone, polypropylene carbonate, ethylene carbonate, and propylene carbonate. For example, the solvent is propylene carbonate, dimethyl sulfoxide, and dimethylformamide.

[0174] The solvent can dissolve and disperse the anode discoloration material and the cathode discoloration material, thereby mixing the anode discoloration material and the cathode discoloration material with each other to ensure the discoloration uniformity of the discoloration layer 21a in the present application and the color uniformity of the discoloration glass 100a in the present application. In some other embodiments, it can be understood that the solvent may be another material that dissolves or disperses the anode discoloration material and the cathode discoloration material and reacts with the anode discoloration material and the cathode discoloration material.

[0175] In an embodiment, the discoloration layer 21a further includes an anti-delamination agent. The anti-delamination agent is a polymer containing an ester group. Specifically, the anti-delamination agent is at least one of polyacrylate, polymethacrylate, and polyaromatic ester. For example, the anti-delamination agent is polymethyl methacrylate. The concentration of the anti-delamination agent is in the range of 1% by weight to 6% by weight. For example, the concentration of the anti-delamination agent is in the range of 4% by weight to 6% by weight.

[0176] The anti-delamination agent can prevent the delamination problem of the discoloration layer 21a, ensure the uniform dispersion of each component of the discoloration layer 21a, and improve the discoloration uniformity of the discoloration layer 21a. On the other hand, the anti-delamination agent can also extend the service life of each component of the discoloration layer 21a.

[0177] In an embodiment, the discoloration layer 21a further includes an electrolyte to improve the ionic conductivity of the discoloration layer 21a, improve the discoloration response speed of the discoloration layer 21a, and improve the response speed of the discoloration glass 100a in the present application.

[0178] The electrolyte is at least one of lithium trifluoromethanesulfonate, lithium perchlorate, lithium tetrafluoroborate, and lithium hexafluorophosphate. For example, the electrolyte is lithium tetrafluoroborate. The content of the electrolyte is in the range of 0.05 mol / L to 1 mol / L. For example, the concentration of the electrolyte is 0.5 mol / L.

[0179] In one embodiment, the discoloration layer 21a further contains a thickening agent to adjust the viscosity of the discoloration layer 21a and avoid delamination from the first conductive layer 221a or the second conductive layer 222a caused by the low viscosity of the discoloration layer 21a.

[0180] The thickening agent is at least one of the following: polyamide, polyimide, polycarbonate, polymethacrylate, polyacrylate, polysilane, polysiloxane, polyvinyl acetate, polymethacrylonitrile, polyacrylonitrile, polyvinylphenol, polyvinyl alcohol, and polyvinylidene dihalide. For example, the thickening agent is polyvinylidene fluoride. The content of the thickening agent is in the range of 0.05% to 3% by weight. For example, the content of the thickening agent is in the range of 0.05% to 1.5% by weight.

[0181] In embodiments, the discoloration layer 21a further contains an antioxidant to improve its durability and extend its service life. The antioxidant is a sterically unhindered organic phenol compound. For example, the antioxidant is at least one of 1,3,5-tri-tert-butylphenol, 1,5-tert-butyl-3-methylphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-dipentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole.

[0182] In some other embodiments, the antioxidant may be an organic alkenyl ester compound instead. For example, the antioxidant is at least one of methyl methacrylate, ethyl methacrylate, etc., and is at least one of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 1,5-tert-butyl-3-methylphenol, and methyl methacrylate.

[0183] In this embodiment, the concentration of the antioxidant is in the range of 20 mmol / L to 500 mmol / L. For example, the concentration of the antioxidant is in the range of 50 mmol / L to 100 mmol / L.

[0184] In embodiments, the color-changing layer 21a further contains a UV inhibitor to improve the photostability of the color-changing layer 21a and extend its service life. The UV inhibitor is at least one of 2-ethyl-2-cyano-3,3-diphenyl acrylate, (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 3-[3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionate amyl ester, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-ethyl-2'-ethoxypropionanilide. For example, the UV inhibitor is 2-hydroxy-4-methoxybenzophenone.

[0185] The amount of UV protection agent is in the range of 1% to 4% by weight. For example, the amount of UV protection agent is in the range of 3% to 4% by weight.

[0186] In an embodiment, as shown in FIGS. 11 and 12, in the first direction 001, the L*a*b value is measured for the entire structure formed by the cooperation of the first glass substrate board 11a, the first base material layer 31, the first conductive layer 221a, and the first protective layer 241a. L*>80, -3<a*<3, and -10<b*<-1. For example, L*>85, -1.5<a*<0, and -8<b*<-4.

[0187] The L*a*b value can reflect the lightness, red-green degree, and yellow-blue degree of the structure with respect to light. That is, the larger the range of the L*a*b value of the structure, the less the amount of light absorbed by the structure when light passes through the structure, corresponding to the small absorption rate of the structure with respect to light. The range of the L*a*b value of the structure formed by the cooperation of the first glass substrate board 11a, the first base material layer 31, the first conductive layer 221a, and the first protective layer 241a is set to L*>80, -3<a*<3, and -10<b*<-1. Thereby, the effects of the first glass substrate board 11a, the first base material layer 31, the first conductive layer 221a, and the first protective layer 241a can be guaranteed, and the influence of the first glass substrate board 11a, the first base material layer 31, the first conductive layer 221a, and the first protective layer 241a on light can be further reduced, and it can be understood that the discoloration effect of the discoloring glass 100a in the present application can be guaranteed.

[0188] The beneficial effects that can be achieved by the discoloring glass 100a in the present application will be described through a comparison by reference between three possible embodiments (Example 3, Example 4, and Example 5) of the discoloring glass 100a in the present application and a typical embodiment (Comparative Example 2) in the prior art.

[0189] Example 3 A discoloring glass 100a is provided. The discoloring glass 100a includes a first glass substrate board 11a, a second glass substrate board 12a, and a discoloring assembly 20a, and the discoloring assembly 20a is sandwiched between the first glass substrate board 11a and the second glass substrate board 12a.

[0190] The discoloration assembly 20a includes a discoloration layer 21a, a first conductive layer 221a, a second conductive layer 222a, and a diffusion ring 231a. In the first direction 001, the first conductive layer 221a is located between the discoloration layer 21a and the first glass substrate board 11a, the second conductive layer 222a is located between the discoloration layer 21a and the second glass substrate board 12a, and the diffusion ring 231a is positioned around the discoloration layer 21a on the first conductive layer 221a and insulated from the second conductive layer 222a and the discoloration layer 21a. The diffusion ring 231a is electrically connected to the positive terminal of an external circuit, and the second conductive layer 222a is electrically connected to the negative terminal of an external circuit. In addition, the length and width of the discoloration glass 100a are both 40 mm, and the coloring response time and decolorization response time of the discoloration glass 100a were tested at a test voltage of 1.3 V.

[0191] Example 4 A discoloration glass 100a is provided. The discoloration glass 100a includes a first glass substrate board 11a, a second glass substrate board 12a, and a discoloration assembly 20a, wherein the discoloration assembly 20a is sandwiched between the first glass substrate board 11a and the second glass substrate board 12a.

[0192] The discoloration assembly 20a includes a discoloration layer 21a, a first conductive layer 221a, a second conductive layer 222a, and a diffusion ring 231a. In the first direction 001, the first conductive layer 221a is located between the discoloration layer 21a and the first glass substrate board 11a, the second conductive layer 222a is located between the discoloration layer 21a and the second glass substrate board 12a, and the diffusion ring 231a is positioned around the discoloration layer 21a on the first conductive layer 221a and is insulated from the second conductive layer 222a and the discoloration layer 21a. The diffusion ring 231a is electrically connected to the negative terminal of an external circuit, and the second conductive layer 222a is electrically connected to the positive terminal of an external circuit. In addition, the length and width of the discoloration glass 100a are both 40 mm, and the coloring response time and decolorization response time of the discoloration glass 100a were tested at a test voltage of 1.3 V.

[0193] Example 5 A discoloring glass 100a is provided. The discoloring glass 100a includes a first glass substrate board 11a, a second glass substrate board 12a, and a discoloring assembly 20a, and the discoloring assembly 20a is sandwiched between the first glass substrate board 11a and the second glass substrate board 12a.

[0194] The discoloring assembly 20a includes a discoloring layer 21a, a first conductive layer 221a, a second conductive layer 222a, a diffusion ring 231a, and a second diffusion ring 232a. In a first direction 001, the first conductive layer 221a is located between the discoloring layer 21a and the first glass substrate board 11a, and the second conductive layer 222a is located between the discoloring layer 21a and the second glass substrate board 12a.

[0195] The diffusion ring 231a is disposed on the first conductive layer 221a around the discoloring layer 21a, and the second diffusion ring 232a is disposed on the second conductive layer 222a around the discoloring layer 21a. The diffusion ring 231a and the second diffusion ring 232a are insulated from each other and are both insulated from the discoloring layer 21a. The diffusion ring 231a is electrically connected to the positive electrode of an external circuit, and the second diffusion ring 231a is electrically connected to the negative electrode of the external circuit. In addition, both the length and width of the discoloring glass 100a are 40 mm, and the coloring response time and the bleaching response time of the discoloring glass 100a were tested with a test voltage of 1.3 V.

[0196] Comparative Example 2 A discoloring glass 100a' is provided. The discoloring glass 100a' includes a first glass substrate board 11a', a second glass substrate board 12a', and a discoloring assembly 20a', and the discoloring assembly 20a' is sandwiched between the first glass substrate board 11a' and the second glass substrate board 12a'.

[0197] The color-changing assembly 20a' includes a color-changing layer 21a', a first conductive layer 22a', and a second conductive layer 23a'. The first conductive layer 22a' and the second conductive layer 23a' are located on two opposing sides of the color-changing layer 21a'. The first conductive layer 22a' is electrically connected to the positive terminal of an external circuit, and the second conductive layer 23a' is electrically connected to the negative terminal of an external circuit. In addition, the color-changing glass 100a' has a length and width of 40 mm, and the color-changing response time and decolorization response time of the color-changing glass 100a' were tested at a test voltage of 1.3 V.

[0198] Test statistics regarding the response speed of the discolored glass in Examples 3, 4, 5, and Comparative Example 2 were collected, and the results are shown in Table 1.

[0199] [Table 2]

[0200] From the obtained test data, it can be concluded that the color response times of the color-changing glass 100a in Examples 3, 4, and 5 are all shorter than the color response time of the color-changing glass 100a' in Comparative Example 1. This is because Examples 3, 4, and 5 all use the annular diffusion ring 231a provided in this application. In this way, it is ensured that an external current can be conducted to the corresponding first conductive layer 221a or the corresponding second conductive layer 222a, and the diffusion time of the current in the corresponding first conductive layer 221a or the second conductive layer 222a can be further shortened, thereby reducing the time required to conduct an external current from two opposing sides of the color-changing layer 21a. Therefore, the color response times of the color-changing glass 100a in Examples 3, 4, and 5 are all shorter than the color response time in Comparative Example 2.

[0201] In addition, the obtained test data can be further concluded to show that the decolorization response times of the color-changing glass 100a in Examples 3, 4, and 5 are all shorter than the decolorization response time of the color-changing glass 100a' in Comparative Example 2. This is because Examples 3, 4, and 5 all use the annular diffusion ring 231a provided in this application. In this way, it is ensured that an external current can be conducted to the corresponding first conductive layer 221a or the corresponding second conductive layer 222a, and the diffusion time of the current in the corresponding first conductive layer 221a or the second conductive layer 222a can be further reduced, thereby reducing the time required to block the external current from the two opposing sides of the color-changing layer 21a. Therefore, the decolorization response times of the color-changing glass 100a in Examples 3, 4, and 5 are all shorter than the decolorization response time in Comparative Example 2.

[0202] In conclusion, the present invention differs from the prior art in that an annular diffusion ring 231a is placed on the color-changing glass 100a, and the diffusion ring 231a is placed around the color-changing layer 21a, thereby causing the external current to be first diffused by the diffusion ring 231a and then transmitted to the corresponding first conductive layer 221a or the corresponding second conductive layer 222a. In this way, the external current is diffused from the edge region to the central region of the corresponding first conductive layer 221a or the corresponding second conductive layer 222a, thereby shortening the diffusion time of the current in the first conductive layer 221a or the second conductive layer 222a, shortening the coloring response time and decolorization response time required for the current to act on the color-changing layer 21a, and improving the response speed of the color-changing glass 100a in the present invention.

[0203] In some embodiments, the present application further provides an anode electrochromic material, an electrochromic composition, and an electrochromic apparatus.

[0204] An anode electrochromic material is provided, and the molecular structure of the anode electrochromic material is given by formula (I): [ka] It is represented by [this].

[0205] In formula (I), R1 to R6 are each independently one of the following: H, OH, F, Cl, Br, I, CN, NO2, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0206] Y is an alkylene group having a single bond or 1 to 4 carbon atoms.

[0207] X1 is N, NR 21 , or S, and X2 is N, NR 22 It is O, or S. 21 and R 22 Each of these is independently one of the following: hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0208] In some embodiments, the substituted or unsubstituted alkyl group has 1 to 18 carbon atoms, the substituted or unsubstituted alkoxy group has 1 to 18 carbon atoms, the substituted or unsubstituted aryl group has 6 to 18 carbon atoms, and the substituted or unsubstituted heterocyclic group has 2 to 18 carbon atoms.

[0209] In some embodiments, the substituents in the substituted alkyl group, substituted alkoxy group, substituted aryl group, substituted amino group, and substituted heterocyclic group are at least one of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group.

[0210] In some embodiments, the substituted or unsubstituted heterocyclic group includes one of the following: a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyranyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thiothioanyl group, a substituted or unsubstituted quinolinyl group, and a substituted or unsubstituted indoleyl group.

[0211] In some embodiments, R1 and R2 are each independently one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group, and R3, R4, R5, and R6 are H.

[0212] In some embodiments, the coloring response time of the anode electrochromic material is in the range of 0 to 3 seconds, and the decolorization response time of the anode electrochromic material is in the range of 0 to 15 seconds.

[0213] In some embodiments, the difference between the transmittance of the decolorized state and the transmittance of the colored state of the anode electrochromic material in the visible light region is in the range of 55% to 80%.

[0214] In some embodiments, the method for preparing an anode electrochromic material is as follows: The process involves adding raw materials 1 and 2 to an organic solvent, mixing them uniformly, adding a catalyst to obtain a mixed solution, and reacting the mixed solution at 60°C to 90°C for 12 to 96 hours to obtain an anode electrochromic material. Includes: [ka]

[0215] The catalyst comprises a strong base, or a combination of a weak base and cuprous iodide, wherein the strong base is at least one of sodium hydroxide, potassium hydroxide, sodium cyanide, sodium hydride, and butyllithium, and the weak base is at least one of sodium carbonate and potassium carbonate.

[0216] In some embodiments, electrochromic compositions are provided that include a cathode electrochromic material, a solvent, and the aforementioned anode electrochromic material.

[0217] In some embodiments, the concentration of the anode electrochromic material in the electrochromic composition is in the range of 10 mmol / L to 150 mmol / L.

[0218] In some embodiments, the cathode electrochromic material comprises a viologen compound, the viologen compound having a molecular structure of formula (II): [ka] It includes compounds represented by [the specified formula / method].

[0219] In formula (II), R7 and R8 are each independently one of the following: an alkyl group, alkenyl group, alkynyl group, aralkyl group, alkenyl alkyl group, alkynyl alkyl group, monohydroxyalkyl group or polyhydroxyalkyl group, monoamine alkyl group or polyamine alkyl group, monosubstituted haloalkyl group or polysubstituted haloalkyl group, monoalkoxy group or polyalkoxy group, phosphonium alkyl group, siloxyalkyl group, alkyl carboxylate, alkyl phosphonate, alkyl isocyanate, carboxylate, phosphonate group, isocyanate, pyridyl group, pyrrolyl group, furyl group, pyranyl group, thienyl group, quinolinyl group, and indoleyl group, each having 1 to 18 carbon atoms.

[0220] R9~R 16Each of these is independently one of the following: H, OH, F, Cl, Br, I, CN, NO2, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0221] X is an anion, and the anion includes one of the following: halides, borates, fluoroborates, tetraarylborates, metal hexafluorides or metalloid hexafluorides, sulfates, sulfonates, sulfonamides, carboxylates, perchlorates, and tetrachloroferrates.

[0222] In some embodiments, the concentration of the cathode electrochromic material in the electrochromic composition is in the range of 30 mmol / L to 120 mmol / L.

[0223] In some embodiments, the solvent includes at least one of 3-methylsulfolane, dimethyl sulfoxide, dimethylformamide, tetraethylene glycol dimethyl ether, polyethylene glycol, ethoxyethanol, acetonitrile, glutaronitrile, 2-acetylbutyrolactone, cyclopentanone, β-propiolactone, γ-butyrolactone, γ-valerolactone, polypropylene carbonate, ethylene carbonate, and propylene carbonate.

[0224] In some embodiments, the electrochromic composition further comprises at least one of the following: a delamination inhibitor, an antioxidant, a UV stabilizer, a thickener, and an ionic conductivity enhancer.

[0225] The delamination inhibitor comprises one of the following: polyacrylate, polymethacrylate, and polyaromatic ester.

[0226] The product comprises at least one of the following: antioxidants, 1,3,5-tri-tert-butylphenol, 1,5-tert-butyl-3-methylphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethylpiperidine, di-tert-butylamine, methyl methacrylate, and ethyl methacrylate.

[0227] The UV stabilizer comprises at least one of the following: 2-ethyl-2-cyano-3,3-diphenyl acrylate, (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionate amyl ester, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-ethyl-2'-ethoxypropionanilide.

[0228] The thickener includes one of the following: polyamide, polyimide, polycarbonate, polyester, polyether, polymethacrylate, polyacrylate, polysilane, polysiloxane, polyvinyl acetate, polymethacrylonitrile, polyacrylonitrile, polyvinylphenol, polyvinyl alcohol, polyvinylidene dihalides, and copolymers thereof.

[0229] The ion conductivity enhancer includes one of the following: lithium trifluoromethanesulfonate, lithium perchlorate, lithium tetrafluoroborate, and lithium hexafluorophosphate.

[0230] In some embodiments, the mass percentage of the delamination inhibitor in the electrochromic composition is in the range of 1% to 6%, the molar concentration of the antioxidant is in the range of 0.02 mol / L to 0.5 mol / L, the mass percentage of the UV stabilizer is in the range of 1% to 4%, the mass percentage of the thickener is in the range of 0.05% to 3%, and the concentration of the ion conductivity enhancer is in the range of 0.05 mol / L to 0.5 mol / L.

[0231] In some embodiments, an electrochromic apparatus is further provided, comprising a first electrode, a second electrode, and an electrochromic layer disposed between the first and second electrodes. The electrochromic layer comprises an anode electrochromic material according to any one of the embodiments described above, or an electrochromic composition according to any one of the embodiments described above.

[0232] In some embodiments, electronic devices including the aforementioned electrochromic apparatus are further provided.

[0233] Embodiments of the present invention are implemented, thereby significantly improving the electrochemical performance of electrochromic devices and solving problems in the prior art such as slow coloring and decolorization response speeds, uneven coloring, insufficient cycle stability, and short service life of electrochromic devices.

[0234] The specific configurations of the anode electrochromic material, electrochromic composition, and electrochromic apparatus are as follows.

[0235] In recent years, due to their superior performance and energy-saving and environmentally friendly properties, electrochromic materials are well-suited to future development trends in intelligent materials and have extremely broad application prospects in large-screen information displays, "smart windows," anti-glare rearview mirrors, electrochromic displays, and electronic inks. Electrochromism is a phenomenon in which, when an electric field is applied to a color-changing material or an electric current is conducted through it, the optical properties (transmittance, reflectance, or absorptance of light) of the material change stably and reversibly in the wavelength range including visible light wavelengths. From the perspective of appearance effects, electrochromism is expressed as a reversible change in color and transparency. When a voltage is applied to an electrochromic material, the visible light transmittance of the material decreases, and the material appears as a darker color. This phenomenon is called "coloring." When the application of voltage is stopped, the visible light transmittance of the material increases. This phenomenon is called "decolorization." Among the many electrochromic materials, organic electrochromic materials have been extensively studied because they possess superior optical performance and have a high potential for performance optimization through molecular design. Among organic electrochromic materials, viologens and their derivatives are widely studied. Viologens and their derivatives possess good cyclic reversibility and stable redox states, making them the most widely used color-changing materials in electrochromic devices. Since viologen compounds are cathode color-changing materials, people typically select a different anode material to form a complementary color-changing material with the viologen compound, thereby creating electrochromic devices with superior performance compared to using viologen compounds alone. However, most anode electrochromic materials currently suffer from problems such as slow response speed, non-uniform color change, and short cycle life.Therefore, it is necessary to develop an anode electrochromic material that forms an electrochromic material complementary to the biogenic cathode electrochromic material and use the anode electrochromic material in an electrochromic device, thereby improving the discoloration response speed, improving the coloring and bleaching display effects, and extending the service life of the electrochromic device.

[0236] In view of this, an embodiment of the present application provides an anode electrochromic material, and the molecular structure of the anode electrochromic material is represented by the formula (I): [Chemical formula] It is represented by.

