Electrochromic material, preparation method thereof and low-emissivity glass assembly

Abstract

The invention provides an electrochromic material, a preparation method thereof and a low-emissivity glass assembly. The electrochromic material comprises an electrochromic glass base material and an electrochromic film layer which are arranged in a laminated mode. The film layer structure of the electrochromic film layer comprises a first transparent conductive layer, a cathode electrochromic layer, an ion conduction layer, an anode electrochromic layer, a dielectric layer and a second transparent conductive layer which are sequentially laminated in the direction from the electrochromic glass substrate to the outside; and the material of the ion conduction layer comprises NiWOx or WOx. By optimizing the material of the thin film in the electrochromic material, the optical modulation performance of the electrochromic material is improved, the modulation amplitude is further increased, and the coloring time is shortened; and meanwhile, the radiance of the glass assembly is further reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of material processing, relates to an electrochromic material, and particularly relates to an electrochromic material, a preparation method thereof, and a low-emissivity glass assembly. Background Art

[0002] With the continuous improvement of people's energy-saving and intelligent requirements in the fields of architecture and automobiles, low-emissivity glass assemblies have been widely used in these fields due to their excellent heat insulation performance. Traditional low-emissivity glass reduces the emissivity of the glass by depositing multiple layers of metal or metal oxide films on the glass surface, effectively preventing indoor heat from dissipating to the outside, achieving a good heat insulation and preservation effect, and reducing the energy consumption of buildings and automobiles to a certain extent.

[0003] However, traditional low-emissivity glass has limitations. Its optical properties are fixed and cannot adjust the light transmittance and heat insulation performance of the glass in real time according to changes in the external environmental light and temperature. When the sunlight is strong, too much solar radiation enters the room or the car, resulting in too high a temperature inside the room or the car, increasing the air-conditioning cooling load and consuming a large amount of energy; when the light is insufficient, the low light transmittance of the glass makes the light inside the room or the car dim, affecting the visual experience, and additional lighting equipment needs to be turned on, further consuming energy.

[0004] The emergence of electrochromic materials brings hope for solving the above problems. An electrochromic material is a functional material whose optical properties (such as light transmittance, reflectance, etc.) can reversibly change under the action of an electric field. Applying an electrochromic material to a low-emissivity glass assembly can endow the glass assembly with the ability to dynamically adjust the light transmittance according to requirements. However, for existing electrochromic materials, some have the problem of slow color change response speed. It takes a long time from applying voltage to achieving obvious color and light transmittance changes and cannot adapt to environmental changes in time; some materials have poor cycle stability, and their performance significantly decreases after multiple electrochromic cycles, affecting the service life; and some materials have complex preparation processes and high costs, restricting their large-scale application.

[0005] Currently, there is an urgent need in the market for an electrochromic material with excellent comprehensive performance, a simple preparation process, and controllable cost, as well as a low-emissivity glass assembly based on this material, to meet the urgent needs of the building, automobile and other industries for energy-saving and intelligent glass products. Summary of the Invention

[0006] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide an electrochromic material, a preparation method thereof, and a low-emissivity glass assembly. The present invention improves the optical modulation performance of the electrochromic material by optimizing the materials of the thin films in the electrochromic material, further increases the modulation amplitude, reduces the coloring time, and at the same time further reduces the emissivity of the glass assembly.

[0007] To achieve the object of this invention, the following technical solutions are adopted in this invention:

[0008] In a first aspect, this invention provides an electrochromic material, characterized in that the electrochromic material comprises an electrochromic glass substrate and an electrochromic thin film layer arranged in a laminated manner;

[0009] The film layer structure of the electrochromic thin film layer includes, in a direction from the electrochromic glass substrate outwards, a first transparent conductive layer, a cathode electrochromic layer, an ion conduction layer, an anode electrochromic layer, a dielectric layer, and a second transparent conductive layer, which are arranged in a laminated manner in sequence;

[0010] The material of the ion conduction layer comprises NiWO x or WO x .

[0011] In this invention, by optimizing the material of the ion conduction layer in the electrochromic thin film layer, the improvement of the optical modulation performance of the electrochromic material is realized, the modulation amplitude is further increased, and the coloring time is reduced;

[0012] Furthermore, using NiWO x or WO x as the ion conduction layer can improve the coloring speed of the electrochromic material while reducing the leakage current.

[0013] As a preferred technical solution of this invention, the thickness of the electrochromic glass substrate is 0.2 - 3 mm, for example, it can be 0.2 mm, 0.5 mm, 1 mm, 2 mm, 3 mm, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0014] Preferably, the material of the electrochromic glass substrate comprises float glass.

[0015] As a preferred technical solution of this invention, the material of the first transparent conductive layer comprises ITO conductive glass.

[0016] Preferably, the thickness of the first transparent conductive layer is 100 - 300 nm, for example, it can be 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0017] Preferably, the material of the cathode electrochromic layer comprises tungsten oxide.

[0018] Preferably, the thickness of the cathode electrochromic layer is 200 - 500 nm, for example, it can be 200 nm, 300 nm, 400 nm, 500 nm, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0019] Preferably, the material of the dielectric layer includes lithium.

[0020] Preferably, the thickness of the dielectric layer is 100 - 150 nm. For example, it can be 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0021] Preferably, the material of the anodic electrochromic layer includes nickel tungsten oxide.

[0022] Preferably, the atomic ratio of tungsten to nickel in the nickel tungsten oxide is (45 - 55):(55 - 45). For example, it can be 45:55, 50:50, or 50:45, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0023] Preferably, the thickness of the anodic electrochromic layer is 200 - 500 nm. For example, it can be 200 nm, 300 nm, 400 nm, 500 nm, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0024] Preferably, the material of the second transparent conductive layer includes ITO conductive glass.