[0237] In formula (I), R1 to R6 are each independently one of H, OH, F, Cl, Br, I, CN, NO2, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group. [[ID=^17]]

[0238] Y is a single bond or an alkylene group having 1 to 4 carbon atoms.

[0239] [[ID=^^23]]X1 is N, N-R 21 , or S, and X2 is N, N-R 22 , O, or S. R 21 and R 22 are each independently one of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0240] In some configurations, the substituted or unsubstituted alkyl group has 1 to 18 carbon atoms. In some configurations, the substituted or unsubstituted alkyl group may have 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 15, or 18 carbon atoms. In some embodiments, the substituted or unsubstituted alkyl group may be, for example, a substituted or unsubstituted methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 4-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylpentyl group, 5-methylpentyl group, 2-ethylbutyl group, 3-ethylbutyl group, heptyl group, octyl group, nonyl group, or decyl group.

[0241] In some configurations, the substituted or unsubstituted alkoxy group has 1 to 18 carbon atoms. In some configurations, the substituted or unsubstituted alkoxy group may have 1, 2, 3, 4, 5, 9, 10, 13, 15, 16, or 18 carbon atoms. In some embodiments, the substituted or unsubstituted alkoxy group may be, for example, a substituted or unsubstituted methoxy group, ethoxy group, propoxy group, butoxy group, isobutoxy group, or tert-butoxy group.

[0242] In some configurations, the substituted or unsubstituted aryl group has 6 to 18 carbon atoms. In some configurations, the substituted or unsubstituted aryl group may have 6, 7, 9, 10, 12, 13, 15, or 18 carbon atoms. In some embodiments, the substituted or unsubstituted aryl group may be, for example, a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, tetraphenyl group, or tetrahydronaphthyl group.

[0243] In some configurations, substituted or unsubstituted heterocyclic groups have 2 to 18 carbon atoms. In some configurations, substituted or unsubstituted heterocyclic groups may have 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 15, 16, or 18 carbon atoms. Substituted or unsubstituted heterocyclic groups may be monocyclic or polycyclic heterocyclic groups. Heteroatoms in heterocyclic groups may contain at least one of O, N, or S.

[0244] In the configuration of the present application, the substituted or unsubstituted heterocyclic group may be a five-membered heterocyclic group or a six-membered heterocyclic group, and may include a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyranyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thiothioanyl group, a substituted or unsubstituted quinolinyl group, and a substituted or unsubstituted indoleyl group. In some specific embodiments, the heterocyclic group may be, for example, a tetrahydrofuran ring, a tetrahydrothiophene ring, a hexahydropyrrole ring, a tetrahydropyran ring, a tetrahydropyridine ring, or a tetrahydrothiothioan ring.

[0245] In some configurations, the substituents in substituted alkyl groups, substituted alkoxy groups, substituted aryl groups, substituted amino groups, and substituted heterocyclic groups are one of the following: a halogen atom (F, Cl, Br, or I), a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. In some embodiments of the present application, the substituted alkyl group may be, for example, a haloalkyl group or an arylalkyl group. The haloalkyl group may be, for example, a trifluoromethyl group, a trifluoroethyl group, or a dichloroethyl group. The arylalkyl group may be, for example, a phenylalkyl group (benzyl group, phenylethyl group, or phenylpropyl group), a naphthylmethyl group, a naphthylbenzyl group, or the like.

[0246] In some configurations, R1 and R2 are each independently one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group, and R3, R4, R5, and R6 are H. When R1 and R2 in the present application are electron-donating groups such as a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, more electrons can be uniformly and symmetrically provided to the structure of the anode electrochromic material provided in the present application from two sides of 5,10-dihydrophenazine or its analog represented by structure B in formula (I), thereby increasing the electron cloud density of the anode electrochromic material and improving the color change response rate of the anode electrochromic material. In some configurations of the present application, the anode electrochromic material is represented by formulas (III) to (VI): [ka] It may be a compound represented by .

[0247] In the anoelectrochromic material provided in this embodiment of the present application, the six-membered heterocyclic structure (A) in formula (I) is grafted onto the N atom of 5,10-dihydrophenazine or an analog (B) to form an anoelectrochromic material with the structure represented by formula (I). This anoelectrochromic material has a good color change response rate, a uniform color change effect, and low manufacturing costs, and by using this anoelectrochromic material in an electrochromic device, the color change performance of the electrochromic device can be effectively improved. This is because there is a strong intermolecular interaction between the six-membered heterocyclic structure in the compound represented by formula (I) and the N atom of 5,10-dihydrophenazine or an analog, resulting in significant steric hindrance for the compound as a whole. The structure of the compound is less stable than that of a linear compound or an N-terminal substitution compound modified by a linear compound. The greater instability of the structure of the compound forming the anoelectrochromic material indicates that electron extraction from and injection into the material is easier. Therefore, electrochromic devices prepared using this compound have a higher color change response rate. In addition, when the N atom is located in the para position compared to other positions of the heteroatom in the six-membered heterocyclic structure (e.g., ortho or meta position), the raw materials can be obtained more easily and at a lower cost, and the difficulty of synthesis is reduced, which contributes to a reduction in manufacturing costs. Therefore, the anodic electrochromic material provided in this embodiment of the present application has a low manufacturing cost, a high color change response rate, and a good color change effect.

[0248] In the configuration of the present application, the coloring response time of the anode electrochromic material is in the range of 0 to 3 seconds, and the decolorization response time of the anode electrochromic material is in the range of 0 to 15 seconds. In some configurations of the present application, the coloring response time of the anode electrochromic material may be 0.5 seconds, 1.0 seconds, 1.1 seconds, 1.2 seconds, 1.3 seconds, 1.4 seconds, 1.5 seconds, 1.6 seconds, 1.7 seconds, 1.8 seconds, 1.9 seconds, 2.0 seconds, 2.2 seconds, 2.5 seconds, 2.8 seconds, or 3 seconds. In some embodiments of the present application, the decolorization response time of the anode electrochromic material may be divided into a decolorization response time when the power is off and a decolorization response time when it is short-circuited. In this application, the decolorization response time of the anode electrochromic material during a short circuit may be 1.0 seconds, 2.0 seconds, 3.0 seconds, 4.0 seconds, 4.5 seconds, 4.8 seconds, 5.1 seconds, 5.3 seconds, 5.4 seconds, 5.6 seconds, 5.7 seconds, 6.0 seconds, 6.5 seconds, 7.0 seconds, 7.2 seconds, 7.5 seconds, 7.8 seconds, 8.0 seconds, 8.3 seconds, 8.6 seconds, 8.9 seconds, or 9.0 seconds, and the decolorization response time during power off may be 9.5 seconds, 10.0 seconds, 10.2 seconds, 10.8 seconds, 11.1 seconds, 11.6 seconds, 11.4 seconds, 12.3 seconds, 13.0 seconds, 14.0 seconds, or 15.0 seconds. The structure of the anode electrochromic material provided in this application has large steric hindrance and high electron density, which allows the coloring response time and decolorization response time to be controlled within a fast range.

[0249] In the configuration of the present invention, the difference between the transmittance of the decolorized state and the transmittance of the colored state of the anode electrochromic material in the visible light region is in the range of 55% to 80%. In some configurations of the present invention, the difference between the transmittance of the decolorized state and the transmittance of the colored state of the anode electrochromic material in the visible light region before and after each cycle is in the range of 55% to 80%. The difference between the transmittance in the decolorized state and the transmittance in the colored state in the visible light region may be 55%, 55.6%, 57%, 58%, 60%, 63.9%, 64.3%, 64.5%, 65.1%, 65.3%, 66.0%, 66.1%, 68.4%, 68.9%, 69.1%, 70.2%, 70.5%, 71.3%, 71.7%, 72.4%, 72.5%, 72.7%, 73.2%, 74%, 75%, 76%, 78%, or 80%. The anode electrochromic material of this application can achieve a good electrochromic effect when the difference between the transmittance in the decolorized state and the transmittance in the colored state is in the range of 55% to 80%. In some embodiments of the present application, after 50,000 energization cycles, the difference between the decolorized and colored transmittances of the anode electrochromic material in the visible light region may be 55.6%, 63.9%, 64.5%, 65.1%, 65.3%, 66%, or 66.1%. The cycle performance of the anode electrochromic material provided in the present application is stable, and the cycle life of the prepared electrochromic device is longer.

[0250] In response to this, embodiments of the present application further provide a method for preparing an anode electrochromic material, the following steps: The steps include adding raw material 1 and raw material 2 to an organic solvent, mixing them uniformly, adding a catalyst to obtain a mixed solution, and reacting the mixed solution at 60°C to 90°C for 12 to 96 hours to obtain the aforementioned anode electrochromic material in the embodiment of the present invention. Includes: [ka]

[0251] The catalyst comprises a strong base, or a combination of a weak base and cuprous iodide, wherein the strong base is at least one of sodium hydroxide, potassium hydroxide, sodium cyanide, sodium hydride, and butyllithium (e.g., tetraisobutyllithium), and the weak base is at least one of sodium carbonate and potassium carbonate. Under the presence of the base, dihydrophenazine or its analogue dehydrogenates the nitrogen atom and imparts a negative charge to the nitrogen atom.

[0252] In some configurations of the present invention, the catalyst may be a combination of a weak base and cuprous iodide, and the specific reaction synthesis route is given by formula (a): [ka] This will be shown.

[0253] In the configuration of this invention, each reactant for preparing the anode electrochromic material may be supplied in a molar ratio of starting material 1:starting material 2:catalyst = 1:(1-2):(1-3). The organic solvent may be toluene, N,N-dimethylformamide, DMSO, or chloroform. For example, the organic solvent is toluene. The product synthesized according to formula (a) can be separated and purified by silica gel column chromatography to obtain a crude anode electrochromic material. The crude anode electrochromic material can be redissolved in a commonly used organic solvent and recrystallized to obtain a purified anode electrochromic material. Commonly used organic solvents may be, for example, acetonitrile, ethanol, methanol, dichloromethane, chloroform, or ethyl acetate.

[0254] In the method for preparing an anoelectrochromic material provided in this embodiment of the present application, the starting materials, a six-membered heterocyclic compound and 5,10-dihydrophenazine or its analogues, are readily and inexpensively obtainable. In addition, the nitrogen atom of 5,10-dihydrophenazine or its analogues is located at the para position of the heteroatom in the six-membered heterocyclic structure, which contributes to lower synthetic difficulty, milder reaction conditions, a simpler preparation process, and easier handling compared to other positions (e.g., ortho or meta).

[0255] Embodiments of the present application further provide an electrochromic composition comprising a cathode electrochromic material, a solvent, and the aforementioned anode electrochromic material in embodiments of the present application. The electrochromic composition provided in embodiments of the present application comprises both the aforementioned anode electrochromic material and cathode electrochromic material in the present application, and is a complementary combination of electrochromic materials. Electrochromic devices made from complementary color-changing materials offer advantages such as high response speed, long operating life, energy savings, rich colorability, and the ability to maximize light transmittance, and are highly valuable for widespread use and applications.

[0256] In the configuration of the present invention, the concentration of the anode electrochromic material in the electrochromic composition is in the range of 10 mmol / L to 150 mmol / L. In some configurations of the present invention, the concentration of the anode electrochromic material may be 10 mmol / L, 20 mmol / L, 30 mmol / L, 40 mmol / L, 50 mmol / L, 60 mmol / L, 65 mmol / L, 70 mmol / L, 75 mmol / L, 80 mmol / L, 85 mmol / L, 90 mmol / L, 100 mmol / L, 110 mmol / L, 120 mmol / L, 140 mmol / L, or 150 mmol / L.

[0257] In the configuration of this application, the cathode electrochromic material contains a viologen compound. As described above, the viologen compound has a molecular structure of formula (II): [ka] It includes compounds represented by [the specified formula / method].

[0258] In formula (II), R7 and R8 are each independently one of the following: an alkyl group, alkenyl group, alkynyl group, aralkyl group, alkenyl alkyl group, alkynyl alkyl group, monohydroxyalkyl group or polyhydroxyalkyl group, monoamine alkyl group or polyamine alkyl group, monosubstituted haloalkyl group or polysubstituted haloalkyl group, monoalkoxy group or polyalkoxy group, phosphonium alkyl group, siloxyalkyl group, alkyl carboxylate, alkyl phosphonate, alkyl isocyanate, carboxylate, phosphonate group, isocyanate, pyridyl group, pyrrolyl group, furyl group, pyranyl group, thienyl group, quinolinyl group, and indoleyl group, each having 1 to 18 carbon atoms.

[0259] R9 to R 16 Each of these is independently one of the following: H, OH, F, Cl, Br, I, CN, NO2, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0260] X is an anion, and the anion comprises one of the following: halides, borates, fluoroborates, tetraarylborates, metallic hexafluorides or metalloid hexafluorides, sulfates, sulfonates, sulfonamides, carboxylates, perchlorates, and tetrachloroferrates. In some configurations of the present application, X is F - Cl - , Br - , I - BF4 - PF6 - SbF6 - AsF6 - ClO4 - , SO3CF3 - , N(CN)2 -, N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - Al(OC(CF3)3)4 - , bis(trifluoromethylsulfonyl)imido anion, or BAr4 - This may be the case, where Ar is an aryl group or a fluorinated aryl group. In the configuration of this application, X is -BAr4 and Ar is a pentafluorophenyl group.

[0261] Specifically, in the configuration of this application, the cathode electrochromic material is ethyl viologen ditetrafluoroborate, and the molecular structure of the cathode electrochromic material is given by formula (VII): [ka] It is represented by [this].

[0262] The cathode electrochromic material in this embodiment of the present application is a viologen compound, which has good cyclic reversibility and a stable redox state, and when combined with the anode electrochromic material in this embodiment, forms a complementary color-changing material, thereby improving the overall cyclic reversibility and stability of the material.

[0263] In the configuration of the present invention, the concentration of the cathode electrochromic material in the electrochromic composition is in the range of 30 mmol / L to 120 mmol / L. In some configurations of the present invention, the concentration of the cathode electrochromic material may be 30 mmol / L, 40 mmol / L, 50 mmol / L, 60 mmol / L, 70 mmol / L, 80 mmol / L, 85 mmol / L, 90 mmol / L, 95 mmol / L, 100 mmol / L, 110 mmol / L, or 120 mmol / L.

[0264] In the configuration of the present application, the solvent comprises at least one of 3-methylsulfolane, dimethyl sulfoxide, dimethylformamide, tetraethylene glycol dimethyl ether, polyethylene glycol, ethoxyethanol, acetonitrile, glutaronitrile, 2-acetylbutyrolactone, cyclopentanone, β-propiolactone, γ-butyrolactone, γ-valerolactone, polypropylene carbonate, ethylene carbonate, and propylene carbonate. The electrochromic composition provided in the present application uses the aforementioned solvent, thereby uniformly dispersing the anode electrochromic material and cathode electrochromic material in the composition, resulting in a more uniform color change effect of the resulting electrochromic composition.

[0265] In the configuration of this application, the electrochromic composition further comprises at least one of a delamination inhibitor, an antioxidant, a UV stabilizer, a thickener, and an ion conductivity enhancer. By adding a delamination inhibitor and a UV stabilizer to the electrochromic composition, the service life of the material can be extended. By adding an ion conductivity enhancer, the discoloration response rate of the material can be accelerated. By adding an antioxidant, deactivation of the material due to oxidation can be prevented, improving the durability of the electrochromic composition and extending its service life. By adding a thickener, the structural stability of the material can be enhanced.

[0266] In the configuration of this application, the delamination inhibitor comprises one of polyacrylate, polymethacrylate, and polyaromatic ester. The mass percentage of the delamination inhibitor in the electrochromic composition is in the range of 1% to 6%. In some configurations of this application, the mass percentage of the delamination inhibitor may be 1%, 2%, 3%, 4%, 4.5%, 5%, 5.5%, or 6%. The delamination inhibitor in the electrochromic composition can slow down the degradation of the material due to delamination and extend the cycle life of the electrochromic composition.

[0267] In the composition of this application, antioxidants, 1,3,5-tri-tert-butylphenol, 1,5-tert-butyl-3-methylphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3' The composition comprises at least one of ,5'-dipentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethylpiperidine, di-tert-butylamine, methyl methacrylate, and ethyl methacrylate. In some embodiments, the antioxidant may be at least one of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 1,5-tert-butyl-3-methylphenol, and methyl methacrylate. The molar concentration of the antioxidant in the electrochromic composition is in the range of 0.02 mol / L to 0.5 mol / L. In some embodiments of the present application, the molar concentration of the antioxidant may be 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, 0.1 mol / L, 0.15 mol / L, 0.18 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, 0.4 mol / L, or 0.5 mol / L. By adding an antioxidant, the loss of the color-changing ability of the anode electrochromic material due to oxidative deactivation can be prevented, and the uniformity of the color change and the service life of the electrochromic composition can be improved.

[0268] In the configuration of the present application, the UV stabilizer comprises at least one of 2-ethyl-2-cyano-3,3-diphenyl acrylate, (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 3-[3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionate amyl ester, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-ethyl-2'-ethoxypropionanilide. The mass percentage of the UV stabilizer in the electrochromic composition is in the range of 1% to 4%. In some configurations of the present application, the mass percentage of the UV stabilizer may be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, or 4%. By adding a UV stabilizer, the stability of the electrochromic composition can be improved, and the cycle life of the composition can be extended.

[0269] In the configuration of this application, the thickener comprises one of the following: polyamide, polyimide, polycarbonate, polyester, polyether, polymethacrylate, polyacrylate, polysilane, polysiloxane, polyvinyl acetate, polymethacrylonitrile, polyacrylonitrile, polyvinylphenol, polyvinyl alcohol, polyvinylidene dihalides, and copolymers thereof. The mass percentage of the thickener in the electrochromic composition is in the range of 0.05% to 3%. In some configurations of this application, the mass percentage of the thickener may be 0.05%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 2%, 2.5%, or 3%. The thickener can enhance the structural stability of the material, thereby resulting in more uniform discoloration and a longer service life of the resulting electrochromic apparatus.

[0270] In the configuration of this application, the ion conductivity enhancer comprises one of lithium trifluoromethanesulfonate, lithium perchlorate, lithium tetrafluoroborate, and lithium hexafluorophosphate. The concentration of the ion conductivity enhancer in the electrochromic composition is in the range of 0.05 mol / L to 0.5 mol / L. In some configurations of this application, the concentration of the ion conductivity enhancer may be 0.05 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.05 mol / L, 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, or 0.5 mol / L. By adding an ion conductivity enhancer to the electrochromic composition, the ion conductivity of the material can be improved, thereby enabling the electrochromic composition to obtain a faster electrochromic response rate.

[0271] By adding all of the above-mentioned additives—a delamination inhibitor, an antioxidant, a UV stabilizer, an ion conductivity enhancer, and a thickener—to the electrochromic composition according to the amounts specified in this application, the cycle stability, response speed, and service life of the composition can be synergistically improved.

[0272] The electrochromic composition provided in this embodiment of the present application has excellent color change response speed, uniform color change effect, good cycle stability, and low manufacturing cost. By using this electrochromic composition in an electrochromic device, the color change response time and decolorization response time of the color change device can be increased, the color change display effect can be improved, the service life can be extended, manufacturing costs can be reduced, and the optical and electrochemical performance of the electrochromic device can be effectively improved.

[0273] Embodiments of the present application provide an electrochromic apparatus comprising a first electrode, a second electrode, and an electrochromic layer disposed between the first electrode and the second electrode. The electrochromic layer comprises the anode electrochromic material or the electrochromic composition described herein. In the configuration of the present application, as shown in Figure 13, the electrochromic apparatus 100b comprises a first substrate board 10b, a first electrode 20b, a second substrate board 11b, a second electrode 21b, an electrochromic layer 30b, and a sealing member 40b. The first electrode 20b is disposed on the first substrate board 10b, the second electrode 21a is disposed on the second substrate board 11b, and the electrochromic layer 30b is disposed between the first electrode 20b and the second electrode 21b. The sealing member 40b is disposed between the first electrode 20b and the second electrode 21b and joins the first electrode 20b and the second electrode 21b to each other. When an electrochromic device is in operation, a specific voltage is applied between a first electrode and a second electrode, causing the electrochromic layer material to undergo a redox reaction under the voltage and change color. When the electrochromic layer uses the anode electrochromic material or electrochromic composition provided in this application, the color change response speed of the electrochromic device can be improved, and the color change display effect and cycle stability of the device can be improved.

[0274] Embodiments of the present application further provide electronic devices including the aforementioned electrochromic devices in embodiments of the present application. Electronic devices include electrochromic rearview mirrors for vehicles, sunroofs for vehicles, VR glasses, electrochromic windows for buildings and aircraft, sunglasses and goggles, electrochromic displays, and the like.

[0275] Embodiments of the present invention will be described below using several embodiments.

[0276] Example 6 (1) Preparation of anode electrochromic materials (represented by formula (III)) 22.7 g of 3,7-dimethylphenothiazine and 16.3 g of 4-bromohexahydropyridine were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux condensation for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (III) with the molecular structure shown below: [ka] I obtained it.

[0277] (2) Preparation of electrochromic compositions An electrochromic composition was prepared according to the following chemical composition: 60 mmol / L of anode electrochromic material (III), 60 mmol / L of ethyl viologen ditetrafluoroborate, 0.1 mol / L of lithium perchlorate, 4 wt% of ethyl polyacrylate, 3 wt% of 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% of polyvinylidene fluoride, and the remainder of propylene carbonate.

[0278] (3) Preparation of electrochromic apparatus The electrochromic composition provided in step (2) of Example 6 was sandwiched between two glass plates plated with an ITO layer, and sealed using a frame sealant to prepare the electrochromic apparatus of Example 6 of the present application, which was 40 mm in both length and width, had a housing space thickness of 62 μm, and the transmittance of a single ITO glass plate was 92%.

[0279] Example 7 (1) Preparation of anode electrochromic materials (represented by formula (IV)) 22.7 g of 3,7-dimethylphenothiazine and 18.0 g of 4-bromotetrahydrothion were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (IV) with the molecular structure shown below: [ka] I obtained it.

[0280] (2) Preparation of electrochromic compositions An electrochromic composition was prepared according to the following chemical composition: 60 mmol / L of anode electrochromic material (IV), 60 mmol / L of ethyl viologen ditetrafluoroborate, 0.1 mol / L of lithium perchlorate, 4 wt% of ethyl polyacrylate, 3 wt% of 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% of polyvinylidene fluoride, and the remainder of propylene carbonate.

[0281] (3) Preparation of electrochromic apparatus The electrochromic apparatus of Example 6 of this application, with a length and width of 40 mm, was prepared by sandwiching the electrochromic composition provided in step (2) of Example 7 between two glass plates plated with an ITO layer and encapsulating it using a flame sealant. The thickness of the containment space was 62 μm, and the transmittance of a single ITO glass plate was 92%.

[0282] Example 8 (1) Preparation of anode electrochromic materials (represented by formula (V)) 28.7 g of 3,7-diethoxyphenothiazine and 18.0 g of 4-bromotetrahydrothion were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (V) with the molecular structure shown below: [ka] I obtained it.

[0283] (2) Preparation of electrochromic compositions An electrochromic composition was prepared according to the following chemical composition: 60 mmol / L of anode electrochromic material (V), 60 mmol / L of ethyl viologen ditetrafluoroborate, 0.1 mol / L of lithium perchlorate, 4 wt% of ethyl polyacrylate, 3 wt% of 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% of polyvinylidene fluoride, and the remainder of propylene carbonate.

[0284] (3) Preparation of electrochromic apparatus The electrochromic apparatus of Example 7 of this application, with a length and width of 40 mm, was prepared by sandwiching the electrochromic composition provided in step (2) of Example 8 between two glass plates plated with an ITO layer and encapsulating it using a flame sealant. The thickness of the containment space was 62 μm, and the transmittance of a single ITO glass plate was 92%.

[0285] Example 9 (1) Preparation of anode electrochromic materials (represented by formula (VI)) 35.2 g of 3,7-diphenylphenothiazine and 18.0 g of 4-bromotetrahydrothion were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (VI) with the molecular structure shown below: [ka] I obtained it.

[0286] (2) Preparation of electrochromic compositions An electrochromic composition was prepared according to the following chemical composition: 60 mmol / L of anode electrochromic material (VI), 60 mmol / L of ethyl viologen ditetrafluoroborate, 0.1 mol / L of lithium perchlorate, 4 wt% of ethyl polyacrylate, 3 wt% of 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% of polyvinylidene fluoride, and the remainder of propylene carbonate.

[0287] (3) Preparation of electrochromic apparatus The electrochromic apparatus of Example 8 of this application, with a length and width of 40 mm, was prepared by sandwiching the electrochromic composition provided in step (2) of Example 9 between two glass plates plated with an ITO layer and encapsulating it using a flame sealant. The thickness of the containment space was 62 μm, and the transmittance of a single ITO glass plate was 92%.

[0288] Example 10 (1) Preparation of electrochromic compositions An electrochromic composition was prepared according to the following chemical composition: 60 mmol / L of anode electrochromic material (III), 60 mmol / L of ethyl viologen ditetrafluoroborate, 0.5 mol / L of lithium perchlorate, 4 wt% of ethyl polyacrylate, 3 wt% of 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% of polyvinylidene fluoride, and the remainder of propylene carbonate.

[0289] (2) Preparation of electrochromic apparatus The electrochromic apparatus of Example 1 of the present application, having a length and width of 40 mm, was prepared by sandwiching the electrochromic composition provided in step (2) of Example 10 between two glass plates plated with an ITO layer and encapsulating it using a flame sealant. The thickness of the containment space was 62 μm, and the transmittance of a single ITO glass plate was 92%.

[0290] Example 11 (1) Preparation of electrochromic compositions An electrochromic composition was prepared according to the following chemical composition: 60 mmol / L of anode electrochromic material (III), 60 mmol / L of ethyl viologen ditetrafluoroborate, 0.1 mol / L of lithium tetrafluoroborate, 4 wt% of ethyl polyacrylate, 3 wt% of 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% of polyvinylidene fluoride, and the remainder of propylene carbonate.

[0291] (2) Preparation of electrochromic apparatus The electrochromic apparatus of Example 6 of this application, with a length and width of 40 mm, was prepared by sandwiching the electrochromic composition provided in step (2) of Example 11 between two glass plates plated with an ITO layer and encapsulating it using a flame sealant. The thickness of the containment space was 62 μm, and the transmittance of a single ITO glass plate was 92%.

[0292] Example 12 (1) Preparation of electrochromic compositions An electrochromic composition was prepared according to the following chemical composition: 60 mmol / L of anode electrochromic material (III), 60 mmol / L of ethyl viologen ditetrafluoroborate, 0.5 mol / L of lithium tetrafluoroborate, 4 wt% of ethyl polyacrylate, 3 wt% of 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% of polyvinylidene fluoride, and the remainder of propylene carbonate.

[0293] (2) Preparation of electrochromic apparatus The electrochromic apparatus of Example 6 of this application, with a length and width of 40 mm, was prepared by sandwiching the electrochromic composition provided in step (2) of Example 12 between two glass plates plated with an ITO layer and encapsulating it using a flame sealant. The thickness of the containment space was 62 μm, and the transmittance of a single ITO glass plate was 92%.

[0294] Comparative Example 3 (1) Preparation of electrochromic compositions An electrochromic composition was prepared according to the following chemical composition: 60 mmol / L phenothiazine, 60 mmol / L ethyl viologen ditetrafluoroborate, 0.1 mol / L lithium perchlorate, 4 wt% ethyl polyacrylate, 3 wt% 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% polyvinylidene fluoride, and the remainder propylene carbonate.

[0295] (2) Preparation of electrochromic apparatus The electrochromic apparatus of this comparative example of the present application, having a length and width of 40 mm, was prepared by sandwiching the electrochromic composition provided in step (1) of Comparative Example 3 between two glass plates plated with an ITO layer and encapsulating it using a flame sealant. The thickness of the containment space was 62 μm, and the transmittance of a single ITO glass plate was 92%.

[0296] The following tests were performed on the electrochromic apparatuses prepared in Examples 6-12 and Comparative Example 3.

[0297] (1) Discoloration performance test At a test voltage of 1.2V, the coloring response time, decolorization response time when the power was turned off, and decolorization response time when the device was short-circuited were tested for each electrochromic device. The test results are shown in Table 2.

[0298] [Table 3]

[0299] The test results in Table 2 show that the coloring response time, decolorization response time when the power is turned off, and decolorization response time when the electrochromic apparatus in Examples 6 to 12 were all shorter than those of Comparative Example 3. This indicates that the anode electrochromic material provided in the embodiments of the present application can improve the coloring and decolorization rates of the prepared electrochromic apparatus. Examples 8, 10, 11, and 12 show that the addition of lithium salts, which are ion conductivity improvers, increases the color change rate of the apparatus and enhances the color change performance of the apparatus, and that the effect of lithium tetrafluoroborate is slightly stronger than that of lithium perchlorate.

[0300] (2) Cycle life test At a test voltage of 1.2V, the state of each electrochromic device was observed after 0 energization cycles, 20,000 energization cycles, and 50,000 energization cycles, and the light transmittance (T) at the time of decolorization was measured. v=0 ) and light transmittance (T v=1.2 The difference between the light transmittance before discoloration and the light transmittance after discoloration (ΔT = T) was measured. V=0 -T V=1.2 The life cycle was calculated by applying a voltage of 1.2V for 5 seconds and then a voltage of 0V for 10 seconds, which was defined as one cycle. The results of the cycle life test are shown in Tables 3 and 4.

[0301] [Table 4]

[0302] [Table 5]

[0303] Tables 3 and 4 show that in Examples 6 to 12, there was no significant change in discoloration performance or uniformity after 50,000 discoloration cycles. In Example 6, the discoloration performance deteriorated slightly, and the solution had non-fading mottling at the edges and corners of the apparatus. In Examples 6 to 12, the difference between the light transmittance before and after discoloration could be maintained at over 55%. However, in Comparative Example 3, after 50,000 discoloration cycles, the discoloration performance deteriorated significantly, the overall color of the apparatus became darker, the edges and corners had non-fading mottling, and the difference between the light transmittance before and after discoloration could be reduced to 50.2%. This demonstrates that the cycle life of the prepared electrochromic apparatus can be improved by using the anode electrochromic material provided in the embodiments of the present application.

[0304] The present application further provides another anode electrochromic material, another electrochromic composition, and another electrochromic apparatus.

[0305] In some embodiments, the anode electrochromic material is a compound whose molecular structure is represented by formula (a1), and / or a compound whose molecular structure is represented by formula (a2): [ka] Includes.

[0306] In equations (a1) and (a2), R1 to R 18Each of these is independently one of the following: H, OH, F, Cl, Br, I, CN, NO2, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0307] Y is an alkylene group having a single bond or 1 to 4 carbon atoms.

[0308] X1 is N, NR 21 , or S, and X2 is N, NR 22 It is O, or S. 21 and R 22 Each of these is independently one of the following: hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0309] In some embodiments, the substituted or unsubstituted alkyl group has 1 to 18 carbon atoms, the substituted or unsubstituted alkoxy group has 1 to 18 carbon atoms, the substituted or unsubstituted aryl group has 6 to 18 carbon atoms, and the substituted or unsubstituted heterocyclic group has 2 to 18 carbon atoms.

[0310] In some embodiments, the substituents in the substituted alkyl group, substituted alkoxy group, substituted aryl group, substituted amino group, and substituted heterocyclic group are at least one of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0311] In some embodiments, the substituted or unsubstituted heterocyclic group includes one of the following: a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyranyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thiothioanyl group, a substituted or unsubstituted quinolinyl group, and a substituted or unsubstituted indolyl group.

[0312] In some embodiments, R1, R3, R4, R5, R6, and R8 to R 18 is H. R2 and R7 are each independently one of the following: a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group.

[0313] In some embodiments, the coloring response time of the anode electrochromic material is in the range of 0 to 3 seconds, and the decolorization response time of the anode electrochromic material is in the range of 0 to 15 seconds.

[0314] In some embodiments, the difference between the transmittance of the decolorized state and the transmittance of the colored state of the anode electrochromic material in the visible light region is in the range of 55% to 80%.

[0315] In some embodiments, the following steps: The process involves adding raw material 1 or raw material 2 and raw material 3 to an organic solvent, mixing them uniformly, adding a catalyst to obtain a mixed solution, and reacting the mixed solution at 60°C to 90°C for 12 to 96 hours to obtain an anode electrochromic material. A method for preparing an anode electrochromic material, including the following, is further provided: [ka] [ka]

[0316] The catalyst comprises a strong base, or a combination of a weak base and cuprous iodide, wherein the strong base is at least one of sodium hydroxide, potassium hydroxide, sodium cyanide, sodium hydride, and butyllithium, and the weak base is at least one of sodium carbonate and potassium carbonate.

[0317] In some embodiments, electrochromic compositions comprising a cathode electrochromic material, a solvent, and an anode electrochromic material according to any one of claims 1 to 7 are further provided.

[0318] In some embodiments, the concentration of the anode electrochromic material in the electrochromic composition is in the range of 10 mmol / L to 150 mmol / L.

[0319] In some embodiments, the cathode electrochromic material comprises a viologen compound, the viologen compound having a molecular structure of formula (a3): [ka] It includes compounds represented by [the specified formula / method].

[0320] In formula (a3), R 30 and R 31 Each of these is independently one of the following groups having 1 to 18 carbon atoms: alkyl group, alkenyl group, alkynyl group, aralkyl group, alkenyl alkyl group, alkynyl alkyl group, monohydroxyalkyl group or polyhydroxyalkyl group, monoamine alkyl group or polyamine alkyl group, monosubstituted haloalkyl group or polysubstituted haloalkyl group, monoalkoxy group or polyalkoxy group, phosphonium alkyl group, siloxyalkyl group, alkyl carboxylate, alkyl phosphonate, alkyl isocyanate, carboxylate, phosphonate group, isocyanate, pyridyl group, pyrrolyl group, furyl group, pyranyl group, thienyl group, quinolinyl group, and indoleyl group.

[0321] R 32 ~R 39 Each of these is independently one of the following: H, OH, F, Cl, Br, I, CN, NO2, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0322] X is an anion, and the anion includes one of the following: halides, borates, fluoroborates, tetraarylborates, metal hexafluorides or metalloid hexafluorides, sulfates, sulfonates, sulfonamides, carboxylates, perchlorates, and tetrachloroferrates.

[0323] In some embodiments, the concentration of the cathode electrochromic material in the electrochromic composition is in the range of 30 mmol / L to 120 mmol / L.

[0324] In some embodiments, the solvent includes at least one of 3-methylsulfolane, dimethyl sulfoxide, dimethylformamide, tetraethylene glycol dimethyl ether, polyethylene glycol, ethoxyethanol, acetonitrile, glutaronitrile, 2-acetylbutyrolactone, cyclopentanone, β-propiolactone, γ-butyrolactone, γ-valerolactone, polypropylene carbonate, ethylene carbonate, and propylene carbonate.

[0325] In some embodiments, the electrochromic composition further comprises at least one of the following: a delamination inhibitor, an antioxidant, a UV stabilizer, a thickener, and an ionic conductivity enhancer.

[0326] The delamination inhibitor comprises one of the following: polyacrylate, polymethacrylate, and polyaromatic ester.

[0327] The product comprises at least one of the following: antioxidants, 1,3,5-tri-tert-butylphenol, 1,5-tert-butyl-3-methylphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethylpiperidine, di-tert-butylamine, methyl methacrylate, and ethyl methacrylate.

[0328] The UV stabilizer comprises at least one of the following: 2-ethyl-2-cyano-3,3-diphenyl acrylate, (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionate amyl ester, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-ethyl-2'-ethoxypropionanilide.

[0329] The thickener includes one of the following: polyamide, polyimide, polycarbonate, polyester, polyether, polymethacrylate, polyacrylate, polysilane, polysiloxane, polyvinyl acetate, polymethacrylonitrile, polyacrylonitrile, polyvinylphenol, polyvinyl alcohol, polyvinylidene dihalides, and copolymers thereof.

[0330] The ion conductivity enhancer includes one of the following: lithium trifluoromethanesulfonate, lithium perchlorate, lithium tetrafluoroborate, and lithium hexafluorophosphate.

[0331] In some embodiments, the mass percentage of the delamination inhibitor in the electrochromic composition is in the range of 1% to 6%, the molar concentration of the antioxidant is in the range of 0.02 mol / L to 0.5 mol / L, the mass percentage of the UV stabilizer is in the range of 1% to 4%, the mass percentage of the thickener is in the range of 0.05% to 3%, and the molar concentration of the ion conductivity enhancer is in the range of 0.05 mol / L to 0.5 mol / L.

[0332] In some embodiments, an electrochromic apparatus is further provided, comprising a first electrode, a second electrode, and an electrochromic layer disposed between the first and second electrodes. The electrochromic layer comprises the aforementioned anode electrochromic material or the aforementioned electrochromic composition.

[0333] In some embodiments, electronic devices including the aforementioned electrochromic apparatus are further provided.

[0334] Embodiments of the present invention are implemented, thereby significantly improving the electrochemical performance of electrochromic devices and solving problems in the prior art such as slow coloring and decolorization response speeds, uneven coloring, insufficient cycle stability, and short service life of electrochromic devices.

[0335] The specific configurations of other anode electrochromic materials, other electrochromic compositions, and other electrochromic devices are as follows:

[0336] Hereinafter, embodiments of the present invention will be described with reference to the attached drawings of the embodiments of the present invention.

[0337] In recent years, due to their superior performance and energy-saving and environmentally friendly properties, electrochromic materials are well-suited to future development trends in intelligent materials and have extremely broad application prospects in large-screen information displays, "smart windows," anti-glare rearview mirrors, electrochromic displays, and electronic inks. Electrochromism is a phenomenon in which, when an electric field is applied to a color-changing material or an electric current is conducted through it, the optical properties (transmittance, reflectance, or absorptance of light) of the material change stably and reversibly in the wavelength range including visible light wavelengths. From the perspective of appearance effects, electrochromism is expressed as a reversible change in color and transparency. When a voltage is applied to an electrochromic material, the visible light transmittance of the material decreases, and the material appears as a darker color. This phenomenon is called "coloring." When the application of voltage is stopped, the visible light transmittance of the material increases. This phenomenon is called "decolorization." Among the many electrochromic materials, organic electrochromic materials have been extensively studied because they possess superior optical performance and have a high potential for performance optimization through molecular design. Among organic electrochromic materials, viologens and their derivatives are widely studied. Viologens and their derivatives possess good cyclic reversibility and stable redox states, making them the most widely used color-changing materials in electrochromic devices. Since viologen compounds are cathode color-changing materials, people typically select a different anode material to form a complementary color-changing material with the viologen compound, thereby creating electrochromic devices with superior performance compared to using viologen compounds alone. However, most anode electrochromic materials currently suffer from problems such as slow response speed, non-uniform color change, and short cycle life.Therefore, it is necessary to develop an anode electrochromic material that forms an electrochromic material complementary to the viologen cathode electrochromic material and to use this anode electrochromic material in an electrochromic device. This will improve the color change response speed, enhance the coloring and decolorization display effect, and extend the service life of the electrochromic device.

[0338] In view of this, embodiments of the present application provide an anode electrochromic material comprising a compound whose molecular structure is represented by formula (a1) and / or a compound whose molecular structure is represented by formula (a2): [ka] Includes.

[0339] In equations (a1) and (a2), R1 to R 18 Each of these is independently one of the following: H, OH, F, Cl, Br, I, CN, NO2, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0340] Y is an alkylene group having a single bond or 1 to 4 carbon atoms.

[0341] X1 is N, NR 21 , or S, and X2 is N, NR 22 It is O, or S. 21 and R 22 Each of these is independently one of the following: hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0342] In the configuration of the present application, the substituted or unsubstituted alkyl group has 1 to 18 carbon atoms. In some configurations, the substituted or unsubstituted alkyl group may have 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 15, or 18 carbon atoms. In some embodiments, the substituted or unsubstituted alkyl group may be, for example, a substituted or unsubstituted methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 4-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylpentyl group, 5-methylpentyl group, 2-ethylbutyl group, 3-ethylbutyl group, heptyl group, octyl group, nonyl group, or decyl group.

[0343] In the configuration of this application, the substituted or unsubstituted alkoxy group has 1 to 18 carbon atoms. In some configurations, the substituted or unsubstituted alkoxy group may have 1, 2, 3, 4, 5, 9, 10, 13, 15, 16, or 18 carbon atoms. In some embodiments, the substituted or unsubstituted alkoxy group may be, for example, a substituted or unsubstituted methoxy group, ethoxy group, propoxy group, butoxy group, isobutoxy group, or tert-butoxy group.

[0344] In the configuration of this application, the substituted or unsubstituted aryl group has 6 to 18 carbon atoms. In some configurations, the substituted or unsubstituted aryl group may have 6, 7, 9, 10, 12, 13, 15, or 18 carbon atoms. In some embodiments, the substituted or unsubstituted aryl group may be, for example, a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, tetraphenyl group, or tetrahydronaphthyl group.

[0345] In the configuration of this application, the substituted or unsubstituted heterocyclic group has 2 to 18 carbon atoms. In some configurations, the substituted or unsubstituted heterocyclic group may have 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 15, 16, or 18 carbon atoms. The substituted or unsubstituted heterocyclic group may be a monocyclic or polycyclic heterocyclic group. The heteroatom in the heterocyclic group may contain at least one of O, N, or S.

[0346] In the configuration of the present application, the substituted or unsubstituted heterocyclic group may be a five-membered heterocyclic group or a six-membered heterocyclic group, and may include any one of the following: a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyranyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thiothioanyl group, a substituted or unsubstituted quinolinyl group, and a substituted or unsubstituted indoleyl group. In some specific embodiments, the heterocyclic group may be, for example, a tetrahydrofuran ring, a tetrahydrothiophene ring, a hexahydropyrrole ring, a tetrahydropyran ring, a tetrahydropyridine ring, or a tetrahydrothiothioane ring.