[0025] Preferably, the thickness of the second transparent conductive layer is 300 - 800 nm. For example, it can be 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0026] Preferably, the thickness of the ion conduction layer is 50 - 150 nm. For example, it can be 50 nm, 70 nm, 90 nm, 110 nm, 130 nm, 150 nm, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0027] In the present invention, the ion conduction layer directly affects the optical modulation performance of the electrochromic material. If its thickness is too thin, the leakage current will increase; conversely, if its thickness is too thick, the color change speed will slow down.

[0028] More specifically, although the material of the ion conduction layer is the same as that of the anodic electrochromic layer or the cathodic electrochromic layer, the process conditions during the coating process are different, so that the ion conduction layer has different functions from the electrochromic layer. More specifically, the electrochromic layer is used to store lithium ions and lock the lithium ions inside the film layer; however, the internal structure of the film layer of the ion conduction layer cannot store lithium ions, and lithium ions can pass through freely.

[0029] In a second aspect, the present invention provides a method for preparing an electrochromic material as provided in the first aspect, the preparation method comprising:

[0030] By means of vacuum magnetron sputtering coating, a first transparent conductive layer, a cathode electrochromic layer, an ion conduction layer, a dielectric layer, an anode electrochromic layer and a second transparent conductive layer are sequentially deposited on an electrochromic glass substrate, and then wire interconnection is carried out to obtain the electrochromic material.

[0031] As a preferred technical solution of the present invention, during the deposition of the first transparent conductive layer, the power density of magnetron sputtering is 2-6 kw / m, for example, it can be 2 kw / m, 3 kw / m, 4 kw / m, 5 kw / m or 6 kw / m, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0032] Preferably, during the deposition of the first transparent conductive layer, the coating temperature of magnetron sputtering is 250-300 °C, for example, it can be 250 °C, 260 °C, 270 °C, 280 °C, 290 °C or 300 °C, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0033] Preferably, during the deposition of the first transparent conductive layer, the coating pressure of magnetron sputtering is 0.5-1 Pa, for example, it can be 0.5 Pa, 0.6 Pa, 0.7 Pa, 0.8 Pa, 0.9 Pa or 1.0 Pa, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0034] Preferably, during the deposition of the first transparent conductive layer, the gases for magnetron sputtering include oxygen and argon.

[0035] Preferably, during the deposition of the first transparent conductive layer, the oxygen flow rate of magnetron sputtering is 0.5-1% of the total gas flow rate, for example, it can be 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0036] Preferably, during the deposition of the first transparent conductive layer, the argon flow rate in magnetron sputtering is 100-500 sccm, for example, it can be 100 sccm, 200 sccm, 300 sccm, 400 sccm or 500 sccm, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0037] Preferably, during the deposition of the first transparent conductive layer, the sputtering rate of magnetron sputtering is 0.5 - 1 m / min. For example, it can be 0.5 m / min, 0.6 m / min, 0.7 m / min, 0.8 m / min, 0.9 m / min, or 1 m / min, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0038] Preferably, during the deposition of the cathode electrochromic layer, the power density of magnetron sputtering is 12 - 18 kw / m. For example, it can be 12 kw / m, 14 kw / m, 16 kw / m, or 18 kw / m, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0039] Preferably, during the deposition of the cathode electrochromic layer, the coating temperature of magnetron sputtering is 280 - 350 °C. For example, it can be 280 °C, 300 °C, 320 °C, 340 °C, or 350 °C, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0040] Preferably, during the deposition of the cathode electrochromic layer, the coating pressure of magnetron sputtering is 1.5 - 3.5 Pa. For example, it can be 1.5 Pa, 1.9 Pa, 2.3 Pa, 2.7 Pa, 3.1 Pa, or 3.5 Pa, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0041] Preferably, during the deposition of the cathode electrochromic layer, the magnetron sputtering gas includes oxygen and argon.

[0042] Preferably, during the deposition of the cathode electrochromic layer, the oxygen flow rate in magnetron sputtering is 20 - 100% of the total gas flow rate. For example, it can be 20%, 40%, 60%, 80%, or 100%, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0043] Preferably, during the deposition of the cathode electrochromic layer, the argon flow rate in magnetron sputtering is 200 - 1000 sccm. For example, it can be 200 sccm, 400 sccm, 600 sccm, 800 sccm, or 1000 sccm, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0044] Preferably, during the deposition of the cathode electrochromic layer, the sputtering rate of magnetron sputtering is 0.5 - 1 m / min. For example, it can be 0.5 m / min, 0.7 m / min, 0.9 m / min, or 1.0 m / min, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0045] Preferably, during the deposition of the ion-conducting layer, the power density of magnetron sputtering is 5-10 kw / m, for example, it can be 5 kw / m, 6 kw / m, 7 kw / m, 8 kw / m, 9 kw / m or 10 kw / m, etc., but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0046] Preferably, during the deposition of the ion-conducting layer, the coating temperature of magnetron sputtering is 20-50 °C, for example, it can be 20 °C, 30 °C, 40 °C or 50 °C, etc., but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0047] Preferably, during the deposition of the ion-conducting layer, the coating pressure of magnetron sputtering is 2-4 Pa, for example, it can be 2 Pa, 2.5 Pa, 3 Pa, 3.5 Pa or 4 Pa, etc., but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0048] It should be noted that if the coating temperature during the magnetron sputtering of the ion-conducting layer is too high, it will cause the film layer to be dense, the ion shuttle to be blocked, and the discoloration speed to slow down. If the coating temperature is too low, it will cause (the lower the better, no impact);

[0049] In addition, if the coating pressure of the ion-conducting layer is too high, it will cause the deposition speed to slow down. If the coating pressure is too low, it will cause the film layer to be dense, hinder the ion shuttle, and slow down the discoloration speed.

[0050] Preferably, during the deposition of the ion-conducting layer, the gas for magnetron sputtering is oxygen.

[0051] Preferably, during the deposition of the ion-conducting layer, the oxygen flow rate of magnetron sputtering is 500-800 sccm, for example, it can be 500 sccm, 600 sccm, 700 sccm or 800 sccm, etc., but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0052] Preferably, during the deposition of the ion-conducting layer, the speed of magnetron sputtering is 0.5-1 m / min, for example, it can be 0.5 m / min, 0.6 m / min, 0.7 m / min, 0.8 m / min, 0.9 m / min or 1 m / min, etc., but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0053] As a preferred technical solution of the present invention, during the deposition of the anode electrochromic layer, the power density of magnetron sputtering is 15-20 kw / m, for example, it can be 15 kw / m, 16 kw / m, 17 kw / m, 18 kw / m, 19 kw / m or 20 kw / m, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0054] Preferably, during the deposition of the anode electrochromic layer, the coating temperature of magnetron sputtering is 50-100 °C, for example, it can be 50 °C, 60 °C, 70 °C, 80 °C, 90 °C or 100 °C, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0055] Preferably, during the deposition of the anode electrochromic layer, the coating pressure of magnetron sputtering is 0.5-3 Pa, for example, it can be 0.5 Pa, 1 Pa, 2 Pa or 3 Pa, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0056] It should be noted that if the coating pressure during the magnetron sputtering of the anode electrochromic layer is too high, the deposition rate will become slow, and if the coating pressure is too low, the dense film layer will result in slow ion movement;

[0057] In addition, if the coating power density of the anode electrochromic layer is too high, the coating temperature will increase, resulting in an overly dense film layer. If the coating power density is too low, the coating speed will become slow, affecting the production capacity.

[0058] Preferably, during the deposition of the anode electrochromic layer, the magnetron sputtering gas includes oxygen and argon.

[0059] Preferably, during the deposition of the anode electrochromic layer, the flow rate of oxygen during magnetron sputtering is 20-100% of the total gas flow rate, for example, it can be 20%, 40%, 60%, 80% or 100%, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0060] Preferably, during the deposition of the anode electrochromic layer, the argon flow rate of magnetron sputtering is 500-1000 sccm, for example, it can be 500 sccm, 700 sccm, 900 sccm or 1000 sccm, etc., but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0061] Preferably, during the deposition of the anode electrochromic layer, the sputtering rate of magnetron sputtering is 0.1 - 0.6 m / min. For example, it can be 0.1 m / min, 0.2 m / min, 0.4 m / min, 0.6 m / min, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0062] As a preferred technical solution of the present invention, during the deposition of the dielectric layer, the power density during magnetron sputtering is 5 - 8 kw / m. For example, it can be 5 kw / m, 6 kw / m, 7 kw / m, 8 kw / m, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0063] Preferably, during the deposition of the dielectric layer, the coating temperature of magnetron sputtering is 50 - 80 °C. For example, it can be 50 °C, 60 °C, 70 °C, 80 °C, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0064] Preferably, during the deposition of the dielectric layer, the coating pressure of magnetron sputtering is 0.5 - 1 Pa. For example, it can be 0.5 Pa, 0.6 Pa, 0.7 Pa, 0.8 Pa, 0.9 Pa, 1.0 Pa, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0065] Preferably, during the deposition of the dielectric layer, the argon flow rate of magnetron sputtering is 300 - 800 sccm. For example, it can be 300 sccm, 400 sccm, 500 sccm, 600 sccm, 700 sccm, 800 sccm, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0066] Preferably, during the deposition of the dielectric layer, the sputtering rate of magnetron sputtering is 0.5 - 1 m / min. For example, it can be 0.5 m / min, 0.7 m / min, 0.9 m / min, 1 m / min, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0067] Preferably, during the deposition of the second transparent conductive layer, the power density of magnetron sputtering is 2 - 6 kw / m. For example, it can be 2 kw / m, 3 kw / m, 4 kw / m, 5 kw / m, 6 kw / m, etc., but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0068] Preferably, during the deposition of the second transparent conductive layer, the coating temperature of magnetron sputtering is 20 to 60 °C, for example, it can be 20 °C, 30 °C, 40 °C, 50 °C or 60 °C, etc., but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0069] Preferably, during the deposition of the second transparent conductive layer, the coating pressure of magnetron sputtering is 0.2 to 0.8 Pa, for example, it can be 0.2 Pa, 0.4 Pa, 0.6 Pa or 0.8 Pa, etc., but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0070] Preferably, during the deposition of the second transparent conductive layer, the gases for magnetron sputtering include oxygen and argon.

[0071] Preferably, during the deposition of the second transparent conductive layer, the oxygen flow rate of magnetron sputtering is 0.1 to 0.8% of the total gas flow rate, for example, it can be 0.1%, 0.2%, 0.4%, 0.6% or 0.8%, etc., but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0072] Preferably, during the deposition of the second transparent conductive layer, the argon flow rate of magnetron sputtering is 200 to 500 sccm, for example, it can be 200 sccm, 300 sccm, 400 sccm or 500 sccm, etc., but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0073] Preferably, during the deposition of the second transparent conductive layer, the sputtering speed of magnetron sputtering is 0.5 to 1 m / min, for example, it can be 0.5 m / min, 0.6 m / min, 0.8 m / min or 1 m / min, etc., but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0074] In a third aspect, the present invention provides a low-emissivity glass assembly, and the low-emissivity glass assembly includes the electrochromic material provided in the first aspect;

[0075] The low-emissivity glass assembly sequentially includes, from the outer tempered glass substrate inward: an outer tempered glass substrate, an electrochromic material, a metal frame, and an inner glass substrate;

[0076] The electrochromic material includes an electrochromic glass substrate and an electrochromic thin film layer; the electrochromic thin film layer is disposed between the electrochromic glass substrate and the metal frame.