[0347] In the configuration of the present application, the substituents in the substituted alkyl group, substituted alkoxy group, substituted aryl group, substituted amino group, and substituted heterocyclic group are at least one of the following: a halogen atom (F, Cl, Br, or I), a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group. In some embodiments of the present application, the substituted alkyl group may be, for example, a haloalkyl group or an arylalkyl group. The haloalkyl group may be, for example, a trifluoromethyl group, a trifluoroethyl group, a dichloroethyl group, etc. The arylalkyl group may be, for example, a phenylalkyl group (benzyl group, phenylethyl group, or phenylpropyl group), a naphthylmethyl group, a naphthylbenzyl group, etc.

[0348] In the configuration of this application, R1, R3, R4, R5, R6, and R8~R 18 is H. R2 and R7 are each independently one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. When R2 and R7 in the present application are electron-donating groups such as a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, more electrons can be uniformly and symmetrically provided to the structure of the anode electrochromic material provided in the present application from two sides of 5,10-dihydrophenazine or its analog represented by structure C in formulas (a1) and (a2), thereby increasing the electron cloud density of the anode electrochromic material and improving the color change response rate of the anode electrochromic material. In some embodiments of the present application, the anode electrochromic material is defined by formulas (a4) to (a11): [ka] It may be a compound represented by .

[0349] In the anoelectrochromic material provided in this embodiment of the present application, a benzo six-membered heterocyclic structure represented by structure A in formula (a1) or a tricyclodibenzo six-membered heterocyclic structure represented by structure B in formula (a2) is grafted onto the N atom of 5,10-dihydrophenazine or its analogues represented by structure C in formulas (a1) and (a2) to form an anoelectrochromic material of the structure represented by formula (a1) or formula (a2). This anoelectrochromic material has a good color change response rate, a uniform color change effect, and low manufacturing costs, and by using this anoelectrochromic material in an electrochromic device, the color change performance of the electrochromic device can be effectively improved. When the anoelectrochromic material loses electrons to form a positively charged structure, the fact that the groups connected to this positively charged structure retain more electrons indicates that the anoelectrochromic material is more stable and that the rate of formation of the anoelectrochromic material in the electrocatalytic state is faster. The benzo six-membered heterocyclic structure in the compound represented by formula (a1) and the tricyclodibenzo six-membered heterocyclic structure in the compound represented by formula (a2) can both provide more electrons to the anodic electrochromic material than a monocyclic six-membered heterocyclic structure. In addition, there is a strong intermolecular interaction between the benzo six-membered heterocyclic structure in the compound represented by formula (a1) and the tricyclodibenzo six-membered heterocyclic structure in the compound represented by formula (a2) and the N atom of 5,10-dihydrophenazine or its analogues. The compound as a whole has significant steric hindrance, which is an unstable factor for the overall structure of the compound compared to linear or linearly modified N-terminal substitution compounds. When the electrocatalytic state disappears, the structure with significant steric hindrance can quickly revert to its original structure. Therefore, electrochromic devices prepared using this compound have a higher color change response rate.In addition, when the N atom is located at position 4 of the benzo six-membered heterocyclic structure or position 9 of the dibenzo six-membered heterocyclic structure, i.e., at the benzyl position of the benzene ring, compared to other positions (e.g., ortho or meta), the raw materials are less expensive and easier to obtain, and the synthesis is less difficult, which contributes to reducing manufacturing costs. Therefore, the anoelectrochromic material provided in this embodiment of the present application has low manufacturing costs, a high color change response rate, and a good color change effect.

[0350] In the configuration of the present invention, the coloring response time of the anode electrochromic material is in the range of 0 to 3 seconds, and the decolorization response time of the anode electrochromic material is in the range of 0 to 15 seconds. In some embodiments of the present invention, the coloring response time of the anode electrochromic material may be 1.57 seconds, 1.64 seconds, 1.69 seconds, 1.72 seconds, 1.75 seconds, 1.82 seconds, 1.88 seconds, or 1.91 seconds. In some configurations of the present invention, the decolorization response time of the anode electrochromic material may be divided into a decolorization response time when the power is off and a decolorization response time when it is short-circuited. In some embodiments of the present application, the decolorization response time when the power is off may be 11.22 seconds, 12.01 seconds, 12.57 seconds, 12.77 seconds, 12.88 seconds, 12.89 seconds, 13.14 seconds, or 13.55 seconds; the decolorization response time when short-circuited may be 4.42 seconds, 4.99 seconds, 5.56 seconds, 5.66 seconds, 5.90 seconds, 6.21 seconds, 6.44 seconds, or 6.81 seconds. The structure of the anode electrochromic material provided in the present application has large steric hindrance and high electron density, thereby enabling control of the coloring response time and decolorization response time within a fast range.

[0351] In the configuration of this application, the difference between the decolorized state transmittance and the colored state transmittance of the anode electrochromic material in the visible light region is in the range of 55% to 80%. In some configurations of this application, the difference between the decolorized state transmittance and the colored state transmittance of the anode electrochromic material in the visible light region before and after each cycle is both in the range of 55% to 80%. The difference between the decolorized state transmittance and the colored state transmittance in the visible light region may be 55%, 60%, 65%, 70%, 75%, or 80%. The anode electrochromic material of this application can achieve a good electrochromic effect when the difference between the decolorized state transmittance and the colored state transmittance is in the range of 55% to 80%. In some embodiments of the present application, after 50,000 cycles, the difference between the decolorized and colored transmittances of the anode electrochromic material in the visible light region may be 60.1%, 60.4%, 61.0%, 61.1%, 62.1%, 62.5%, 62.7%, or 60.1%. The cycle performance of the anode electrochromic material provided in the present application is stable, and the cycle life of the prepared electrochromic device is longer.

[0352] In the anoelectrochromic material provided in the first embodiment of the present invention, a benzo six-membered heterocyclic structure represented by structure A of formula (a1) or a tricyclodibenzo six-membered heterocyclic structure represented by structure B of formula (a2) is grafted onto the N atom of 5,10-dihydrophenazine or an analog represented by structure C in formulas (a1) and (a2) to form an anoelectrochromic material having the structure represented by formula (a1) or formula (a2). This anoelectrochromic material has excellent color change response speed, uniform color change effect, and low manufacturing cost. By using this anoelectrochromic material in an electrochromic device, the coloring response time and decolorization response time of the color change device can be increased, the color change display effect can be improved, and manufacturing costs can be reduced, while solving the problems of slow response speed, non-uniform color change, and high manufacturing cost of existing anoelectrochromic materials.

[0353] In response to this, embodiments of the present application further provide a method for preparing an anode electrochromic material, the following steps: The steps include adding raw material 1 or raw materials 2 and 3 to an organic solvent, mixing them uniformly, adding a catalyst to obtain a mixed solution, and reacting the mixed solution at 60°C to 90°C for 12 to 96 hours to obtain an anode electrochromic material according to the first embodiment of the present invention. Includes: [ka]

[0354] The catalyst comprises a strong base, or a combination of a weak base and cuprous iodide, wherein the strong base is at least one of sodium hydroxide, potassium hydroxide, sodium cyanide, sodium hydride, and butyllithium (e.g., tetraisobutyllithium), and the weak base is at least one of sodium carbonate and potassium carbonate. Under the action of the base, dihydrophenazine or its analogue dehydrogenates the nitrogen atom and imparts a negative charge to the nitrogen atom.

[0355] In some configurations, the catalyst may be a weak base and cuprous iodide, and specific reaction synthesis pathways are given by formulas (a) and (b): [ka] This will be shown.

[0356] In the configuration of this invention, each reactant for preparing the anode electrochromic material may be supplied in a mass ratio of 3:1:1:3 or 3:1:2:1:3. The organic solvent may be toluene, N,N-dimethylformamide, dimethyl sulfoxide, or chloroform. The product synthesized according to formula (a) or (b) can be separated and purified by silica gel column chromatography to obtain a crude anode electrochromic material. The crude anode electrochromic material can be redissolved in a commonly used organic solvent and recrystallized to obtain a purified anode electrochromic material. In some configurations, the commonly used organic solvent may be, for example, acetonitrile, ethanol, methanol, dichloromethane, chloroform, or ethyl acetate.

[0357] In the method for preparing anoelectrochromic materials provided in this embodiment of the present application, the starting materials, a benzo six-membered heterocycle, a tricyclodibenzo six-membered heterocycle, and 5,10-dihydrophenazine or its analogues, are readily and inexpensively obtainable. In addition, the nitrogen atom of 5,10-dihydrophenazine or its analogues is located at position 4 of the benzo six-membered heterocycle structure or position 9 of the dibenzo six-membered heterocycle structure, i.e., the benzyl position of the benzene ring, which contributes to lower synthetic difficulty, milder reaction conditions, a simpler preparation process, and easier handling compared to other positions (e.g., ortho or meta).

[0358] Embodiments of the present application further provide an electrochromic composition comprising a cathode electrochromic material, a solvent, and the aforementioned anode electrochromic material in embodiments of the present application. The electrochromic composition provided in embodiments of the present application comprises both the aforementioned anode electrochromic material and cathode electrochromic material in the present application, and is a complementary combination of electrochromic materials. Electrochromic devices made from complementary color-changing materials offer advantages such as high response speed, long operating life, energy savings, rich colorability, and the ability to maximize light transmittance, and are highly valuable for widespread use and applications.

[0359] In the configuration of the present application, the concentration of the anode electrochromic material is in the range of 10 mmol / L to 150 mmol / L. In some embodiments of the present application, the concentration of the anode electrochromic material may be 10 mmol / L, 20 mmol / L, 30 mmol / L, 40 mmol / L, 50 mmol / L, 60 mmol / L, 65 mmol / L, 70 mmol / L, 75 mmol / L, 80 mmol / L, 85 mmol / L, 90 mmol / L, 100 mmol / L, 110 mmol / L, 120 mmol / L, 130 mmol / L, 140 mmol / L, or 150 mmol / L.

[0360] In the configuration of this application, the cathode electrochromic material comprises a viologen compound, the viologen compound having a molecular structure of formula (a3): [ka] It includes compounds represented by [the specified formula / method].

[0361] In formula (a3), R 30 and R 31Each of these is independently one of the following groups having 1 to 18 carbon atoms: alkyl group, alkenyl group, alkynyl group, aralkyl group, alkenyl alkyl group, alkynyl alkyl group, monohydroxyalkyl group or polyhydroxyalkyl group, monoamine alkyl group or polyamine alkyl group, monosubstituted haloalkyl group or polysubstituted haloalkyl group, monoalkoxy group or polyalkoxy group, phosphonium alkyl group, siloxyalkyl group, alkyl carboxylate, alkyl phosphonate, alkyl isocyanate, carboxylate, phosphonate group, isocyanate, pyridyl group, pyrrolyl group, furyl group, pyranyl group, thienyl group, quinolinyl group, and indoleyl group.

[0362] R 32 ~R 39 Each of these is independently one of the following: H, OH, F, Cl, Br, I, CN, NO2, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.

[0363] X is an anion, and the anion includes one of the following: halides, borates, fluoroborates, tetraarylborates, metal hexafluorides or metalloid hexafluorides, sulfates, sulfonates, sulfonamides, carboxylates, perchlorates, and tetrachloroferrates.

[0364] In some configurations of this application, X is F - Cl - , Br - , I - BF4 - PF6 - SbF6 - AsF6 - ClO4 - , SO3CF3 - , N(CN)2 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 -, Al(OC(CF3)3)4, bis(trifluoromethylsulfonyl)imido anion, or BAr4 - This may be the case, where Ar is an aryl group or a fluorinated aryl group. In embodiments of the present application, X is -BAr4 and Ar is a pentafluorophenyl group.

[0365] Specifically, in the embodiments of the present application, the cathode electrochromic material has a molecular structure of formula (a12): [ka] It is ethyl viologen ditetrafluoroborate, represented by [formula].

[0366] The cathode electrochromic material in this embodiment of the present application is a viologen compound, which has good cyclic reversibility and a stable redox state, and can be combined with the anode electrochromic material in this embodiment to form a complementary color-changing material, thereby improving the overall cyclic reversibility and stability of the material.

[0367] In the configuration of the present application, the concentration of the cathode electrochromic material is in the range of 30 mmol / L to 120 mmol / L. In some embodiments of the present application, the concentration of the cathode electrochromic material may be 30 mmol / L, 40 mmol / L, 50 mmol / L, 60 mmol / L, 70 mmol / L, 80 mmol / L, 85 mmol / L, 90 mmol / L, 95 mmol / L, 100 mmol / L, 110 mmol / L, or 120 mmol / L.

[0368] In the configuration of the present application, the solvent comprises at least one of 3-methylsulfolane, dimethyl sulfoxide, dimethylformamide, tetraethylene glycol dimethyl ether, polyethylene glycol, ethoxyethanol, acetonitrile, glutaronitrile, 2-acetylbutyrolactone, cyclopentanone, β-propiolactone, γ-butyrolactone, γ-valerolactone, polypropylene carbonate, ethylene carbonate, and propylene carbonate. The electrochromic composition provided in the present application uses the aforementioned solvent, thereby uniformly dispersing the anode electrochromic material and cathode electrochromic material in the solvent, resulting in a more uniform color change effect of the resulting electrochromic composition.

[0369] In the configuration of this application, the electrochromic composition further comprises at least one of a delamination inhibitor, an antioxidant, a UV stabilizer, a thickener, and an ion conductivity enhancer. By adding a delamination inhibitor and a UV stabilizer to the electrochromic composition, the service life of the material can be extended. By adding an ion conductivity enhancer, the discoloration response rate of the material can be accelerated. By adding an antioxidant, deactivation of the material due to oxidation can be prevented. By adding a thickener, the structural stability of the material can be enhanced.

[0370] In the configuration of the present application, the delamination inhibitor comprises one of polyacrylate, polymethacrylate, and polyaromatic ester. The mass percentage of the delamination inhibitor in the electrochromic composition is in the range of 1% to 6%. In some embodiments of the present application, the mass percentage of the delamination inhibitor may be 1%, 2%, 3%, 4%, 4.5%, 5%, 5.5%, or 6%. The delamination inhibitor in the electrochromic composition can slow down the degradation of the material due to delamination and extend the cycle life of the electrochromic composition.

[0371] In the composition of this application, antioxidants, 1,3,5-tri-tert-butylphenol, 1,5-tert-butyl-3-methylphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3' The composition comprises at least one of the following: ,5'-dipentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethylpiperidine, di-tert-butylamine, methyl methacrylate, and ethyl methacrylate. The molar concentration of the antioxidant in the electrochromic composition is in the range of 0.02 mol / L to 0.5 mol / L. In some embodiments of the present application, the molar concentration of the antioxidant may be 0.02 mol / L, 0.03 mol / L, 0.05 mol / L, 0.08 mol / L, 0.1 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, 0.4 mol / L, or 0.5 mol / L. By adding the antioxidant, the loss of the color-changing ability of the anode electrochromic material due to oxidative deactivation can be prevented, and the uniformity of the color change and the service life of the electrochromic composition can be improved.

[0372] In the composition of this application, the UV stabilizer comprises at least one of 2-ethyl-2-cyano-3,3-diphenyl acrylate, (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 3-[3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionate amyl ester, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-ethyl-2'-ethoxypropionanilide. The mass percentage of the UV stabilizer in the electrochromic composition is in the range of 1% to 4%. In some embodiments of this application, the mass percentage of the UV stabilizer may be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, or 4%. By adding a UV stabilizer, the stability of the electrochromic composition can be improved, and the cycle life of the composition can be extended.

[0373] In the configuration of this application, the thickener comprises one of the following: polyamide, polyimide, polycarbonate, polyester, polyether, polymethacrylate, polyacrylate, polysilane, polysiloxane, polyvinyl acetate, polymethacrylonitrile, polyacrylonitrile, polyvinylphenol, polyvinyl alcohol, polyvinylidene dihalides, and copolymers thereof. The mass percentage of the thickener in the electrochromic composition is in the range of 0.05% to 3%. In some embodiments of this application, the mass percentage of the thickener may be 0.05%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 2%, 2.5%, or 3%. The thickener can enhance the structural stability of the material, thereby resulting in more uniform discoloration and a longer service life of the resulting electrochromic apparatus.

[0374] In the configuration of this application, the ion conductivity enhancer comprises one of lithium trifluoromethanesulfonate, lithium perchlorate, lithium tetrafluoroborate, and lithium hexafluorophosphate. The concentration of the ion conductivity enhancer in the electrochromic composition is in the range of 0.05 mol / L to 0.5 mol / L. In some embodiments of this application, the concentration of the ion conductivity enhancer may be 0.05 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.05 mol / L, 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, or 0.5 mol / L. By adding the ion conductivity enhancer to the electrochromic composition, the ion conductivity of the material can be improved, thereby enabling the electrochromic composition to obtain a faster electrochromic response rate.

[0375] By adding all of the above-mentioned additives—a delamination inhibitor, an antioxidant, a UV stabilizer, an ion conductivity enhancer, and a thickener—to the electrochromic composition according to the amounts described in this application, they can exert a synergistic effect on each other and improve the cycle stability, response speed, and service life of the composition.

[0376] The electrochromic composition provided in this embodiment of the present application has excellent color change response speed, uniform color change effect, good cycle stability, and low manufacturing cost. By using this electrochromic composition in an electrochromic device, the color change response time and decolorization response time of the color change device can be increased, the color change display effect can be improved, the service life can be extended, manufacturing costs can be reduced, and the optical and electrochemical performance of the electrochromic device can be effectively improved.

[0377] Embodiments of the present application provide an electrochromic apparatus comprising a first electrode, a second electrode, and an electrochromic layer disposed between the first electrode and the second electrode. The electrochromic layer comprises the anode electrochromic material or the electrochromic composition described herein. In the configuration of the present application, as shown in Figure 14, the electrochromic apparatus 100c comprises a first substrate board 10c, a first electrode 20c, a second substrate board 11c, a second electrode 21c, an electrochromic layer 30c, and a sealing member 40c. The first electrode 20c is disposed on the first substrate board 10c, the second electrode 21c is disposed on the second substrate board 11c, and the electrochromic layer 30c is disposed between the first electrode 20c and the second electrode 21c. The sealing member 40c is disposed between the first electrode 20c and the second electrode 21c and joins the first electrode 20c and the second electrode 21c to each other. When an electrochromic device is in operation, a specific voltage is applied between a first electrode and a second electrode, causing the electrochromic layer material to undergo a redox reaction under the voltage and change color. When the electrochromic layer uses the anode electrochromic material or electrochromic composition provided in this application, the color change response speed of the electrochromic device can be improved, and the color change display effect and cycle stability of the device can be improved.

[0378] Embodiments of the present application further provide electronic devices including the aforementioned electrochromic devices in embodiments of the present application. Electronic devices include electrochromic rearview mirrors for vehicles, sunroofs for vehicles, VR glasses, electrochromic windows for buildings and aircraft, sunglasses and goggles, electrochromic displays, and the like.

[0379] Embodiments of the present invention will be described below using several embodiments.

[0380] Example 13 22.7 g of 3,7-dimethylphenothiazine and 22.7 g of 4-bromobenzotetrahydrothion were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (a4) with the molecular structure shown below: [ka] I obtained it.

[0381] Example 14 28.7 g of 3,7-diethoxyphenothiazine and 22.7 g of 4-bromobenzotetrahydrothion were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (V) with the molecular structure shown below: [ka] I obtained it.

[0382] Example 15 20.0 g of phenothiazine and 22.7 g of 4-bromobenzotetrahydrothion were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (VI) with the molecular structure shown below: [ka] I obtained it.

[0383] Example 16 35.2 g of 3,7-dinitrophenothiazine and 22.7 g of 4-bromobenzotetrahydrothion were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (VII) with the molecular structure shown below: [ka] I obtained it.

[0384] Example 17 22.7 g of 3,7-dimethylphenothiazine and 27.6 g of 9-bromothioanthracene were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (VIII) with the molecular structure shown below: [ka] I obtained it.

[0385] Example 18 28.7 g of 3,7-diethoxyphenothiazine and 27.6 g of 9-bromothioanthracene were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (IX) with the molecular structure shown below: [ka] I obtained it.

[0386] Example 19 20.0 g of phenothiazine and 27.6 g of 9-bromothioanthracene were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (X) with the molecular structure shown below: [ka] I obtained it.

[0387] Example 20 35.2 g of 3,7-diphenylphenothiazine and 27.6 g of 9-bromothioanthracene were dissolved in 500 g of toluene. After homogeneous mixing, 13.2 g of potassium carbonate and 2 g of cuprous iodide were added. The temperature was raised to 60°C to 90°C, and the reaction was carried out under reflux for 12 to 96 hours to obtain a reaction product containing the anode electrochromic material. The reaction product was separated and purified by silica gel column chromatography to obtain the crude anode electrochromic material. This crude anode electrochromic material was dissolved in acetonitrile and recrystallized to obtain the purified anode electrochromic material (XI) with the molecular structure shown below: [ka] I obtained it.

[0388] Comparative Example 4 Phenothiazine was selected as the anode electrochromic material.

[0389] Electrochromic compositions were prepared using the anode electrochromic materials prepared in Examples 13 to 20 and Comparative Example 4. The components of the electrochromic compositions and their concentrations were as follows: 60 mmol / L of anode electrochromic material, 60 mmol / L of ethyl viologen ditetrafluoroborate, 0.1 mol / L of lithium perchlorate, 4 wt% of ethyl polyacrylate, 3 wt% of 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% of polyvinylidene fluoride, and the remainder of propylene carbonate. The prepared electrochromic composition was sandwiched between two glass plates plated with an ITO layer, and sealed using a frame sealant to prepare an electrochromic apparatus with a length and width of 40 mm, a housing thickness of 62 μm, and a transmittance of 92% through a single ITO glass plate.