[0077] As a preferred technical solution of the present invention, an interlayer is further disposed between the outer tempered glass substrate and the electrochromic glass substrate.

[0078] Preferably, the thickness of the interlayer is 0.5 to 1.5 mm. For example, it can be 0.5 mm, 0.7 mm, 0.9 mm, 1.1 mm, 1.3 mm, 1.5 mm, etc., but is not limited to the listed values. Other values within the numerical range that are not listed are equally applicable.

[0079] Preferably, the interlayer includes any one of SGP film, PVB film or EVA film.

[0080] As a preferred technical solution of the present invention, the thickness of the outer tempered glass substrate is 5 to 10 mm. For example, it can be 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, etc., but is not limited to the listed values. Other values within the numerical range that are not listed are equally applicable.

[0081] Preferably, the metal frame includes an aluminum profile.

[0082] Preferably, the thickness of the aluminum profile is 20 to 50 mm. For example, it can be 20 mm, 30 mm, 40 mm, 50 mm, etc., but is not limited to the listed values. Other values within the numerical range that are not listed are equally applicable.

[0083] Preferably, the thickness of the inner glass substrate is 5 to 10 mm. For example, it can be 5 mm, 6 mm, 8 mm, 10 mm, etc., but is not limited to the listed values. Other values within the numerical range that are not listed are equally applicable.

[0084] Preferably, the material of the inner glass substrate includes float glass.

[0085] Preferably, the preparation method of the low-emissivity glass assembly includes the following steps:

[0086] (1) Vacuum laminating the electrochromic material and the outer tempered glass substrate with a film to obtain a semi-finished product;

[0087] (2) Protectively encapsulating the metal frame, the inner glass substrate and the semi-finished product obtained in step (1) to obtain the low-emissivity glass assembly.

[0088] Preferably, the preparation method further includes pre-treating the outer tempered glass substrate, the electrochromic thin film layer, the metal frame and the inner glass substrate.

[0089] Preferably, the pre-treatment includes quality inspection and surface cleaning carried out in sequence.

[0090] Preferably, the degree of vacuum in the step (1) of vacuum laminating is 10 to 50 Pa. For example, it can be 10 Pa, 20 Pa, 30 Pa, 40 Pa, 50 Pa, etc., but it is not limited to the listed values, and other values within the numerical range that are not listed are equally applicable.

[0091] The numerical range described in the present invention includes not only the above-listed point values, but also any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0092] Compared with the prior art, the present invention has the following beneficial effects:

[0093] (1) By optimizing the material of the thin film in the electrochromic material, the present invention realizes the improvement of the optical modulation performance of the electrochromic material, further increases the modulation amplitude, and reduces the coloring time.

[0094] (2) The infrared transmittance of the low-emissivity glass component provided by the present invention is <1%, which further improves its optical comfort, making it have super heat insulation ability and higher energy-saving efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] Figure 1 It is a schematic structural diagram of an electrochromic thin film layer in the electrochromic material provided in Embodiment 1 of the present invention;

[0096] Figure 2 It is a schematic structural diagram of the low-emissivity glass component provided by the present invention;

[0097] Among them, 1 is an outer tempered glass substrate, 2 is an interlayer, 3 is an electrochromic glass substrate, 4 is an electrochromic thin film layer, 5 is a metal frame, 6 is an inner glass substrate; 4-1 is a first transparent conductive layer, 4-2 is a cathode electrochromic layer, 4-3 is an ion conduction layer, 4-4 is an anode electrochromic layer, 4-5 is a dielectric layer, and 4-6 is a second transparent conductive layer. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0098] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0099] Embodiment 1

[0100] This embodiment provides an electrochromic material, as Figure 1 shown, the electrochromic material includes an electrochromic glass substrate 3 and an electrochromic thin film layer 4 which are laminated;

[0101] The film layer structure of the electrochromic film layer 4 includes, in the direction from the electrochromic glass substrate 3 outwards, a first transparent conductive layer 4-1, a cathode electrochromic layer 4-2, an ion conduction layer 4-3, an anode electrochromic layer 4-4, a dielectric layer 4-5, and a second transparent conductive layer 4-6, which are sequentially stacked.

[0102] The electrochromic glass substrate 3 is a float glass with a thickness of 1.5 mm;

[0103] The first transparent conductive layer 4-1 is an ITO conductive glass with a thickness of 200 nm; the cathode electrochromic layer 4-2 is tungsten oxide with a thickness of 350 nm; the ion conduction layer 4-3 is NiWO x ; the anode electrochromic layer 4-4 is nickel tungsten oxide with a thickness of 350 nm, the dielectric layer 4-5 is lithium with a thickness of 100 nm; the second transparent conductive layer 4-6 is an ITO conductive glass with a thickness of 600 nm.

[0104] The preparation method of the electrochromic material includes:

[0105] Using the method of vacuum magnetron sputtering coating, the first transparent conductive layer 4-1, the cathode electrochromic layer 4-2, the ion conduction layer 4-3, the anode electrochromic layer 4-4, the dielectric layer 4-5, and the second transparent conductive layer 4-6 are sequentially coated on the electrochromic glass substrate 3, and then wire interconnection is carried out to obtain the electrochromic material;

[0106] During the coating process of the first transparent conductive layer 4-1, the power density of magnetron sputtering is 4 kw / m, the coating temperature is 280 °C, the coating pressure is 0.65 Pa, the flow rate of oxygen is 0.75% of the total gas flow rate, the flow rate of argon is 300 sccm, and the speed is 0.5 m / min;