[0390] The electrochromic apparatus prepared in Examples 13 to 20 and Comparative Example 4 of this application was subjected to the following tests: (1) Discoloration performance test At a test voltage of 1.3V, the coloring response time, decolorization response time when the power was turned off, and decolorization response time when the device was short-circuited were tested for each electrochromic device. The test results are shown in Table 5.

[0391] [Table 6]

[0392] From the test results in Table 5, it can be seen that the coloring response time, decolorization response time when the power is turned off, and decolorization response time when the electrochromic devices of Examples 13 to 20 are all shorter than those of Comparative Example 4. This indicates that the anode electrochromic material provided in the embodiments of the present application can improve the coloring and decolorization speeds of the prepared electrochromic devices.

[0393] (2) Cycle life test At a test voltage of 1.2V, the state of each electrochromic device was observed after 0 energization cycles, 20,000 energization cycles, and 50,000 energization cycles, and the light transmittance (T) at the time of decolorization was measured. v=0 ) and light transmittance (T v=1.2 The difference between the light transmittance before discoloration and the light transmittance after discoloration (ΔT = T) was measured. V=0 -T V=1.2 The life cycle was calculated. One cycle consisted of applying a voltage of 1.2V for 5 seconds and then a voltage of 0V for 10 seconds. The results of the cycle life test are shown in Tables 6 and 7.

[0394] [Table 7]

[0395] [Table 8]

[0396] Tables 6 and 7 show that in Examples 13 to 20, there was no significant change in discoloration performance or uniformity after 50,000 discoloration cycles, and the difference between the light transmittance before and after discoloration could be maintained at 60% or more. However, in Comparative Example 4, after 50,000 discoloration cycles, the discoloration performance deteriorated significantly, the overall color of the device became darker, the edges and corners had persistent mottling, and the difference between the light transmittance before and after discoloration decreased to 51.9%. This indicates that the cycle life of the prepared electrochromic device can be improved by using the anode electrochromic material provided in the embodiments of the present application.

[0397] This application further provides phenazine compounds containing a crosslinked ring structure and their applications, as well as electrochromic apparatus and its applications.

[0398] A phenazine compound containing a crosslinked ring structure is provided, and this compound is given by formula b1: [ka] It is a structure represented by [this].

[0399] R1, R2, R3, R4, R5, R6, R7, and R8 are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkenylalkyl group, a substituted or unsubstituted alkynylalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted heterocyclic aryl group, a substituted or unsubstituted arcyl group, a substituted or unsubstituted alkoxy group, a halogen, a cyano group, a nitro group, a carboxylate group, a phosphonate group, or an isocyanate group. R9 is a substituted or unsubstituted alkyl group having 1 to 2 consecutive methylene structures.

[0400] Regarding the aforementioned phenazine compounds, Substituted or unsubstituted alkyl groups are substituted or unsubstituted C1-C 14 It is an alkyl group, Substituted or unsubstituted alkenyl groups are substituted or unsubstituted C2-C 14 It is an alkenyl group, Substituted or unsubstituted aryl groups are substituted or unsubstituted C7-C 14 It is an aryl group, Substituted or unsubstituted aralkyl groups are substituted or unsubstituted C8-C 14 It is an aralkyl group, Substituted or unsubstituted heterocyclic aryl groups are substituted or unsubstituted C2-C 14 It is a heterocyclic aryl group, A substituted or unsubstituted arcyl group is a substituted or unsubstituted C3-C3 group. 14 It is an arcyl group, Substituted or unsubstituted alkoxy groups are substituted or unsubstituted C1-C1 14 It is an alkoxy group.

[0401] For the aforementioned phenazine compounds, R1, R2, R3, R4, R5, R6, R7, and R8 are, independently, an alkyl group, an alkenyl group, an alkynyl group, an alkenyl alkyl group, an alkynyl alkyl group, a monohydroxyalkyl group, a polyhydroxyalkyl group, a monoamine alkyl group, a polyamine alkyl group, a monosubstituted haloalkyl group, a polysubstituted haloalkyl group, a monoalkyloxyalkyl group, a polyalkyloxyalkyl group, a phosphonium alkyl group, a siloxyalkyl group, an alkyl carboxylate group, an alkylphosphonate group, an alkyl isocyanate group, a nitro group, a carboxylate group, a phosphonate group, an isocyanate group, a pyridyl group, a pyrrolyl group, a furyl group, a pyranyl group, a thienyl group, a quinolinyl group, or an indoleyl group.

[0402] In some embodiments, R1, R2, R3, R4, R5, R6, R7, and R8 are independently H, C1-C 10 Alkyl groups, C1-C3 alkoxy groups, nitro groups, nitrile groups, C6-C 10 Aryl group, or C2~C 10 It is a heterocyclic aryl group.

[0403] Regarding the aforementioned phenazine compounds, the alkyl group in R9 is an alkyl group substituted with a halogen, alkyl group, alkenyl group, alkynyl group, alkenyl alkyl group, alkynyl alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, monoamine alkyl group, polyamine alkyl group, substituted haloalkyl group, monoalkyloxyalkyl group, polyalkyloxyalkyl group, phosphonium alkyl group, siloxyalkyl group, alkylcarboxylate group, alkylphosphonate group, alkylisocyanate group, carboxylate group, phosphonate group, isocyanate group, pyridyl group, pyrrolyl group, furyl group, pyranyl group, thienyl group, quinolinyl group, or indoleyl group, and the substitution includes monosubstituted and polysubstituted groups.

[0404] For example, R9 consists of two unsubstituted methylene groups.

[0405] Regarding the aforementioned phenazine compounds, the compounds are represented by formulas b5, b6, b7, b8, b9, b10, and b11: [ka] It is at least one of the compounds represented by [the formula].

[0406] This application further provides applications for phenazine compounds as anode color change materials in electrochromic devices.

[0407] The present application further provides an electrochromic apparatus. A first base material, the first base material having a first conductive surface, A second base material, the second base material having a second conductive surface, and Includes.

[0408] The first conductive surface and the second conductive surface are combined using a sealing member to form a sealed cavity. A color-changing medium is placed inside the sealed cavity, and the anode color-changing material in the color-changing medium comprises a phenazine compound according to any one of the embodiments described above.

[0409] In some embodiments, the color change medium comprises a cathode color change material, an anode color change material, a solvent, and an optional auxiliary agent.

[0410] In some embodiments, the color-changing medium includes an anode color-changing material in a concentration of 30 mmol / L to 120 mmol / L and a cathode color-changing material in a concentration of 30 mmol / L to 120 mmol / L.

[0411] In some embodiments, the additive is at least one of a delamination inhibitor, a UV stabilizer, a thickener, and an electrolyte.

[0412] In some embodiments, in a color-changing medium, The content of the delamination inhibitor is in the range of 1% to 6% by weight, and / or The UV stabilizer content is in the range of 1% to 4% by weight, and / or The thickening agent content is in the range of 0.05% to 3% by weight, and / or The electrolyte content is in the range of 0.05 mol / L to 0.5 mol / L.

[0413] In some embodiments, the color-changing medium comprises 30 mmol / L to 120 mmol / L of an anode color-changing material, 30 mmol / L to 120 mmol / L of a cathode color-changing material, 1% to 6% by weight of an interlayer delamination inhibitor, 1% to 4% by weight of a UV stabilizer, 0.05% to 3% by weight of a thickener, 0.05 mol / L to 0.5 mol / L of an electrolyte, and a solvent.

[0414] The present invention further provides applications for the aforementioned electrochromic apparatus in the preparation of at least one of the following: glass curtain walls, architectural glass windows, automotive glass products, spectacle lenses, and electronic devices.

[0415] The specific configurations of phenazine compounds containing a cross-linked ring structure and their applications, as well as electrochromic apparatus and its applications, are as follows.

[0416] The endpoints of the ranges and any values ​​disclosed herein are not limited to exact ranges or values. These ranges or values ​​should be understood to include values ​​close to them. For numerical ranges, one or more new numerical ranges can be obtained by combining the endpoints of each range, the endpoints of each range with individual points, and individual points with each other, and these numerical ranges are deemed to be specifically disclosed herein.

[0417] This application provides a phenazine compound containing a crosslinked ring structure, the compound having formula b1: [ka] It is a structure represented by [this].

[0418] R1, R2, R3, R4, R5, R6, R7, and R8 are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkenylalkyl group, a substituted or unsubstituted alkynylalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted heterocyclic aryl group, a substituted or unsubstituted arcyl group, a substituted or unsubstituted alkoxy group, a halogen, a cyano group, a nitro group, a carboxylate group, a phosphonate group, an isocyanate group, a pyridyl group, a pyrrolyl group, a furyl group, a pyranyl group, a thienyl group, a quinolinyl group, or an indoleyl group. R9 is a substituted or unsubstituted alkyl group having 1 to 2 consecutive methylene structures. The phenazine compounds containing the crosslinked ring structure of this application are used as anodic color change materials having good compatibility, a fast response rate, uniform color change, and a long cycle life.

[0419] According to the structure of this application, the substituted or unsubstituted alkyl group is a substituted or unsubstituted C1-C 14 It is an alkyl group. Phenazine compounds containing a crosslinked ring structure, and having this structure, are used as anodic color change materials that have good compatibility, a fast response rate, uniform color change, and a long cycle life.

[0420] According to the structure of this application, the substituted or unsubstituted alkenyl group is a substituted or unsubstituted C2-C 14 It is an alkenyl group. Phenazine compounds with this structure are used as anodic color change materials that have good compatibility, a fast response rate, uniform color change, and a long cycle life.

[0421] According to the structure of this application, the substituted or unsubstituted aryl group is a substituted or unsubstituted C7-C 14 It is an aryl group. Phenazine compounds with this structure are used as anodic color change materials that have good compatibility, a fast response rate, uniform color change, and a long cycle life.

[0422] According to the structure of this application, the substituted or unsubstituted aralkyl group is a substituted or unsubstituted C8-C 14 It is an aralkyl group.

[0423] According to the structure of this application, the substituted or unsubstituted heterocyclic aryl group is a substituted or unsubstituted C2-C 14 It is a heterocyclic aryl group. Phenazine compounds with this structure are used as anodic color change materials that have good compatibility, a fast response rate, uniform color change, and a long cycle life.

[0424] According to the structure of this application, the substituted or unsubstituted arcyl group is a substituted or unsubstituted C3-C 14 It is an acyl group. Phenazine compounds with this structure are used as anodic color change materials that have good compatibility, a fast response rate, uniform color change, and a long cycle life.

[0425] According to the structure of this application, the substituted or unsubstituted alkoxy group is a substituted or unsubstituted C1-C 14 It is an alkoxy group. Phenazine compounds with this structure are used as anodic color change materials that have good compatibility, a fast response rate, uniform color change, and a long cycle life.

[0426] In some embodiments, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently an alkyl group, an alkenyl group, an alkynyl group, an alkenylalkyl group, an alkynylalkyl group, a monohydroxyalkyl group, a polyhydroxyalkyl group, a monoaminealkyl group, a polyaminealkyl group, a monosubstituted haloalkyl group, a polysubstituted haloalkyl group, a monoalkyloxyalkyl group, a polyalkyloxyalkyl group, a phosphoniumalkyl group, a siloxyalkyl group, an alkylcarboxylate group, an alkylphosphonate group, an alkylisocyanate group, a nitro group, a carboxylate group, a phosphonate group, an isocyanate group, a pyridyl group, a pyrrolyl group, a furyl group, a pyranyl group, a thienyl group, a quinolinyl group, or an indolyl group. The phenazine compound of this structure is used as an anode discoloring material having good compatibility, a fast response rate, uniform discoloration, and a long cycle life.

[0427] In some embodiments, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently H, C1-C 10 alkyl group, C1-C3 alkoxy group, nitro group, nitrile group, C6-C 10 aryl group, or C2-C 10 heterocyclic aryl group. The phenazine compound of this structure is used as an anode discoloring material having good compatibility, a fast response rate, uniform discoloration, and a long cycle life.

[0428] In some embodiments, the alkyl group in R9 is an alkyl group substituted with a halogen, alkyl group, alkenyl group, alkynyl group, alkenyl alkyl group, alkynyl alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, monoamine alkyl group, polyamine alkyl group, substituted haloalkyl group, monoalkyloxyalkyl group, polyalkyloxyalkyl group, phosphonium alkyl group, siloxyalkyl group, alkylcarboxylate group, alkylphosphonate group, alkylisocyanate group, carboxylate group, phosphonate group, isocyanate group, pyridyl group, pyrrolyl group, furyl group, pyranyl group, thienyl group, quinolinyl group, or indoleyl group, and the substitutions include monosubstituted and polysubstituted groups.

[0429] In some embodiments, R9 consists of two unsubstituted methylene groups. Phenazine compounds of this structure are used as anodic color change materials with good compatibility, fast response rate, uniform color change, and long cycle life.

[0430] In some embodiments, embodiments of the present application use at least one of the compounds represented by formulas b5, b6, b7, b8, b9, b10, and b11 as examples to illustrate the advantages of the present application. However, the scope of the present application is not limited thereto. [ka]

[0431] To facilitate comparison, in the embodiments of the present application, formula b4: [ka] The advantages of this invention will be explained through comparison, using compounds represented by as examples.

[0432] This application provides for the use of the phenazine compound as an anode color change material in electrochromic apparatus.

[0433] This application provides an electrochromic apparatus (shown in Figure 15). The electrochromic apparatus is A first base material 1n, wherein the first base material 1n has a first conductive surface 2n, A second base material 5n, wherein the second base material 5n has a second conductive surface 4n, and Includes.

[0434] The first conductive surface 2n and the second conductive surface are combined using a sealing member to form a sealed cavity. A color-changing medium is placed inside the sealed cavity, and the anode color-changing material in the color-changing medium contains a phenazine compound according to the present invention. An electrochromic device of this structure has good stability and strong color-changing ability.

[0435] In this application, the cavity 3n may be formed and defined by connecting the first conductive surface 2n and the second conductive surface using frame sealant 6n and frame sealant 7n.

[0436] According to the configuration of this application, in Figure 15, The first base material 1n and the second base material 5n are the first transparent conductive substrate and the second transparent conductive substrate, respectively. The first conductive surface 2n and the second conductive surface 4n are transparent conductive layers, each of which may include a base layer on the substrate material and a conductive layer on the base layer. The base layer is mainly made of an oxide such as aluminum oxide, titanium oxide, nickel oxide, or niobium oxide and has a thickness of 20 nm to 100 nm. The conductive layer may be at least one of tin oxide, zinc oxide, indium tin oxide, indium gallium zinc oxide composite, fluorine-doped tin oxide, aluminum-doped zinc oxide, and fluorine-doped zinc oxide and has a thickness of 150 nm to 250 nm and a sheet resistance of less than 25 Ω.

[0437] In the present application, the conductive layer is in contact with the cavity 3n. The cavity 3n is a cavity between two substrate materials and is filled with a discoloration solution prepared using an anode discoloration material, a cathode discoloration material, and a series of auxiliaries. The thickness of the cavity is, for example, in the range of 50 μm to 300 μm.

[0438] In the present application, the widths of the frame sealants 6n and 7n are, for example, in the range of 3 mm to 5 mm.

[0439] In the present application, there are no special requirements for the formulation of the discoloration medium, and all commonly used discoloration media can be used in the present application. In the present application, for example, the discoloration medium includes a cathode discoloration material, an anode discoloration material, a solvent, and an optional auxiliary.

[0440] In the present application, there are no special requirements for the type of the cathode discoloration material, and all commonly used cathode discoloration materials can be used in the present application. In the present application, for example, the cathode discoloration material has the formula b2:

Chemical formula

[0441] R 10 and R 11 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted heterocyclic aryl group, a substituted or unsubstituted arsyl group, a substituted or unsubstituted alkoxy group, an isocyanate group, or a carboxyl group.

[0442] R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、and R 19These are, independently, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a halogen, a cyano group, or a nitro group.

[0443] R 20 These are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted heterocyclic aryl groups, or substituted or unsubstituted arcyl groups.

[0444] X is at least one of halogens, borates, fluoroborates, tetraarylborates, hexafluorometalates, hexafluorosemimetalates, sulfates, sulfonates, sulfonamides, carboxylates, perchlorates, and tetrachloroferrates.

[0445] In some embodiments, R 10 and R 11 Each of these is independently an alkyl group, an alkenyl group, an alkynyl group, an alkenyl alkyl group, an alkynyl alkyl group, a monohydroxyalkyl group or polyhydroxyalkyl group, a monoamine alkyl group or polyamine alkyl group, a monosubstituted haloalkyl group or polysubstituted haloalkyl group, a monoalkyloxyalkyl group or polyalkyloxyalkyl group, a phosphonium alkyl group, a siloxyalkyl group, an alkyl carboxylate, an alkylphosphonate, an alkyl isocyanate, a carboxylate, a phosphonate group, an isocyanate, a pyridyl group, a pyrrolyl group, a furyl group, a pyranyl group, a thienyl group, a quinolinyl group, or an indoleyl group.

[0446] In this application, R 10 and R 11 They may be the same or different. In the configuration of this application, R 10 and R 11This group may independently be, but is not limited to, an alkyl group, an alkenyl group, an alkynyl group, an alkenyl alkyl group, an alkynyl alkyl group, a monohydroxyalkyl group or polyhydroxyalkyl group, a monoamine alkyl group or polyamine alkyl group, a monosubstituted haloalkyl group or polysubstituted haloalkyl group, a monoalkyloxyalkyl group or polyalkyloxyalkyl group, a phosphonium alkyl group, a siloxyalkyl group, an alkyl carboxylate, an alkyl phosphonate, an alkyl isocyanate, a carboxylate, a phosphonate group, an isocyanate, a pyridyl group, a pyrrolyl group, a furyl group, a pyranyl group, a thienyl group, a quinolinyl group, or an indoleyl group.

[0447] In another configuration of this application, R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 The number of carbon atoms is 18 or less. 20 The number of carbon atoms is 12 or less.

[0448] In yet another configuration of the present application, X may be F, Cl, Br, I, BF4, PF6, SbF6, AsF6, ClO4, SO3CF3, N(CF3SO2)2, C(CF3SO2)3, N(SO2C2F5)2, or BAr4, where Ar is an aryl group or a fluorinated aryl group. In a specific configuration, X may be -BAr4, where Ar is a pentafluorophenyl group. In yet another specific configuration of the present application, X may be a tetrafluoroborate. In yet another specific configuration of the present application, X may be a bis(trifluoromethylsulfonyl)imide anion. Specifically, the cathode color change material may include at least one of ethyl viologen ditetrafluoroborate and n-butyl viologen ditetrafluoroborate.

[0449] In the configuration of this application, the cathode discoloration material is formula b3 [ka] It is a compound represented by [this symbol].

[0450] In this application, the uniformity of the anode electrochromic material's color change is ensured by dissolving and dispersing the anode electrochromic material and cathode color change material using a solvent. The solvent may be any commercially available organic solvent that can dissolve or disperse each component in the color change medium and does not react with each component in the color change medium. In the configuration of this application, the solvent may include at least one of sulfones, amides, ethers, alcohols, nitriles, ketones, and esters. Specifically, the solvent may include, but is not limited to, at least one of 3-methylsulfolane, dimethyl sulfoxide, dimethylformamide, tetraethylene glycol dimethyl ether, ethoxyethanol, acetonitrile, glutaronitrile, 3-hydroxypropionitrile, 2-methylglutaronitrile, 2-acetylbutyrolactone, cyclopentanone, β-propiolactone, γ-butyrolactone, γ-valerolactone, polypropylene carbonate, ethylene carbonate, and propylene carbonate. In the specific configuration, the solvent may be propylene carbonate.

[0451] In the specific configuration of this application, the color-changing medium further includes an auxiliary agent. The addition of the auxiliary agent contributes to improving the performance of the color-changing medium. In the configuration of this application, the auxiliary agent includes at least one of a delamination inhibitor, a UV stabilizer, a thickener, and an electrolyte. In this way, stability and color-changing ability can be improved.

[0452] In the specific configuration of this application, the auxiliary agent includes a delamination inhibitor. Adding a delamination inhibitor helps to avoid delamination problems in the color-changing medium, ensures uniform dispersion of each component, facilitates the realization of a uniform color-changing effect, and contributes to extending the service life of the color-changing medium. In the specific configuration, the delamination inhibitor includes a polymer containing an ester group. Specifically, the polymer containing an ester group may include, but is not limited to, at least one of polyacrylate, polymethacrylate, and polyaromatic ester. In the specific configuration, the delamination inhibitor may be ethyl polyacrylate. In the specific configuration, the content of the delamination inhibitor in the color-changing medium is in the range of 1% to 6% by weight. The delamination inhibitor can improve the delamination resistance of the phenazine compound containing the crosslinking ring, and does not affect the color-changing ability of the phenazine compound containing the crosslinking ring or the color-changing ability of the cathode color-changing material. Specifically, the content of the delamination inhibitor in the color-changing medium may be 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, etc., but is not limited to these. In a specific configuration, the content of the delamination inhibitor in the color-changing medium may be in the range of 4% by weight to 6% by weight. In this way, stability and color-changing ability can be improved.

[0453] In another configuration, the auxiliary agent includes a UV stabilizer. By adding a UV stabilizer, the photostability of the color-changing medium can be improved and the service life of the color-changing medium can be extended. Specifically, the UV stabilizer may include, but is not limited to, at least one of 2-ethyl-2-cyano-3,3-diphenyl acrylate, (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 3-[3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionate amyl ester, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-ethyl-2'-ethoxypropionanilide. In a specific configuration, the UV stabilizer may be 2-(2'-hydroxy-4'-methylphenyl)benzotriazole. In the configuration, the UV stabilizer content in the color-changing medium is in the range of 1% to 4% by weight. The UV stabilizer can improve the stability and service life of the phenazine compound containing the crosslinking ring, without affecting the color-changing ability of the phenazine compound containing the crosslinking ring or the color-changing ability of the cathode color-changing material. Specifically, the UV stabilizer content in the color-changing medium may be, but is not limited to, 1% by weight, 1.5% by weight, 2% by weight, 3% by weight, 3.5% by weight, 4% by weight, etc. In a specific configuration, the UV stabilizer content in the color-changing medium may be in the range of 3% to 4% by weight. In this way, stability and color-changing ability can be improved.

[0454] In yet another configuration, the additive includes a thickening agent. By adding a thickening agent, the viscosity of the color-changing medium can be adjusted, which is beneficial for the use of the color-changing medium in electrochromic devices. Specifically, the thickening agent may be a polymer, which may include, but is not limited to, at least one of the following: polyamide, polyimide, polycarbonate, polymethacrylate, polyacrylate, polysilane, polysiloxane, polyvinyl acetate, polymethacrylonitrile, polyacrylonitrile, polyvinylphenol, polyvinyl alcohol, and polyvinylidene dihalides. In a specific configuration, the thickening agent may be polyvinylidene fluoride. In the configuration, the content of the thickening agent in the color-changing medium is in the range of 0.05% to 3% by weight. In this way, the viscosity of the color-changing medium does not increase excessively, and the usability of the color-changing medium is guaranteed. Specifically, the content of the thickener in the color-changing medium may be, but is not limited to, 0.05% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, etc. In a specific configuration, the content of the thickener in the color-changing medium may be in the range of 0.05% by weight to 1.5% by weight. In this way, stability and color-changing ability can be improved.

[0455] In yet another configuration, the additive includes an electrolyte. By adding an electrolyte, the ionic conductivity of the color-changing medium can be improved, and the color-changing response rate can be increased. Specifically, the electrolyte may include, but is not limited to, at least one of lithium trifluoromethanesulfonate, lithium perchlorate, lithium tetrafluoroborate, and lithium hexafluorophosphate. In a specific configuration, the electrolyte may be lithium perchlorate. In the configuration, the concentration of the electrolyte in the color-changing medium is in the range of 0.05 mol / L to 0.5 mol / L, which helps to significantly improve the ionic conductivity of the color-changing medium. Specifically, the concentration of the electrolyte in the color-changing medium may be, but is not limited to, 0.05 mol / L, 0.1 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, etc. In this way, stability and color-changing ability can be improved.

[0456] In a specific configuration, the electrolyte content in the color-changing medium may be in the range of 0.05 mol / L to 0.1 mol / L. In the configuration of this application, the color-changing medium comprises a phenazine compound containing a crosslinking ring in a concentration of 30 mmol / L to 120 mmol / L, a cathode color-changing material in a concentration of 30 mmol / L to 120 mmol / L, and a solvent.

[0457] In another configuration of the present application, the color-changing medium comprises a phenazine compound containing a crosslinking ring in a concentration of 65 mmol / L to 85 mmol / L, a cathode color-changing material in a concentration of 80 mmol / L to 120 mmol / L, and a solvent. In yet another configuration of the present application, the color-changing medium comprises a phenazine compound containing a crosslinking ring in a concentration of 30 mmol / L to 120 mmol / L, a cathode color-changing material in a concentration of 30 mmol / L to 120 mmol / L, a delamination inhibitor in a concentration of 1% to 6% by weight, and a solvent.

[0458] In yet another configuration of the present invention, the color-changing medium comprises a phenazine compound containing a crosslinking ring in a concentration of 30 mmol / L to 120 mmol / L, a cathode color-changing material in a concentration of 30 mmol / L to 120 mmol / L, a UV stabilizer in a concentration of 1% to 4% by weight, and a solvent. In this way, stability and color-changing ability can be improved.

[0459] In yet another configuration of the present application, the color-changing medium comprises a phenazine compound containing a crosslinking ring in a concentration of 30 mmol / L to 120 mmol / L, a cathode color-changing material in a concentration of 30 mmol / L to 120 mmol / L, a thickener in a concentration of 0.05 wt% to 3 wt%, and a solvent. In yet another configuration of the present application, the color-changing medium comprises a phenazine compound containing a crosslinking ring in a concentration of 30 mmol / L to 120 mmol / L, a cathode color-changing material in a concentration of 30 mmol / L to 120 mmol / L, an electrolyte in a concentration of 0.05 mol / L to 0.5 mol / L, and a solvent. In this way, stability and color-changing ability can be improved.

[0460] In yet another configuration of the present application, the color change medium comprises a phenazine compound containing a crosslinking ring in a concentration of 30 mmol / L to 120 mmol / L, a cathode color change material in a concentration of 30 mmol / L to 120 mmol / L, a delamination inhibitor in a concentration of 1% to 6% by weight, a UV stabilizer in a concentration of 1% to 4% by weight, a thickener in a concentration of 0.05% to 3% by weight, an electrolyte in a concentration of 0.05 mol / L to 0.5 mol / L, and a solvent.

[0461] In yet another configuration of the present application, the color-changing medium comprises 30 mmol / L to 120 mmol / L of anode color-changing material, 30 mmol / L to 120 mmol / L of cathode color-changing material, 1% to 6% by weight of an interlayer delamination inhibitor, 1% to 4% by weight of a UV stabilizer, 0.05% to 3% by weight of a thickener, 0.05 mol / L to 0.5 mol / L of an electrolyte, and a solvent. In this way, stability and color-changing ability can be improved.

[0462] In yet another configuration of the present application, the color-changing medium comprises a phenazine compound containing a crosslinking ring in a concentration of 60 mmol / L to 85 mmol / L, a cathode color-changing material in a concentration of 80 mmol / L to 120 mmol / L, a delamination inhibitor in a concentration of 4% to 6% by weight, a UV stabilizer in a concentration of 3% to 4% by weight, a thickener in a concentration of 0.05% to 1.5% by weight, an electrolyte in a concentration of 0.05 mol / L to 0.1 mol / L, and a solvent. In this way, stability and color-changing ability can be improved.

[0463] In this application, there are no special requirements for the method of preparing the color-changing medium, and it may be carried out according to the prior art, for example, by adding a phenazine compound containing a crosslinking ring and a cathode color-changing material to a solvent, adding an optional auxiliary agent and mixing them uniformly to obtain a color-changing medium. In this way, stability and color-changing ability can be improved.

[0464] In the configuration of this invention, the method for preparing the color-changing medium includes adding a phenazine compound containing a crosslinking ring, a cathode color-changing material, and an auxiliary agent to a solvent and mixing them uniformly to obtain the color-changing medium.

[0465] In this application, there are no special requirements for the method of synthesizing the compounds. According to the configuration of this application, the method of synthesizing the compounds is as follows: Dissolve reactant 1 (phenazine compound) in toluene while stirring in a three-necked flask, and slowly add a toluene solution of NaH; after the addition is complete, allow the reaction to proceed at room temperature for 2 to 10 hours; slowly add a toluene solution of reactant 2 (substituted alkane, the substituent is selected according to the target product, e.g., 1,2-dibromoethane) dropwise; raise the temperature to 60°C to 90°C; heat under reflux for 12 to 96 hours; separate and purify the reactants by silica gel column chromatography to obtain the compounds of this application, e.g., compounds represented by structural formulas b4 to b11. The specific reaction formula is shown in formula Ib. Each group in reactant 1 is represented by formula b1: [ka] It is selected according to the structure of the compound to be obtained, as represented by [the specified method].

[0466] The present application will be described in detail below using specific embodiments as examples.

[0467] Preparation Example 1: Synthesis of Compound b5 While stirring in a three-necked flask, 20.8 g of 5,10-dihydrophenazine was dissolved in 400 g of toluene, and a toluene solution of NaH (6 g of NaH dissolved in 100 g of toluene) was slowly added. After the addition was complete, the reaction was carried out at room temperature for 2 hours. A toluene solution of 1,2-dibromoethane (17 g of 1,2-dibromoethane dissolved in 30 g of toluene) was slowly added dropwise. The temperature was raised to 70°C. Heating under reflux condensation was carried out for 12 hours. The reaction products were separated and purified by silica gel column chromatography to obtain an anoelectrochromic material represented by structural formula V.

[0468] Preparation Example 2: Synthesis of Compound b6 While stirring in a three-necked flask, 21.0 g of 5,10-dihydro-2,8-dimethylphenazine was dissolved in 400 g of toluene, and a toluene solution of NaH (6 g of NaH dissolved in 100 g of toluene) was slowly added. After the addition was complete, the reaction was carried out at room temperature for 2 hours. A toluene solution of 1,2-dibromoethane (17 g of 1,2-dibromoethane dissolved in 30 g of toluene) was slowly added dropwise. The temperature was raised to 70°C. Heating under reflux condensation was carried out for 12 hours. The reaction products were separated and purified by silica gel column chromatography to obtain an anoelectrochromic material represented by structural formula VI.

[0469] Preparation Example 3: Synthesis of Compound b7 While stirring in a three-necked flask, 46.4 g of 5,10-dihydro-2,8-di-n-decylphenazine was dissolved in 400 g of toluene, and a toluene solution of NaH (6 g of NaH dissolved in 100 g of toluene) was slowly added. After the addition was complete, the reaction was carried out at room temperature for 2 hours. A toluene solution of 1,2-dibromoethane (17 g of 1,2-dibromoethane dissolved in 30 g of toluene) was slowly added dropwise. The temperature was raised to 70°C. Heating under reflux was carried out for 12 hours. The reaction products were separated and purified by silica gel column chromatography to obtain an anoelectrochromic material represented by structural formula VII.

[0470] Preparation Example 4: Synthesis of Compound b8 While stirring in a three-necked flask, 24.2 g of 5,10-dihydro-2,8-dimethoxyphenazine was dissolved in 400 g of toluene, and a toluene solution of NaH (6 g of NaH dissolved in 100 g of toluene) was slowly added. After the addition was complete, the reaction was carried out at room temperature for 2 hours. A toluene solution of 1,2-dibromoethane (17 g of 1,2-dibromoethane dissolved in 30 g of toluene) was slowly added dropwise. The temperature was raised to 70°C. Heating under reflux was carried out for 12 hours. The reaction products were separated and purified by silica gel column chromatography to obtain an anode electrochromic material represented by structural formula VIII.

[0471] Preparation Example 5: Synthesis of Compound b9 While stirring in a three-necked flask, 20.8 g of 5,10-dihydro-2,8-dinitrophenazine was dissolved in 400 g of toluene, and a toluene solution of NaH (6 g of NaH dissolved in 100 g of toluene) was slowly added. After the addition was complete, the reaction was carried out at room temperature for 2 hours. A toluene solution of 1,2-dibromoethane (17 g of 1,2-dibromoethane dissolved in 30 g of toluene) was slowly added dropwise. The temperature was raised to 90°C. The mixture was heated under reflux for 20 hours. The reaction products were separated and purified by silica gel column chromatography to obtain an anoelectrochromic material represented by structural formula IX.

[0472] Preparation Example 6: Synthesis of Compound b10 While stirring in a three-necked flask, 20.8 g of 5,10-dihydro-2,8-dicyanophenazine was dissolved in 400 g of toluene, and a toluene solution of NaH (6 g of NaH dissolved in 100 g of toluene) was slowly added. After the addition was complete, the reaction was carried out at room temperature for 2 hours. A toluene solution of 1,2-dibromoethane (17 g of 1,2-dibromoethane dissolved in 30 g of toluene) was slowly added dropwise. The temperature was raised to 90°C. The mixture was heated under reflux for 20 hours. The reaction products were separated and purified by silica gel column chromatography to obtain an anoelectrochromic material represented by structural formula X.

[0473] Preparation Example 7: Synthesis of Compound b11 In a three-necked flask, 20.8 g of 5,10-dihydro-2,8-diphenylphenazine was dissolved in 400 g of toluene while stirring, and a toluene solution of NaH (6 g of NaH dissolved in 100 g of toluene) was slowly added. After the addition was complete, the reaction was carried out at room temperature for 2 hours. A toluene solution of 1,2-dibromoethane (17 g of 1,2-dibromoethane dissolved in 30 g of toluene) was slowly added dropwise. The temperature was raised to 70°C. Heating under reflux condensation was carried out for 12 hours. The reaction products were separated and purified by silica gel column chromatography to obtain an anoelectrochromic material represented by structural formula XI.

[0474] In the following embodiments and comparative examples, the average molecular weight of ethyl polyacrylate was 25w, and the average molecular weight of polyvinylidene fluoride (PVDF) was 25w.

[0475] Comparative Example 5: Preparation of a color-changing medium for compound b4 A color-changing composition is provided, comprising 30 mmol / L of a phenazine compound represented by formula IV, 30 mmol / L of a cathode color-changing material represented by formula III, 0.1 mol / L of lithium perchlorate, 4 wt% of ethyl polyacrylate, 3 wt% of 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% of polyvinylidene fluoride (PVDF), and the remainder being propylene carbonate.

[0476] Example 21: Preparation of a color-changing medium for compound b5 A color-changing composition is provided, comprising a phenazine compound containing a crosslinking ring represented by formula V at a concentration of 30 mmol / L, a cathode color-changing material represented by formula III at a concentration of 30 mmol / L, 0.1 mol / L lithium perchlorate, 4 wt% ethyl polyacrylate, 3 wt% 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% polyvinylidene fluoride (PVDF), and the remainder being propylene carbonate.

[0477] Example 22: Preparation of a color-changing medium for compound b6 A color-changing composition is provided, comprising a phenazine compound containing a crosslinking ring represented by formula VI at a concentration of 30 mmol / L, a cathode color-changing material represented by formula III at a concentration of 30 mmol / L, lithium perchlorate at a concentration of 0.1 mol / L, ethyl polyacrylate at a concentration of 4 wt%, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole at a concentration of 3 wt%, polyvinylidene fluoride (PVDF) at a concentration of 1 wt%, and the remainder being propylene carbonate.

[0478] Example 23: Preparation of a color change medium for compound b7 A color-changing composition is provided, comprising a phenazine compound containing a crosslinking ring represented by formula VII at a concentration of 30 mmol / L, a cathode color-changing material represented by formula III at a concentration of 30 mmol / L, lithium perchlorate at a concentration of 0.1 mol / L, ethyl polyacrylate at a concentration of 4 wt%, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole at a concentration of 3 wt%, polyvinylidene fluoride (PVDF) at a concentration of 1 wt%, and the remainder being propylene carbonate.

[0479] Example 24: Preparation of a color-changing medium for compound b8 A color-changing composition is provided, comprising a phenazine compound containing a crosslinking ring represented by formula VIII at a concentration of 30 mmol / L, a cathode color-changing material represented by formula III at a concentration of 30 mmol / L, 0.1 mol / L lithium perchlorate, 4 wt% ethyl polyacrylate, 3 wt% 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% polyvinylidene fluoride (PVDF), and the remainder being propylene carbonate.

[0480] Example 25: Preparation of a color change medium for compound b9 A color-changing composition is provided, comprising a phenazine compound containing a crosslinking ring represented by formula IX at a concentration of 30 mmol / L, a cathode color-changing material represented by formula III at a concentration of 30 mmol / L, 0.1 mol / L lithium perchlorate, 4 wt% ethyl polyacrylate, 3 wt% 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% polyvinylidene fluoride (PVDF), and the remainder being propylene carbonate.

[0481] Example 26: Preparation of a color-changing medium for compound b10 A color-changing composition is provided, comprising a phenazine compound containing a crosslinking ring represented by formula X at a concentration of 30 mmol / L, a cathode color-changing material represented by formula III at a concentration of 30 mmol / L, 0.1 mol / L lithium perchlorate, 4 wt% ethyl polyacrylate, 3 wt% 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 1 wt% polyvinylidene fluoride (PVDF), and the remainder being propylene carbonate.

[0482] Example 27: Preparation of a color-changing medium for compound b11 A color-changing composition is provided, comprising a phenazine compound containing a crosslinking ring represented by formula XI at a concentration of 30 mmol / L, a cathode color-changing material represented by formula III at a concentration of 30 mmol / L, lithium perchlorate at a concentration of 0.1 mol / L, ethyl polyacrylate at a concentration of 4 wt%, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole at a concentration of 3 wt%, polyvinylidene fluoride (PVDF) at a concentration of 1 wt%, and the remainder being propylene carbonate.

[0483] Cycle life test Electrochromic devices were fabricated using the color-changing compositions provided in Examples 21 to 27 and Comparative Example 5 (as shown in Figure 15, the first transparent conductive substrate, i.e., the first substrate material 1n, and the second transparent conductive substrate, i.e., the second substrate material 5n, were glass plates plated with an ITO layer (transmittance 89%), the connecting layers were frame sealant 6n (thickness 180 μm and width 2.5 mm) and frame sealant 7n (thickness 180 μm and width 2.5 mm), the thickness of the housing space was 62 μm, and the length and width of the electrochromic device were both 40 mm). The cycle life of each electrochromic device was tested with a test voltage of 1.2 V. The test results are shown in Table 8. One cycle was defined as applying a voltage of 1.2 V for 5 seconds to power on and then turning off the power for 10 seconds. The transmittance of the device was tested before and after the cycle.

[0484] [Table 9]

[0485] The experimental results show that, compared to compound b4 (5,10-dihydrophenazine), all structurally modified compounds exhibit an increase in contrast ΔT before and after electrolysis, indirectly demonstrating that the modified compounds have higher stability. Compounds b8 and b11 exhibit particularly excellent stability and still maintain a good light intensity regulating effect even after 50,000 electrolysis cycles. The alkoxy and phenyl groups in the phenazine compounds containing the crosslinked ring represented by compounds b8 and b11 increase the conjugation range and the electron density of the large conjugation of phenothiazine, thereby significantly improving the stability and color-changing ability of the phenazine compounds containing the crosslinked ring. Therefore, using the phenazine compounds containing the crosslinked ring of this application as color-changing materials for electrochromic devices has great application value, commercial prospects, and good industrialization prospects compared to using existing materials in the device.

[0486] This application further provides carbazole compounds and compositions, methods and uses for preparing them, and electrochromic apparatus.

[0487] A carbazole compound, wherein the carbazole compound is of formula (1) or formula (2): [ka] A carbazole compound represented by is provided.

[0488] R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 These are H and OR, respectively, independently. 29 F, Cl, Br, I, CN, NO2, aryl groups, substituted or unsubstituted C1-C18 Alkyl groups, substituted or unsubstituted amino groups, or substituted or unsubstituted C2-C2 groups. 18 It is a non-aromatic heterocyclic group.

[0489] R 19 This includes H, an aryl group, a substituted or unsubstituted C1-C9 alkyl group, or a substituted or unsubstituted C2-C 18 It is a non-aromatic heterocyclic group.

[0490] R 29 H, substituted or unsubstituted C1-C 18 Alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted amino groups, substituted or unsubstituted C2-C2 groups 18 It is a non-aromatic heterocyclic group.

[0491] A1 and A2 are independently N and NR, respectively. 26 It is either O or S.

[0492] R 26 This is H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbocyclic group, or a heterocyclic group.

[0493] In some embodiments, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 Each of these is independently H, an aryl group, or a substituted or unsubstituted C1-C1. 18 It is an alkyl group.

[0494] R 19 is H, an aryl group, or a substituted or unsubstituted C1-C9 alkyl group.

[0495] R29 This is H, a substituted or unsubstituted C1-C9 alkyl group, or a substituted or unsubstituted aryl group.

[0496] R 26 This group consists of H, a substituted or unsubstituted alkyl group, a five-membered heterocyclic group, or a six-membered heterocyclic group, where the five-membered or six-membered heterocyclic group is a tetrahydropyran ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a tetrahydropyridine ring, a hexahydropyrrole ring, or a tetrahydrothion ring.

[0497] In some embodiments, R 19 This is H or a substituted or unsubstituted C1-C9 alkyl group, and the alkyl group contains four or fewer consecutive methylene groups.

[0498] R 29 is H or a substituted or unsubstituted C1-C9 alkyl group.

[0499] R 26 This is H, a substituted or unsubstituted alkyl group, a tetrahydropyran ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, or a tetrahydropyridine ring.

[0500] In some embodiments, R 11 ~R 19 and R 22 ~R 26 Both are hydrogen.

[0501] In some embodiments, the carbazole compound is represented by formulas (3) to (8): [ka] It is one of them.

[0502] In some embodiments, methods for preparing carbazole compounds are further provided, and these methods include (1) A step of uniformly mixing sodium hydride, carbazole, and a carbonyl compound at a first temperature in the presence of a solvent to obtain a mixed solution, (2) The mixed solution is heated to a second temperature to carry out the reaction and then purified to obtain a carbazole compound. Includes.