[0107] During the coating process of the cathode electrochromic layer 4-2, the power density of magnetron sputtering is 15 kw / m, the coating temperature is 300 °C, the coating pressure is 2.5 Pa, the flow rate of oxygen is 50% of the total gas flow rate, the flow rate of argon is 600 sccm, and the speed is 0.7 m / min;

[0108] During the coating process of the ion conduction layer 4-3, the power density of magnetron sputtering is 10 kw / m, the coating temperature is 50 °C, the coating pressure is 3 Pa, the flow rate of oxygen gas is 650 sccm, and the speed is 0.5 m / min;

[0109] During the coating process of the anode electrochromic layer 4-4, the power density of magnetron sputtering is 18 kw / m, the coating temperature is 50 °C, the coating pressure is 2 Pa, the flow rate of oxygen is 40% of the total gas flow rate, the flow rate of argon is 750 sccm, and the speed is 0.4 m / min;

[0110] During the deposition of the dielectric layer 4-5, the power density of magnetron sputtering is 6.5 kw / m, the coating temperature is 60 °C, the coating pressure is 0.7 Pa, the argon flow rate is 550 sccm, and the speed is 0.6 m / min;

[0111] During the deposition of the second transparent conductive layer 4-6, the power density of magnetron sputtering is 4 kw / m, the coating temperature is 30 °C, the coating pressure is 0.4 Pa, the oxygen flow rate is 0.4% of the total gas flow rate, the argon flow rate is 350 sccm, and the speed is 0.6 m / min.

[0112] Example 2

[0113] This example provides an electrochromic material, which includes an electrochromic glass substrate 3 and an electrochromic thin film layer 4 arranged in a stack;

[0114] The film layer structure of the electrochromic thin film layer 4 includes, in the direction from the electrochromic glass substrate 3 outwards, a first transparent conductive layer 4-1, a cathode electrochromic layer 4-2, an ion conduction layer 4-3, an anode electrochromic layer 4-4, a dielectric layer 4-5, and a second transparent conductive layer 4-6, which are arranged in a stack in sequence.

[0115] The electrochromic glass substrate 3 is a float glass with a thickness of 0.2 mm;

[0116] The first transparent conductive layer 4-1 is an ITO conductive glass with a thickness of 100 nm; the cathode electrochromic layer 4-2 is tungsten oxide with a thickness of 200 nm;; the ion conduction layer 4-3 is WO x ; the anode electrochromic layer 4-4 is nickel tungsten oxide with a thickness of 200 nm; the dielectric layer 4-5 is a lithium layer with a thickness of 100 nm, and the second transparent conductive layer 4-6 is an ITO conductive glass with a thickness of 300 nm.

[0117] The preparation method of the electrochromic material includes:

[0118] Using the method of vacuum magnetron sputtering coating, the first transparent conductive layer 4-1, the cathode electrochromic layer 4-2, the ion conduction layer 4-3, the anode electrochromic layer 4-4, the dielectric layer 4-5, and the second transparent conductive layer 4-6 are sequentially deposited on the electrochromic glass substrate 3, and then wire interconnection is carried out to obtain the electrochromic material;

[0119] During the deposition of the first transparent conductive layer 4-1, the power density of magnetron sputtering is 2 kw / m, the coating temperature is 250 °C, the coating pressure is 1 Pa, the flow rate of oxygen is 0.5% of the total gas flow rate, the flow rate of argon is 100 sccm, and the speed is 0.5 m / min;

[0120] During the deposition of the cathode electrochromic layer 4-2, the power density of magnetron sputtering is 12 kw / m, the coating temperature is 280 °C, the coating pressure is 3.5 Pa, the flow rate of oxygen is 20% of the total gas flow rate, the flow rate of argon is 200 sccm, and the speed is 1 m / min;

[0121] During the deposition of the ion-conducting layer 4-3, the power density of magnetron sputtering is 7 kw / m, the coating temperature is 50 °C, the coating pressure is 4 Pa, the flow rate of oxygen is 100% of the total gas flow rate, the flow rate of oxygen is 500 sccm, and the speed is 1 m / min;

[0122] During the deposition of the anode electrochromic layer 4-4, the power density of magnetron sputtering is 15 kw / m, the coating temperature is 20 °C, the coating pressure is 3 Pa, the flow rate of oxygen is 20% of the total gas flow rate, the flow rate of argon is 500 sccm, and the speed is 0.6 m / min;

[0123] During the deposition of the dielectric layer 4-5, the power density of magnetron sputtering is 5 kw / m, the coating temperature is 50 °C, the coating pressure is 1 Pa, the flow rate of argon is 300 sccm, and the speed is 0.5 m / min;

[0124] During the deposition of the second transparent conductive layer 4-6, the power density of magnetron sputtering is 2 kw / m, the coating temperature is 20 °C, the coating pressure is 0.8 Pa, the flow rate of oxygen is 0.1% of the total gas flow rate, the flow rate of argon is 200 sccm, and the speed is 0.5 m / min.

[0125] Example 3

[0126] This example provides an electrochromic material, and the electrochromic material includes an electrochromic glass substrate 3 and an electrochromic thin film layer 4 arranged in a laminated manner;

[0127] The film layer structure of the electrochromic thin film layer 4 includes, in the direction from the electrochromic glass substrate 3 outward, a first transparent conductive layer 4-1, a cathode electrochromic layer 4-2, an ion-conducting layer 4-3, an anode electrochromic layer 4-4, a dielectric layer 4-5, and a second transparent conductive layer 4-6 arranged in a laminated manner in sequence.

[0128] The electrochromic glass substrate 3 is a float glass with a thickness of 3 mm;

[0129] The first transparent conductive layer 4-1 is ITO conductive glass with a thickness of 300 nm; the cathode electrochromic layer 4-2 is tungsten oxide with a thickness of 500 nm; the ion conduction layer 4-3 is NiWO with a thickness of 150 nm x ; the anode electrochromic layer 4-4 is nickel tungsten oxide with a thickness of 500 nm; the dielectric layer 4-5 is a lithium layer with a thickness of 150 nm; the second transparent conductive layer 4-6 is ITO conductive glass with a thickness of 800 nm.