[0503] In some embodiments, during step (1), the carbonyl compound is of formula (9) or formula (10): [ka] It is a structure represented by [this].

[0504] R 28 is H, an aryl group, or a substituted or unsubstituted C1-C9 alkyl group.

[0505] R 20 , R 21 , R 22 , R 23 , R 24 , R 25 The definitions of A1 and A2 are, correspondingly, the same as those according to any one of the embodiments described above.

[0506] In some embodiments, the solvent in step (1) is N,N-dimethylformamide, dimethyl sulfoxide, chloroform, or acetonitrile.

[0507] In some embodiments, during step (1), the molar ratio of carbazole to sodium hydride is 1:(1 to 1.5), and / or the molar ratio of carbazole to carbonyl compound is 1:(1 to 2), and / or the first temperature is in the range of -5°C to 0°C.

[0508] In some embodiments, during step (2), the second temperature is in the range of 60°C to 90°C and / or The reaction time is in the range of 8 to 12 hours.

[0509] In some embodiments, the present application further provides carbazole compounds prepared according to the methods described above.

[0510] In some embodiments, the present application further provides the application of carbazole compounds in electrochromic media.

[0511] In some embodiments, the present application further provides a composition comprising a cathode color change material, an anode color change material, a solvent, a delamination inhibitor, an antioxidant, a UV stabilizer, a thickener, and an ionic conductivity enhancer, wherein the anode color change material comprises a carbazole compound, and the carbazole compound is a carbazole compound according to any one of the embodiments described above.

[0512] In some embodiments, the cathode color change material is given by formula (11): [ka] It is a structure represented by [this].

[0513] R 1 and R 2 These are, independently, substituted or non-substituted C1-C 18 These include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, monoamine alkyl groups or polyamine alkyl groups, monosubstituted haloalkyl groups or polysubstituted haloalkyl groups, monoalkyloxyalkyl groups or polyalkyloxyalkyl groups, phosphonium alkyl groups, siloxyalkyl groups, pyridyl groups, pyrrolyl groups, furyl groups, pyranyl groups, thienyl groups, quinolinyl groups, or indoleyl groups.

[0514] R 3 ~R 10 These are H and OR, respectively, independently. 29 F, Cl, Br, I, CN, NO2, substituted or unsubstituted C1-C 18 It is an alkyl group or an aryl group.

[0515] R29 The definition is the same as that given in any one of the embodiments described above.

[0516] X - F is independent of - Cl - , Br - , I - BF4 - PF6 - SbF6 - AsF6 - ClO4 - carboxylate, ClO4 - , SO3CF3 - , N(CN)2 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - Al(OC(CF3)3)4 - , or BAr4 - This may be the case, and Ar is an aryl group.

[0517] In some embodiments, the solvent is at least one of sulfone solvents, amide solvents, ether solvents, alcohol solvents, nitrile solvents, ketone solvents, and ester solvents.

[0518] In some embodiments, the sulfone solvent is at least one of 3-methylsulfolane and dimethyl sulfoxide.

[0519] In some embodiments, the amide solvent is N,N-dimethylformamide.

[0520] In some embodiments, the ether solvent is tetraethylene glycol dimethyl ether.

[0521] In some embodiments, the alcohol solvent is ethoxyethanol.

[0522] In some embodiments, the nitrile solvent is at least one of acetonitrile, glutalonitrile, 3-hydroxypropionitrile, and 2-methylglutalonitrile.

[0523] In some embodiments, the ketone solvent is at least one of 2-acetylbutyrolactone and cyclopentanone.

[0524] In some embodiments, the ester solvent is at least one of β-propiolactone, γ-butyrolactone, γ-valerolactone, polypropylene carbonate, ethylene carbonate, and propylene carbonate.

[0525] In some embodiments, the delamination inhibitor is a polymer containing an ester group. For example, the delamination inhibitor is at least one of polyacrylates, polymethacrylates, and polyaromatic esters. Another example is ethyl polyacrylate as the delamination inhibitor.

[0526] In some embodiments, the antioxidant is one of a phenol compound, a sterically hindered amine compound, and an ester compound containing a double bond. For example, antioxidants include 1,3,5-tri-tert-butylphenol, 1,5-tert-butyl-3-methylphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5' The antioxidant is at least one of the following: (-dipentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethylpiperidine, di-tert-butylamine, methyl methacrylate, and ethyl methacrylate. As another example, the antioxidant is at least one of the following: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 1,5-tert-butyl-3-methylphenol, and methyl methacrylate.

[0527] In some embodiments, the UV stabilizer is at least one of 2-ethyl-2-cyano-3,3-diphenyl acrylate, (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionate amyl ester, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-ethyl-2'-ethoxypropionanilide, for example, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole.

[0528] In some embodiments, the thickener is a polymer. For example, the thickener is at least one of polyamide, polyimide, polycarbonate, polyester, polyether, polymethacrylate, polyacrylate, polysilane, polysiloxane, polyvinyl acetate, polymethacrylonitrile, polyacrylonitrile, polyvinylphenol, polyvinyl alcohol, and polyvinylidene dihalides.

[0529] In some embodiments, the weight-average molecular weight of the polymer is in the range of 200,000 g / mol to 400,000 g / mol.

[0530] In some embodiments, the ion conductivity enhancer is at least one of lithium trifluoromethanesulfonate, lithium perchlorate, lithium tetrafluoroborate, and lithium hexafluorophosphate, for example, lithium perchlorate.

[0531] In some embodiments, the concentration of the anode-changing material in the composition is in the range of 30 mM to 120 mM, and the concentration of the cathode-changing material is in the range of 30 mM to 120 mM.

[0532] In some embodiments, the antioxidant content is in the range of 20 mM to 500 mM, for example, in the range of 50 mM to 100 mM.

[0533] In some embodiments, the concentration of the ion conductivity enhancer is in the range of 0.05 M to 0.5 M.

[0534] In some embodiments, the content of the delamination inhibitor is in the range of 1% to 6% by weight, the content of the UV stabilizer is in the range of 1% to 4% by weight, and the content of the thickener is in the range of 0.05% to 3% by weight, based on the total mass of the composition.

[0535] In some embodiments, an electrochromic apparatus is further provided, comprising a first conductive surface of a first substrate material, a second conductive surface of a second substrate material, and a cavity defined by a sealing member connecting the first and second conductive surfaces. The electrochromic medium is disposed within the cavity.

[0536] In some embodiments, the electrochromic medium is the aforementioned composition.

[0537] The carbazole compounds and compositions, methods for preparing them and their uses, and the specific configuration of the electrochromic apparatus are as follows.

[0538] The endpoints of the ranges and any numerical values ​​disclosed herein are not limited to exact ranges or values. These ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, one or more new numerical ranges can be obtained by combining the endpoints of each range, the endpoints of each range with individual points, and individual points with each other, and these numerical ranges are deemed to be specifically disclosed herein.

[0539] The terms used in this application are explained below.

[0540] "Halo" refers to halogens, which are fluorine, chlorine, bromine, or iodine.

[0541] Alkyl groups refer to linear or branched alkyl groups, excluding cycloalkyl groups. C1-C 18 An alkyl group refers to an alkyl group having 1 to 18 carbon atoms, and includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl, and n-hexyl groups.

[0542] A carbocyclic group refers to a group containing a cyclic chain, and includes, but is not limited to, aromatic groups such as cyclopropyl, cyclobutyl, cyclopentyl, phenyl, and naphthyl groups.

[0543] A heterocyclic group refers to a group that has a heteroatom in a cyclic chain, and this includes, but is not limited to, a pyridyl group, a furyl group, or a thienyl group. For example, the heteroatom may include, but is not limited to, atoms such as oxygen, sulfur, or nitrogen.

[0544] An alkenyl group refers to a linear or branched alkenyl group. C2-C8 alkenyl groups refer to alkenyl groups having 2 to 8 carbon atoms, and include, but are not limited to, 1-propenyl, 2-propenyl, and different isomers of butenyl, pentenyl, and hexenyl. Alkenyl groups also include polyenes such as 1,2-propadienyl and 2,4-hexadienyl.

[0545] An alkynyl group refers to a linear or branched alkynyl group. C2-C8 alkynyl groups refer to alkynyl groups having 2 to 8 carbon atoms, and include, but are not limited to, 1-propynyl, 2-propynyl, and different isomers of butynyl, pentynyl, and hexynyl. Alkynyl groups also include groups containing multiple triple bonds, such as 2,5-hexadynyl.

[0546] An alkoxy group refers to a group in which an oxygen atom is attached to the end of a linear or branched alkyl group. C1-C8 alkoxy groups refer to alkoxy groups having 1 to 8 carbon atoms, and include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy groups.

[0547] A phosphonium alkyl group is a group represented by the general formula (R27)4P-, where R27 includes an aryl group or a substituted or unsubstituted C1-C9 alkyl group.

[0548] The term "carboxylate" refers to a carboxylate anion, which includes, but is not limited to, formate, acetate, propionate, and butyrate.

[0549] Monoamine alkyl groups or polyamine alkyl groups, monosubstituted haloalkyl groups or polysubstituted haloalkyl groups, monoalkyloxyalkyl groups or polyalkyloxyalkyl groups, and siloxyalkyl groups refer to groups formed by substituting at least one hydrogen atom in an alkyl or alkoxy group with one or more amine groups, halogen atoms, alkoxy groups, and siloxy groups. If there are two or more amine groups, halogen atoms, alkoxy groups, and siloxy groups, these amine groups, halogen atoms, alkoxy groups, and siloxy groups may be the same or different.

[0550] As described above, the first aspect of the present application provides a carbazole compound, the carbazole compound being of formula (1) or formula (2): [ka] It is a structure represented by [this].

[0551] R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 These are H and OR, respectively, independently. 29 F, Cl, Br, I, CN, NO2, aryl groups, substituted or unsubstituted C1-C 18 Alkyl groups, substituted or unsubstituted amino groups, or substituted or unsubstituted C2-C2 groups. 18 It is a non-aromatic heterocyclic group.

[0552] R 19 This includes H, an aryl group, a substituted or unsubstituted C1-C9 alkyl group, or a substituted or unsubstituted C2-C 18 It is a non-aromatic heterocyclic group.

[0553] R 29 H, substituted or unsubstituted C1-C 18 Alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted amino groups, or substituted or unsubstituted C2-C2 groups. 18 It is a non-aromatic heterocyclic group.

[0554] A1 and A2 are independently N and NR, respectively. 26 It is either O or S.

[0555] R 26 This is H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbocyclic group, or a heterocyclic group.

[0556] In some configurations of this application, in some embodiments, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 Each of these is independently H, an aryl group, or a substituted or unsubstituted C1-C1. 18 It is an alkyl group.

[0557] R 19 is H, an aryl group, or a substituted or unsubstituted C1-C9 alkyl group.

[0558] R 29 This is H, a substituted or unsubstituted C1-C9 alkyl group, or a substituted or unsubstituted aryl group.

[0559] R 26 This group consists of H, a substituted or unsubstituted alkyl group, a five-membered heterocyclic group, or a six-membered heterocyclic group, where the five-membered or six-membered heterocyclic group is a tetrahydropyran ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a tetrahydropyridine ring, a hexahydropyrrole ring, or a tetrahydrothion ring.

[0560] In some embodiments, R 19 This is H or a substituted or unsubstituted C1-C9 alkyl group, and the alkyl group contains four or fewer consecutive methylene groups.

[0561] R 29 is H or a substituted or unsubstituted C1-C9 alkyl group.

[0562] R 26 This is H, a substituted or unsubstituted alkyl group, a tetrahydropyran ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, or a tetrahydropyridine ring.

[0563] In some embodiments, R 11 ~R 19 and R 22 ~R 26 Both are hydrogen.

[0564] In some embodiments, the carbazole compound is represented by formulas (3) to (8): [ka] It is one of them.

[0565] A second aspect of the present application provides a method for preparing a carbazole compound, the method being: (1) A step of uniformly mixing sodium hydride, carbazole, and a carbonyl compound at a first temperature in the presence of a solvent to obtain a mixed solution, (2) The mixed solution is heated to a second temperature to carry out the reaction and then purified to obtain a carbazole compound. Includes.

[0566] In some embodiments, during step (1), the carbonyl compound is of formula (9) or formula (10): [ka] It is a structure represented by [this].

[0567] R 28 is H, an aryl group, or a substituted or unsubstituted C1-C9 alkyl group.

[0568] R 20 , R 21 , R 22 , R 23 , R 24 , R 25 The definitions of A1 and A2 are, correspondingly, the same as those in the first aspect of this application.

[0569] In some embodiments, the solvent in step (1) is N,N-dimethylformamide, dimethyl sulfoxide (DMSO), chloroform, or acetonitrile.

[0570] In some embodiments, the molar ratio of carbazole to sodium hydride in step (1) is 1:(1 to 1.5). This range of molar ratio makes it possible to achieve the technical effect of sufficient reaction of carbazole and sufficient generation of reaction intermediates in step (1).

[0571] In some embodiments, the molar ratio of carbazole to carbonyl compound is 1:(1-2). This range of molar ratios allows for the achievement of technical effects such as sufficient reaction of the reaction intermediate and maximization of the yield of the carbazole compound during step (2).

[0572] In some embodiments, the first temperature is in the range of -5°C to 0°C. This temperature range makes it possible to achieve the technical effect in step (1) of lowering the temperature of the mixed solution, preventing substances in it from being released to the outside, and reducing the loss of reactants and products.

[0573] In some embodiments, step (2) includes the steps of slowly adding a 1 mol / L hydrochloric acid solution dropwise to the mixture obtained by the reaction to adjust the pH of the mixture to 1, and after a complete reaction for 1 hour, extracting the solution with ethyl acetate, concentrating the solution, and separating and purifying the solution by silica gel column chromatography to obtain the product, an anode electrochromic material.

[0574] In some embodiments, the second temperature in step (2) is in the range of 60°C to 90°C. This temperature range makes it possible to achieve sufficient reaction and maximize the yield of the carbazole compound during step (2).

[0575] In some embodiments, the reaction time is in the range of 8 to 12 hours. This range of reaction time makes it possible to achieve the technical effect of sufficient reaction and maximization of the yield of the carbazole compound during step (2).

[0576] A third aspect of the present application provides a carbazole compound prepared according to the method of the second aspect of the present application.

[0577] A fourth aspect of the present application provides the application of the carbazole compound according to the first aspect of the present application and / or the carbazole compound according to the third aspect of the present application in an electrochromic medium.

[0578] A fifth aspect of the present application provides a composition comprising a cathode color change material, an anode color change material, a solvent, a delamination inhibitor, an antioxidant, a UV stabilizer, a thickener, and an ion conductivity enhancer, wherein the anode color change material comprises a carbazole compound, and the carbazole compound is a carbazole compound according to the first aspect of the present application.

[0579] In some embodiments, the cathode color change material is given by formula (11): [ka] It is a structure represented by [this].

[0580] R 1 and R 2 These are, independently, substituted or non-substituted C1-C 18 These include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, monoamine alkyl groups or polyamine alkyl groups, monosubstituted haloalkyl groups or polysubstituted haloalkyl groups, monoalkyloxyalkyl groups or polyalkyloxyalkyl groups, phosphonium alkyl groups, siloxyalkyl groups, pyridyl groups, pyrrolyl groups, furyl groups, pyranyl groups, thienyl groups, quinolinyl groups, or indoleyl groups.

[0581] R 3 ~R 10 These are H and OR, respectively, independently. 29 F, Cl, Br, I, CN, NO2, substituted or unsubstituted C1-C 18 It is an alkyl group or an aryl group.

[0582] R 29 The definition is the same as that according to the first aspect of this application.

[0583] X - F is independent of - Cl - , Br - , I - BF4 - PF6 - SbF6 - AsF6- ClO4 - carboxylate, ClO4 - , SO3CF3 - , N(CN)2 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - Al(OC(CF3)3)4 - , or BAr4 - This may be the case, and Ar is an aryl group.

[0584] In some embodiments, the solvent is at least one of sulfone solvents, amide solvents, ether solvents, alcohol solvents, nitrile solvents, ketone solvents, and ester solvents.

[0585] In some embodiments, the sulfone solvent is at least one of 3-methylsulfolane and dimethyl sulfoxide.

[0586] In some embodiments, the amide solvent is N,N-dimethylformamide.

[0587] In some embodiments, the ether solvent is tetraethylene glycol dimethyl ether.

[0588] In some embodiments, the alcohol solvent is ethoxyethanol.

[0589] In some embodiments, the nitrile solvent is at least one of acetonitrile, glutalonitrile, 3-hydroxypropionitrile, and 2-methylglutalonitrile. In some embodiments, the ketone solvent is at least one of 2-acetylbutyrolactone and cyclopentanone.

[0590] In some embodiments, the ester solvent is at least one of β-propiolactone, γ-butyrolactone, γ-valerolactone, polypropylene carbonate, ethylene carbonate, and propylene carbonate.

[0591] In some embodiments, the delamination inhibitor is a polymer containing an ester group. For example, the delamination inhibitor is at least one of polyacrylate, polymethacrylate, and polyaromatic ester. For example, the delamination inhibitor is ethyl polyacrylate.

[0592] In some embodiments, the antioxidant is one of a phenol compound, a sterically hindered amine compound, and an ester compound containing a double bond. For example, antioxidants include 1,3,5-tri-tert-butylphenol, 1,5-tert-butyl-3-methylphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5' The antioxidant is at least one of the following: 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethylpiperidine, di-tert-butylamine, methyl methacrylate, and ethyl methacrylate. For example, the antioxidant is at least one of the following: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 1,5-tert-butyl-3-methylphenol, and methyl methacrylate.

[0593] In some embodiments, the UV stabilizer is at least one of 2-ethyl-2-cyano-3,3-diphenyl acrylate, (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionate amyl ester, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-ethyl-2'-ethoxypropionanilide, for example, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole.

[0594] In some embodiments, the thickener is a polymer. For example, the thickener is at least one polymer comprising polyamide, polyimide, polycarbonate, polyester, polyether, polymethacrylate, polyacrylate, polysilane, polysiloxane, polyvinyl acetate, polymethacrylonitrile, polyacrylonitrile, polyvinylphenol, polyvinyl alcohol, and vinylidene dihalides. The weight-average molecular weight of the polymer is in the range of 200,000 g / mol to 400,000 g / mol.

[0595] In some embodiments, the ion conductivity enhancer is at least one of lithium trifluoromethanesulfonate, lithium perchlorate, lithium tetrafluoroborate, and lithium hexafluorophosphate, for example, lithium perchlorate.

[0596] In some embodiments, the concentration of the anode color-changing material in the composition is in the range of 30 mM to 120 mM, which enables the electrochromic device to achieve the technical effect of color change; the concentration of the cathode color-changing material is in the range of 30 mM to 120 mM, which enables the electrochromic device to achieve the technical effect of color change; the content of the antioxidant is in the range of 20 mM to 500 mM, for example, in the range of 50 mM to 100 mM, which enables the electrochromic device to achieve the technical effect of extending its service life; and the concentration of the ion conductivity enhancer is in the range of 0.05 M to 0.5 M, which enables the electrochromic device to achieve the technical effect of rapid color change.

[0597] In some embodiments, the content of the delamination inhibitor is in the range of 1% to 6% by weight, based on the total mass of the composition, which enables the electrochromic apparatus to achieve the technical effect of uniform discoloration; the content of the UV stabilizer is in the range of 1% to 4% by weight, which enables the electrochromic apparatus to achieve the technical effect of extending its service life; and the content of the thickener is in the range of 0.05% to 3% by weight.

[0598] A sixth aspect of the present application provides an electrochromic apparatus comprising a first conductive surface of a first substrate material, a second conductive surface of a second substrate material, and a cavity defined by a sealing member connecting the first conductive surface and the second conductive surface. An electrochromic medium is disposed within the cavity.

[0599] The electrochromic medium is a composition according to the fifth aspect of the present application.

[0600] The present invention will be described in detail below using embodiments. In the following embodiments, the compounds represented by formulas (3) to (8) are structurally characterized by nuclear magnetic resonance and mass spectrometry.

[0601] Example 28 Compound represented by formula (3) [ka] The method for preparing it is as follows:

[0602] A mixed solution was obtained by homogeneously mixing 3 g of sodium hydride, 16.7 g of carbazole, and 19 g of 2-formyl-4,5-dimethylamino-1,3-dithiol (carbonyl compound) in an ice bath (first temperature) in the presence of 500 g of DMF (solvent).

[0603] The ice bath was removed. The mixed solution was heated to 60°C to 90°C (second temperature), and the condensation reflux reaction was continued for 8 to 12 hours. After the reaction was complete, purification was performed: 1 mol / L hydrochloric acid solution was slowly added dropwise to the completed mixture to adjust the pH of the mixture to 1. After a complete reaction for 1 hour, the solution was extracted with ethyl acetate, concentrated, and separated and purified by silica gel column chromatography to obtain the compound represented by formula (3), i.e., the crude anode electrochromic material. This crude product was recrystallized with an acetonitrile-dichloromethane mixed solution to obtain the purified anode electrochromic material.