[0130] The preparation method of the electrochromic material includes:

[0131] By using the method of vacuum magnetron sputtering coating, the first transparent conductive layer 4-1, the cathode electrochromic layer 4-2, the ion conduction layer 4-3, the anode electrochromic layer 4-4, the dielectric layer 4-5 and the second transparent conductive layer 4-6 are sequentially coated on the electrochromic glass substrate 3, and then wire interconnection is carried out to obtain the electrochromic material;

[0132] During the process of coating the first transparent conductive layer 4-1, the power density of magnetron sputtering is 6 kw / m, the coating temperature is 300 °C, the coating pressure is 0.5 Pa, the flow rate of oxygen is 1% of the total gas flow rate, the argon flow rate is 500 sccm, and the speed is 1 m / min;

[0133] During the process of coating the cathode electrochromic layer 4-2, the power density of magnetron sputtering is 18 kw / m, the coating temperature is 350 °C, the coating pressure is 1.5 Pa, the flow rate of oxygen is 100% of the total gas flow rate, and the speed is 1 m / min;

[0134] During the process of coating the ion conduction layer 4-3, the power density of magnetron sputtering is 12 kw / m, the coating temperature is 80 °C, the coating pressure is 2 Pa, the oxygen flow rate is 100% of the total gas flow rate, and the speed is 0.5 m / min;

[0135] During the process of coating the anode electrochromic layer 4-4, the power density of magnetron sputtering is 20 kw / m, the coating temperature is 60 °C, the coating pressure is 0.5 Pa, the flow rate of oxygen is 100% of the total gas flow rate, and the speed is 0.1 m / min;

[0136] During the process of coating the dielectric layer 4-5, the power density of magnetron sputtering is 8 kw / m, the coating temperature is 80 °C, the coating pressure is 0.5 Pa, the argon flow rate is 800 sccm, and the speed is 1 m / min;

[0137] During the deposition of the second transparent conductive layer 4-6, the power density of magnetron sputtering is 6 kw / m, the coating temperature is 60 °C, the coating pressure is 0.2 Pa, the oxygen flow rate is 0.8% of the total gas flow rate, the argon flow rate is 500 sccm, and the speed is 0.5 m / min.

[0138] Example 4

[0139] This example provides an electrochromic material, and the difference between this electrochromic material and that of Example 1 is only that:

[0140] In this example, the thickness of the ion conduction layer 4-3 is adjusted to 30 nm.

[0141] Example 5

[0142] This example provides an electrochromic material, and the difference between this electrochromic material and that of Example 1 is only that:

[0143] In this example, the thickness of the ion conduction layer 4-3 is adjusted to 180 nm.

[0144] Example 6

[0145] This example provides an electrochromic material, and the difference between this electrochromic material and that of Example 1 is only that:

[0146] In this example, the thickness of the dielectric layer 4-5 is adjusted to 20 nm.

[0147] Example 7

[0148] This example provides an electrochromic material, and the difference between this electrochromic material and that of Example 1 is only that:

[0149] In this example, the thickness of the dielectric layer 4-5 is adjusted to 200 nm.

[0150] Example 8

[0151] This example provides an electrochromic material, which is the same as that of Example 1. The difference between the preparation method of this electrochromic material and that of Example 1 is only that:

[0152] In this example, during the deposition of the ion conduction layer 4-3, the coating temperature of magnetron sputtering is adjusted to 100 °C.

[0153] Example 9

[0154] This example provides an electrochromic material, which is the same as that of Example 1. The difference between the preparation method of this electrochromic material and that of Example 1 is only that:

[0155] In this embodiment, during the deposition of the ion conduction layer 4-3, the coating pressure of magnetron sputtering is adjusted to 0.5 Pa.

[0156] Example 10

[0157] This embodiment provides an electrochromic material, which is the same as that in Example 1. The difference between the preparation method of this electrochromic material and that of Example 1 is only that:

[0158] In this embodiment, during the deposition of the ion conduction layer 4-3, the coating pressure of magnetron sputtering is adjusted to 5 Pa.

[0159] Comparative Example 1

[0160] This comparative example provides an electrochromic material. The difference between this electrochromic material and that in Example 1 is only that:

[0161] In this comparative example, the material of the ion conduction layer 4-3 is adjusted to silicon oxide.

[0162] Comparative Example 2

[0163] This comparative example provides an electrochromic material. The difference between this electrochromic material and that in Example 1 is only that:

[0164] In this comparative example, the material of the ion conduction layer 4-3 is adjusted to silicon aluminum oxide.

[0165] Comparative Example 3

[0166] This comparative example provides an electrochromic material. The difference between this electrochromic material and that in Example 1 is only that:

[0167] In this comparative example, the film layer structure of the electrochromic film layer 4 is adjusted to include, in the direction from the electrochromic glass substrate 3 outwards, a first transparent conductive layer, a cathode electrochromic layer, a dielectric layer, an ion conduction layer, an anode electrochromic layer, and a second transparent conductive layer, which are sequentially stacked.

[0168] Application Example 1

[0169] Using the electrochromic materials provided in the above examples and comparative examples as raw materials, a low-emissivity glass component is prepared. The low-emissivity glass component includes, in the direction from the outer toughened glass substrate inwards, an outer toughened glass substrate 1, an interlayer 2, an electrochromic glass substrate 3, an electrochromic film layer 4, a metal frame 5, and an inner glass substrate 6.