[0604] Example 29 Compound represented by formula (4) [ka] The method for preparing it is as follows:

[0605] A mixed solution was obtained by homogeneously mixing 3 g of sodium hydride, 16.7 g of carbazole, and 19.2 g of 2-formyl-4,5-dimethoxy-1,3-dithiol (carbonyl compound) in an ice bath (first temperature) in the presence of 500 g of DMF (solvent).

[0606] The ice bath was removed. The mixed solution was heated to 60°C to 90°C (second temperature), and the condensation reflux reaction was continued for 8 to 12 hours. After the reaction was complete, purification was performed: 1 mol / L hydrochloric acid solution was slowly added dropwise to the completed mixture to adjust the pH of the mixture to 1. After 1 hour of complete reaction, the solution was extracted with ethyl acetate, concentrated, and separated and purified by silica gel column chromatography to obtain the compound represented by formula (4), i.e., the crude anoelectrochromic material. This crude product was recrystallized with an acetonitrile-dichloromethane mixed solution to obtain the purified anoelectrochromic material.

[0607] Example 30 Compound represented by formula (5) [ka] The method for preparing it is as follows:

[0608] A mixed solution was obtained by homogeneously mixing 3 g of sodium hydride, 16.7 g of carbazole, and 22.4 g of 2-formyl-4,5-dimethylthio-1,3-dithiol (carbonyl compound) in an ice bath (first temperature) in the presence of 500 g of DMF (solvent).

[0609] The ice bath was removed. The mixed solution was heated to 60°C to 90°C (second temperature), and the condensation reflux reaction was continued for 8 to 12 hours. After the reaction was complete, purification was performed: 1 mol / L hydrochloric acid solution was slowly added dropwise to the completed mixture to adjust the pH of the mixture to 1. After a complete reaction for 1 hour, the solution was extracted with ethyl acetate, concentrated, and separated and purified by silica gel column chromatography to obtain the compound represented by formula (5), i.e., the crude anode electrochromic material. This crude product was recrystallized with an acetonitrile-dichloromethane mixed solution to obtain the purified anode electrochromic material.

[0610] Example 31 Compound represented by formula (6) [ka] The method for preparing it is as follows:

[0611] A mixed solution was obtained by homogeneously mixing 3 g of sodium hydride, 16.7 g of carbazole, and 18.8 g of 2-formyl-3,4,5,6-tetrahydro-1,3-dithio[4,5-b]pyrazine (carbonyl compound) in an ice bath (first temperature) in the presence of 500 g of DMF (solvent).

[0612] The ice bath was removed. The mixed solution was heated to 60°C to 90°C (second temperature), and the condensation reflux reaction was continued for 8 to 12 hours. After the reaction was complete, purification was performed: 1 mol / L hydrochloric acid solution was slowly added dropwise to the completed mixture to adjust the pH of the mixture to 1. After a complete reaction for 1 hour, the solution was extracted with ethyl acetate, concentrated, and separated and purified by silica gel column chromatography to obtain the compound represented by formula (6), i.e., the crude anode electrochromic material. This crude product was recrystallized with an acetonitrile-dichloromethane mixed solution to obtain the purified anode electrochromic material.

[0613] Example 32 Compound represented by formula (7) [ka] The method for preparing it is as follows:

[0614] A mixed solution was obtained by homogeneously mixing 3 g of sodium hydride, 16.7 g of carbazole, and 18.9 g of 2-formyl-5,6-dihydro-1,3-dithio[4,5-b]dioxin (a carbonyl compound) in an ice bath (first temperature) in the presence of 500 g of DMF (solvent).

[0615] The ice bath was removed. The mixed solution was heated to 60°C to 90°C (second temperature), and the condensation reflux reaction was continued for 8 to 12 hours. After the reaction was complete, purification was performed: 1 mol / L hydrochloric acid solution was slowly added dropwise to the completed mixture to adjust the pH of the mixture to 1. After 1 hour of complete reaction, the solution was extracted with ethyl acetate, concentrated, and separated and purified by silica gel column chromatography to obtain the compound represented by formula (7), i.e., the crude anoelectrochromic material. This crude product was recrystallized with an acetonitrile-dichloromethane mixed solution to obtain the purified anoelectrochromic material.

[0616] Example 33 Compound represented by formula (8) [ka] The method for preparing it is as follows:

[0617] A mixed solution was obtained by homogeneously mixing 3 g of sodium hydride, 16.7 g of carbazole, and 22.2 g of 2-formyl-5,6-dihydro-1,3-dithio[4,5-b]dithiophene (a carbonyl compound) in an ice bath (first temperature) in the presence of 500 g of DMF (solvent).

[0618] The ice bath was removed. The mixed solution was heated to 60°C to 90°C (second temperature), and the condensation reflux reaction was continued for 8 to 12 hours. After the reaction was complete, purification was performed: 1 mol / L hydrochloric acid solution was slowly added dropwise to the completed mixture to adjust the pH of the mixture to 1. After a complete reaction for 1 hour, the solution was extracted with ethyl acetate, concentrated, and separated and purified by silica gel column chromatography to obtain the compound represented by formula (8), i.e., the crude anode electrochromic material. This crude product was recrystallized with an acetonitrile-dichloromethane mixed solution to obtain the purified anode electrochromic material.

[0619] Preparation of electrochromic media: Multiple electrochromic media (the electrochromic media being the compositions in this application) were prepared by separately using the compounds represented by formulas (3) to (8) and carbazole at a concentration of 60 mM as anodic color change materials. In addition, the electrochromic media further contained a 60 mM cathode electrochromic material, namely the compound represented by formula (11-1), 0.1 M lithium perchlorate, 4 wt% ethyl polyacrylate (weight-average molecular weight 300,000 g / mol), 3 wt% 2-(2'-hydroxy-4'-methylphenyl)benzotriazole, 50 mM 1,5-tert-butyl-3-methylphenol, 1 wt% PVDF (weight-average molecular weight 300,000 g / mol), and the remainder propylene carbonate.

[0620] [ka]

[0621] Discoloration performance test Using the multiple electrochromic media prepared above separately, electrochromic apparatuses with dimensions of 40 mm in length and 40 mm in width were constructed. The coloring response time and decolorization response time of each electrochromic apparatus were tested at a test voltage of 1.3 V. The test results are shown in Table 9. From the experiments, it was found that electrochromic media containing compounds represented by equations (3) to (8) exhibited faster color change and decolorization rates than electrochromic media containing carbazole.

[0622] [Table 10]

[0623] Cycle life test Electrochromic devices were fabricated using the multiple electrochromic media prepared above (the first and second transparent conductive substrates were glass plates plated with an ITO layer, the connecting layer was a frame sealant, the thickness of the containment space was 62 μm, and the transmittance of a single ITO glass plate was 92%). The length and width of the electrochromic devices were both 40 mm. At a test voltage of 1.3 V, after each cycle, the difference ΔT between the light transmittance in the visible light region before discoloration of each electrochromic device and the light transmittance in the visible light region after discoloration of each electrochromic device was tested. The test results are shown in Table 10. One cycle consisted of applying a voltage of 1.3 V for 5 seconds and applying a voltage of 0 V for 10 seconds. The state of the device was observed before and after the cycle, and the transmittance of the device was measured to determine the contrast before and after discoloration (ΔT = T). V=0 -T V=1.3 The following was calculated. From the experiment, it was found that the decay of the color change performance of electrochromic media containing the compounds represented by equations (3) to (8) was significantly slower than that of electrochromic media containing carbazole, which directly indicates a clear improvement in cycle life.

[0624] [Table 11]

[0625] Table 9 shows that electrochromic devices prepared from electrochromic media containing compounds represented by formulas (3) to (8) exhibit a significantly faster response speed (color change time and decolorization time) and superior color change effect compared to those prepared from electrochromic media containing carbazole. Table 10 shows that after 20,000 and 50,000 energization cycles, the difference ΔT between the visible light transmittance before and after color change for electrochromic devices prepared from electrochromic media containing compounds represented by formulas (3) to (8) is greater than the difference ΔT for electrochromic devices prepared from electrochromic media containing carbazole. This demonstrates that electrochromic devices prepared from the compounds prepared in the examples of this application have a superior color change effect compared to electrochromic devices prepared from carbazole in terms of cycle life.

[0626] In some embodiments, the present application further provides a light intensity adjustment device and applications thereof.

[0627] A light intensity adjustment device is provided, which includes a first substrate layer (1), a first conductive layer (Ad), a functional layer (13d), a second conductive layer (Bd), and a second substrate layer (12d), which are sequentially stacked from top to bottom.

[0628] The underside of the first conductive layer (Ad) is bonded to the first electrical conductor (5d), the frame sealant layer (7d), and the insulating layer (6d), and the underside of the insulating layer (6d) is bonded to the second electrical conductor (8d). The second electrical conductor (8d) and the first electrical conductor (5d) are spaced apart from each other, so that the insulating layer (6d), the second electrical conductor (8d), and the first electrical conductor (5d) define and form a cavity. The cross-section of the second electrical conductor (8d) and / or the cross-section of the first electrical conductor (5d) in the horizontal direction is L-shaped, and the functional layer (13d) and the second conductive layer (Bd) are located within the cavity.

[0629] The frame sealant layer (7d), the second conductive layer (Bd), and the first conductive layer (Ad) define and form cavities for filling with light modulating agents to form a functional layer (13d).

[0630] The second conductive layer (Bd) is insulated from the first electrical conductor (5d) via the frame sealant layer (7d), and the second conductive layer (Bd) is in contact with the second electrical conductor (8d). The first electrical conductor (5d) and the second electrical conductor (8d) are configured to be connected to a power source, thereby forming a current loop in series between the power source, the first electrical conductor (5d), the first conductive layer (Ad), the functional layer (13d), the second conductive layer (Bd), and the second electrical conductor (8d).

[0631] In some embodiments, the cross-sections of the second electrical conductor (8d) and the first electrical conductor (5d) in the horizontal direction are both L-shaped and are arranged in an inverted manner; and / or The first conductive layer (Ad) includes a first bottom layer (2d) and a first conductive layer (3d) sequentially stacked from top to bottom, wherein the first conductive layer (3d) is bonded to the upper surface of the functional layer (13d); and / or The second conductive layer (Bd) includes a third conductive layer (10d) and a second bottom layer (11d) sequentially stacked from top to bottom, wherein the third conductive layer (10d) is bonded to the underside of the functional layer (13d); and / or The power supply, the first electrical conductor (5d), the first bottom layer (2d), the first conductive layer (3d), the functional layer (13d), the third conductive layer (10d), the second bottom layer (11d), and the second electrical conductor (8d) form a current loop connected in series.

[0632] In some embodiments, the first conductive layer (Ad) includes a first bottom layer (2d), a first conductive layer (3d), and a first protective layer (4d) bonded sequentially from top to bottom, wherein the protective layer (4d) is bonded to the upper surface of the functional layer (13d); and / or The second conductive layer (Bd) includes a second protective layer (9d), a third conductive layer (10d), and a second bottom layer (11d) bonded sequentially from top to bottom, wherein the second protective layer (9d) is bonded to the underside of the functional layer (13d); and / or The power supply, the first electrical conductor (5d), the first bottom layer (2d), the first conductive layer (3d), the first protective layer (4d), the functional layer (13d), the second protective layer (9d), the third conductive layer (10d), the second bottom layer (11d), and the second electrical conductor (8d) form a current loop connected in series.

[0633] In some embodiments, the material of the first bottom layer (2d) and the second bottom layer (11d) is at least one of titanium dioxide, tantalum pentoxide, niobium pentoxide, silicon dioxide, and magnesium fluoride, for example, niobium pentoxide.

[0634] The thicknesses of the first bottom layer (2d) and the second bottom layer (11d) are in the range of 30 nm to 12d0 nm, for example, 30 nm to 50 nm.

[0635] In some embodiments, the material of the first conductive layer (3d) and the third conductive layer (10d) is at least one of indium tin oxide, tin oxide, antimond-doped tin oxide, fluorine-doped tin oxide, antimond-doped zinc oxide, and aluminum-doped zinc oxide, respectively, for example, indium tin oxide.

[0636] The thicknesses of the first conductive layer (3d) and the third conductive layer (10d) are in the range of 50 nm to 500 nm, for example, 80 nm to 150 nm.

[0637] In some embodiments, the materials of the first protective layer (4d) and the second protective layer (9d) are at least one of titanium, silver, aluminum, platinum, iridium, rhodium, ruthenium, and copper, for example, titanium and / or platinum; and / or The thicknesses of the first protective layer (4d) and the second protective layer (9d) are in the range of 5 nm to 50 nm, respectively.

[0638] In some embodiments, the materials of the first electrical conductor (5d) and the second electrical conductor (8d) are at least one of metallic silver, metallic copper, silver paste, conductive adhesive, and conductive ink, respectively, for example, silver paste.

[0639] The thickness of the first electrical conductor (5d) and the second electrical conductor (8d) is in the range of 40 μm to 1000 μm, for example, in the range of 50 μm to 200 μm; the width of the first electrical conductor (5d) and the second electrical conductor (8d) is in the range of 1 mm to 3 mm.

[0640] In some embodiments, the material of the frame sealant layer (7d) is at least one of phenolic resin, epoxy resin, and organic silica gel adhesive, for example, epoxy resin; and / or the thickness of the frame sealant layer (7d) is in the range of 70 μm to 250 μm and the width of the frame sealant layer (7d) is in the range of 1.2 mm to 4 mm; in some embodiments, the thickness is in the range of 100 μm to 150 μm and the width is in the range of 1.8 mm to 2.2 mm.

[0641] In some embodiments, the functional layer (13d) is configured as a light intensity adjustment functional layer. In some embodiments, the material of the functional layer (13d) includes a cathode color change material, an anode color change material, a solvent, and an optional additive.

[0642] In some embodiments, the auxiliary agent is at least one of a delamination inhibitor, a thickener, an electrolyte, an antioxidant, and a UV inhibitor.

[0643] In some embodiments, the cathode color change material is at least one of viologen, substituted viologen, anthraquinone, and substituted anthraquinone, for example methyl viologen; and / or the concentration of the cathode color change material is in the range of 10 mmol / L to 300 mmol / L, for example 50 mmol / L to 80 mmol / L; and / or The anode color change material is at least one of diphenylamine, substituted diphenylamine, N-substituted compounds of diphenylamine, triphenylamine, substituted triphenylamine, ferrocene, substituted ferrocene, ferrocene salt, substituted ferrocene salt, phenothiazine, substituted phenothiazine, thianthlene, substituted thianthlene, phenazine, substituted phenazine, 5,10-dihydrophenazine, and substituted 5,10-dihydrophenazine, for example, at least one of N-substituted compounds of diphenylamine, substituted phenothiazine, and substituted 5,10-dihydrophenazine; and / or the concentration of the anode color change material is in the range of 10 mmol / L to 300 mmol / L, for example, in the range of 60 mmol / L to 100 mmol / L; and / or The solvent is at least one of sulfones, amides, ethers, alcohols, nitriles, ketones, and esters, for example, at least one of 3-methylsulfolane, dimethyl sulfoxide, dimethylformamide, tetraethylene glycol dimethyl ether, ethoxyethanol, acetonitrile, glutaronitrile, 3-hydroxypropionitrile, 2-methylglutaronitrile, 2-acetylbutyrolactone, cyclopentanone, β-propiolactone, γ-butyrolactone, γ-valerolactone, polypropylene carbonate, ethylene carbonate, and propylene carbonate; another example is at least one of propylene carbonate, dimethyl sulfoxide, and dimethylformamide; and / or The delamination inhibitor is at least one of polyacr...

Claims

1. Reflecting device (1), A first transparent substrate sheet (10) including a first surface (11) and a second surface (12) that are opposite to each other, A transparent conductive layer (20) is disposed on the second surface (12), A second transparent substrate sheet (30) including a third surface (31) and a fourth surface (32) that are opposite to each other, A reflective layer (40) is disposed on the third surface (31) and faces the transparent conductive layer (20), A sealant (70) is connected between the first transparent substrate sheet (10) and the second transparent substrate sheet (30), and the sealant (70), the transparent conductive layer (20), and the reflective layer (40) define a cavity, and the sealant (70) contains filler particles having a dielectric constant of 20 or more. The light-adjusting composition (50) and the cavity located within the cavity A reflective device (1) equipped with the above.

2. The reflector (1) according to claim 1, wherein the dielectric constant of the filler particles is in the range of 25 to 150.

3. The reflective device (1) according to claim 2, wherein the filler particles include at least one of lead titanate, barium titanate, lanthanum titanate, titanium oxide, and zirconium oxide.

4. The reflective device (1) according to any one of claims 1 to 3, wherein the sealant (70) is configured to be hollow in the thickness direction, and the two end faces of the sealant in the thickness direction are connected to the transparent conductive layer and the reflective layer, respectively.

5. The reflective device (1) according to claim 1, wherein the sealant (70) comprises a first sealant (71) and a second sealant (72), and the first sealant (71) and the second sealant (72) define and form the sealant (70).

6. The reflective device (1) according to claim 1 or 5, wherein the shape of the filler particle is one of a rectangular parallelepiped, a cube, a sphere, and a cylinder.

7. The reflective device (1) according to claim 1, wherein the filler particles are spherical and the diameter of the filler particles is in the range of 30 μm to 300 μm.

8. The reflective device (1) according to claim 1, wherein the first transparent substrate sheet (10) comprises one of glass, acrylic, and polyvinyl chloride, and the second transparent substrate sheet (30) comprises one of glass, acrylic, and polyvinyl chloride, and the visible light transmittance of the first transparent substrate sheet (10) and the visible light transmittance of the second transparent substrate sheet (30) are both 80% or more.

9. The transparent conductive layer (20) is subject to the following conditions: The transparent conductive layer (20) comprises at least one of ITO, CTO, ZnO, and InO; The thickness of the transparent conductive layer (20) is in the range of 50 nm to 500 nm; and The visible light transmittance of the transparent conductive layer is 80% or more. A reflective device (1) according to claim 1, satisfying at least one of the following conditions.

10. The reflective layer (40) is subject to the following conditions: The reflective layer (40) comprises one of silver, silver alloy, aluminum, aluminum alloy, chromium, and chromium alloy; The thickness of the reflective layer (40) is in the range of 10 nm to 500 nm; and The reflectivity of the reflective layer is 70% or more: A reflective device (1) according to claim 1, satisfying at least one of the following conditions.

11. The reflective device (1) further comprises a transition layer (60), the transition layer (60) being disposed between the reflective layer (40) and the third surface (31), and the transition layer (60) is composed of SiO, TiO, and Nb ２ O ５ , and Al ２ O ３ The reflective device (1) according to claim 10, comprising at least one of the following.

12. The reflective device (1) according to claim 1, further comprising a first electrode plate (90) and a second electrode plate (100), wherein the first electrode plate (90) is electrically connected to the transparent conductive layer (20) and the second electrode plate (100) is electrically connected to the reflective layer (10).

13. The reflective device (1) according to claim 1, wherein the surface of the transparent conductive layer (20) facing the first transparent substrate sheet (10) includes a contact region that contacts the second surface (12) and a concave region that is recessed in a direction away from the second surface (12), the concave region surrounding the contact region and spaced apart from the second surface (12), a decorative layer disposed between the concave region and the second surface (12), and the reflectivity of the decorative layer is 50% or more.

14. A method for manufacturing a reflective device, The first transparent substrate sheet is prepared, which includes a first surface and a second surface arranged on opposite sides of each other, and a transparent conductive layer is placed on the second surface (S101). The steps include preparing a second transparent substrate sheet including a third surface and a fourth surface arranged on opposite sides of each other, and placing a reflective layer on the third surface (S102), The steps of bringing the transparent conductive layer facing the reflective layer and separating the transparent conductive layer from the reflective layer (S103), The steps include forming a sealant between the first transparent substrate sheet and the second transparent substrate sheet, defining a cavity with the sealant, the transparent conductive layer, and the reflective layer (S104), and injecting a light-adjusting composition into the cavity (S105). Includes, The sealant contains filler particles having a dielectric constant of 20 or more. A method for manufacturing a reflective device.

15. The step of placing the reflective layer on the third surface is, The steps include: arranging a transition layer on the third surface, The steps include: arranging the reflective layer on the surface of the transition layer that is away from the second transparent substrate sheet; A method for manufacturing a reflective device according to claim 14, including the method described in claim 14.

16. The sealant comprises a first sealant and a second sealant, the sealant is formed between the first transparent substrate sheet and the second transparent substrate sheet, the sealant, the transparent conductive layer, and the reflective layer define a cavity, and the light-adjusting composition is injected into the cavity. The first sealant connecting the first transparent substrate sheet and the second transparent substrate sheet is placed between the first transparent substrate sheet and the second transparent substrate sheet, and the first sealant, the transparent conductive layer, and the reflective layer define a cavity having an opening. The steps include: injecting the light-modulating composition into the cavity through the opening; A method for manufacturing a reflective device according to claim 14, including the method described in claim 14.

17. A method for manufacturing a reflective device according to claim 16, further comprising the step (S106) of arranging the second sealant connecting the first transparent substrate sheet and the second transparent substrate sheet between the first transparent substrate sheet and the second transparent substrate sheet to seal the opening.

18. A vehicle (2) equipped with a reflective device (1) according to any one of claims 1 to 13.

Images