[0170] The thickness of the interlayer 2 is 1 mm; the thickness of the outer toughened glass substrate is 8 mm; the metal frame includes an aluminum profile, and the thickness of the aluminum profile is 35 mm; the inner glass substrate is a float glass with a thickness of 6 mm.

[0171] Among them, the structural schematic diagram of the low-emissivity glass component including the electrochromic material provided in Example 1 is as Figure 2 shown.

[0172] Performance detection:

[0173] (1) The electrochromic materials provided in the above-mentioned examples and comparative examples were subjected to optical modulation performance detection, and the results are shown in Table 1;

[0174] The optical modulation performance detection includes: using a spectrophotometer to detect the transmittance of the electrochromic thin film and the time required for the lowest transmittance (coloring time) under the conditions of a tempering voltage of 1-5 V and a spectral range of 380-780 nm; and calculating the adjustment range through the transmittance;

[0175] (2) The low-emissivity glass components containing the electrochromic materials provided in the above-mentioned examples and comparative examples were subjected to infrared transmittance detection, and the results are shown in Table 1.

[0176] Table 1

[0177]

[0178]

[0179] It can be seen from the data in Table 1 that:

[0180] (1) Through comprehensive analysis of Examples 1-3, it can be seen that the electrochromic materials provided by the present invention have good optical modulation performance, which can increase the modulation amplitude of electrochromic products by about 10% and the coloring speed by about 200 s;

[0181] In addition, the infrared transmittance of the glass component containing the electrochromic material provided by the present invention < 1%, has low radiation, and better meets the market demand;

[0182] (2) Through comprehensive analysis of Example 1 and Examples 4-5, it can be seen that too thick a thickness of the ion conduction layer will lead to a slower color change speed. On the contrary, if its thickness is too thin, it will lead to a larger leakage current and the color change speed will also be slower;

[0183] Through comprehensive analysis of Example 1 and Examples 6-7, it can be seen that too thick a thickness of the dielectric layer in the present invention will lead to a smaller modulation amplitude. On the contrary, if its thickness is too thin, it will also lead to a smaller modulation amplitude;

[0184] (3) Through comprehensive analysis of Example 1 and Example 8, it can be seen that too high a coating temperature of the ion conduction layer during magnetron sputtering will lead to a dense film layer and a slower color change speed;

[0185] From a comprehensive analysis of Example 1 and Examples 9-10, it can be seen that if the coating pressure during magnetron sputtering of the ion conduction layer is too high, it will lead to a slower film deposition rate, a thinner film thickness, and a smaller modulation amplitude. Conversely, if the coating pressure is too low, it will lead to a slower densification and discoloration rate of the film layer;

[0186] (4) From a comprehensive analysis of Example 1 and Comparative Examples 1-2, it can be seen that the material of the ion conduction layer affects the optical modulation performance of the electrochromic material;

[0187] If the material of the ion conduction layer is changed to silicon oxide or silicon aluminum oxide, it will lead to a smaller adjustment amplitude and a slower discoloration rate;

[0188] (5) From a comprehensive analysis of Example 1 and Comparative Example 3, it can be seen that if the dielectric layer is adjusted between the cathode electrochromic layer and the ion conduction layer, it will lead to a smaller modulation amplitude and a slower coloring rate.

[0189] In summary, through the optimization of the materials of the thin films in the electrochromic material, the present invention realizes the improvement of the optical modulation performance of the electrochromic material, further increases the modulation amplitude, and reduces the coloring time; at the same time, it further reduces the emissivity of the glass component.

[0190] The applicant declares that the above description is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. An electrochromic material, characterized in that, The electrochromic material includes an electrochromic glass substrate and an electrochromic thin film layer arranged in a stack; The layer structure of the electrochromic thin film layer includes, from the electrochromic glass substrate outwards, a first transparent conductive layer, a cathode electrochromic layer, an ion conduction layer, an anode electrochromic layer, a dielectric layer, and a second transparent conductive layer, which are sequentially arranged in a stack; The material of the ion conducting layer includes NiWO x or WO x .

2. The electrochromic material according to claim 1, characterized in that, The thickness of the electrochromic glass substrate is 0.2 - 3 mm; Preferably, the material of the electrochromic glass substrate includes float glass.

3. The electrochromic material according to claim 1 or 2, characterized in that, The material of the first transparent conductive layer includes ITO conductive glass; Preferably, the thickness of the first transparent conductive layer is 100 - 300 nm; Preferably, the material of the cathode electrochromic layer includes tungsten oxide; Preferably, the thickness of the cathode electrochromic layer is 200 - 500 nm; Preferably, the material of the dielectric layer includes lithium; Preferably, the thickness of the dielectric layer is 100 - 150 nm; Preferably, the material of the anode electrochromic layer includes nickel tungsten oxide; Preferably, the thickness of the anode electrochromic layer is 200 - 500 nm; Preferably, the material of the second transparent conductive layer includes ITO conductive glass; Preferably, the thickness of the second transparent conductive layer is 300 - 800 nm; Preferably, the thickness of the ion conduction layer is 50 - 150 nm.

4. A method for preparing an electrochromic material according to any one of claims 1-3, characterized in that, The preparation method includes: Using the method of vacuum magnetron sputtering coating, sequentially coating a first transparent conductive layer, a cathode electrochromic layer, an ion conduction layer, an anode electrochromic layer, a dielectric layer, and a second transparent conductive layer on the electrochromic glass substrate, and then performing wire interconnection to obtain the electrochromic material.

5. The preparation method according to claim 4, characterized in that, During the process of coating the first transparent conductive layer, the power density of magnetron sputtering is 2 - 6 kw / m; Preferably, during the process of coating the first transparent conductive layer, the coating temperature of magnetron sputtering is 250 - 300 °C; Preferably, during the process of coating the first transparent conductive layer, the coating pressure of magnetron sputtering is 0.5 - 1 Pa; Preferably, during the process of coating the first transparent conductive layer, the gas for magnetron sputtering includes oxygen and argon; Preferably, during the process of coating the first transparent conductive layer, the oxygen flow rate of magnetron sputtering is 0.5 - 1% of the total gas flow rate; Preferably, during the process of coating the first transparent conductive layer, the argon flow rate in magnetron sputtering is 100 - 500 sccm; Preferably, during the process of coating the first transparent conductive layer, the sputtering speed of magnetron sputtering is 0.5 - 1 m / min; Preferably, during the process of coating the cathode electrochromic layer, the power density of magnetron sputtering is 12 - 18 kw / m; Preferably, during the process of coating the cathode electrochromic layer, the coating temperature of magnetron sputtering is 280 - 350 °C; Preferably, during the process of coating the cathode electrochromic layer, the coating pressure of magnetron sputtering is 1.5 - 3.5 Pa; Preferably, during the process of coating the cathode electrochromic layer, the gas for magnetron sputtering includes oxygen and argon; Preferably, during the process of coating the cathode electrochromic layer, the oxygen flow rate in magnetron sputtering is 20 - 100% of the total gas flow rate; Preferably, during the deposition of the cathode electrochromic layer, the argon flow rate in magnetron sputtering is 200 - 1000 sccm; Preferably, during the deposition of the cathode electrochromic layer, the sputtering speed of magnetron sputtering is 0.5 - 1 m / min.

6. The preparation method according to claim 4 or 5, characterized in that, During the deposition of the dielectric layer, the power density during magnetron sputtering is 5 - 8 kw / m; Preferably, during the deposition of the dielectric layer, the coating temperature of magnetron sputtering is 50 - 80 °C; Preferably, during the deposition of the dielectric layer, the coating pressure of magnetron sputtering is 0.5 - 1 Pa; Preferably, during the deposition of the dielectric layer, the argon flow rate in magnetron sputtering is 300 - 800 sccm; Preferably, during the deposition of the dielectric layer, the sputtering speed of magnetron sputtering is 0.5 - 1 m / min; Preferably, during the deposition of the ion-conducting layer, the power density of magnetron sputtering is 5 - 10 kw / m; Preferably, during the deposition of the ion-conducting layer, the coating temperature of magnetron sputtering is 20 - 50 °C; Preferably, during the deposition of the ion-conducting layer, the coating pressure of magnetron sputtering is 2 - 4 Pa; Preferably, during the deposition of the ion-conducting layer, the gas used in magnetron sputtering is oxygen; Preferably, during the deposition of the ion-conducting layer, the oxygen flow rate in magnetron sputtering is 500 - 800 sccm; Preferably, during the deposition of the ion-conducting layer, the sputtering speed of magnetron sputtering is 0.5 - 1 m / min.

7. The preparation method according to any one of claims 4-6, characterized in that, During the deposition of the anode electrochromic layer, the power density of magnetron sputtering is 15 - 20 kw / m; Preferably, during the deposition of the anode electrochromic layer, the coating temperature of magnetron sputtering is 20 - 60 °C; Preferably, during the deposition of the anode electrochromic layer, the coating pressure of magnetron sputtering is 0.5 - 3 Pa; Preferably, during the deposition of the anode electrochromic layer, the gases used in magnetron sputtering include oxygen and argon; Preferably, during the deposition of the anode electrochromic layer, the oxygen flow rate during magnetron sputtering is 20 - 100% of the total gas flow rate; Preferably, during the deposition of the anode electrochromic layer, the argon flow rate in magnetron sputtering is 500 - 1000 sccm; Preferably, during the deposition of the anode electrochromic layer, the sputtering speed of magnetron sputtering is 0.1 - 0.6 m / min; Preferably, during the deposition of the second transparent conductive layer, the power density of magnetron sputtering is 2 - 6 kw / m; Preferably, during the deposition of the second transparent conductive layer, the coating temperature of magnetron sputtering is 20 - 60 °C; Preferably, during the deposition of the second transparent conductive layer, the coating pressure of magnetron sputtering is 0.2 - 0.8 Pa; Preferably, during the deposition of the second transparent conductive layer, the gases used in magnetron sputtering include oxygen and argon; Preferably, during the deposition of the second transparent conductive layer, the oxygen flow rate in magnetron sputtering is 0.1 - 0.8% of the total gas flow rate; Preferably, during the deposition of the second transparent conductive layer, the argon flow rate in magnetron sputtering is 200 - 500 sccm; Preferably, during the deposition of the second transparent conductive layer, the sputtering speed of magnetron sputtering is 0.5 - 1 m / min.

8. A low-emissivity glass component, characterized in that, The low-emissivity glass assembly comprises the electrochromic material according to any one of claims 1-3; The low-emissivity glass assembly sequentially includes, from the outer toughened glass substrate inward: an outer toughened glass substrate, an electrochromic material, a metal frame, and an inner glass substrate; The electrochromic material includes an electrochromic glass substrate and an electrochromic thin film layer; the electrochromic thin film layer is disposed between the electrochromic glass substrate and the metal frame.

9. The low-emissivity glass component according to claim 8, wherein An interlayer is further disposed between the outer toughened glass substrate and the electrochromic glass substrate; Preferably, the thickness of the interlayer is 0.5-1.5 mm; Preferably, the interlayer includes any one of an SGP film, a PVB film, or an EVA film.

10. The low-emissivity glass component according to claim 8 or 9, characterized in that, The thickness of the outer toughened glass substrate is 5-10 mm; Preferably, the metal frame includes an aluminum profile; Preferably, the thickness of the aluminum profile is 20-50 mm; Preferably, the thickness of the inner glass substrate is 5-10 mm; Preferably, the material of the inner glass substrate includes float glass.

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