Energy saving glass with electrochromic interlayer

Abstract

The application relates to the technical field of building glass, in particular to energy-saving glass with an electrochromic interlayer, which comprises the following components: 83-90% of a glass substrate, 1-5% of a transparent conductive layer, 1-3% of an ion storage layer, 1-5% of an ion conductor layer and 1-5% of an electrochromic layer; the transparent conductive layer is tightly combined with the glass substrate to form a transparent electrode; the ion storage layer is located between the transparent conductive layer and the ion conductor layer; and the electrochromic layer is located on the other side of the ion conductor layer. The application aims to provide energy-saving glass with an electrochromic interlayer, and solve the problem that electrochromic glass may be affected by external factors such as temperature, humidity and ultraviolet light during use, resulting in performance decline.

Description

Technical Field

[0001] This invention relates to the field of architectural glass technology, and more specifically, to an energy-saving glass with an electrochromic laminate. Background Technology

[0002] In the field of modern architecture, the demand for smart glass is growing. Electrochromic glass, as a key technology in this field, utilizes the reversible oxidation-reduction reaction of materials under the influence of an electric field to change their optical properties, thereby achieving automatic or manual adjustment of light transmittance and effectively controlling indoor light and solar radiation heat. In building applications, it can significantly reduce energy consumption.

[0003] However, existing electrochromic glass is easily affected by external factors such as temperature, humidity, and ultraviolet radiation during actual use, which causes its performance to decline to varying degrees, seriously limiting its widespread application and promotion.

[0004] In view of the above, this application is hereby submitted. Summary of the Invention

[0005] The purpose of this invention is to provide an energy-saving glass with an electrochromic interlayer, which solves the problem that electrochromic glass may be affected by external factors such as temperature, humidity, and ultraviolet radiation during use, leading to a decline in performance.

[0006] The technical problem solved by this invention is achieved by the following technical solution.

[0007] An electrochromic laminated energy-saving glass, comprising, by mass fraction:

[0008] The glass substrate comprises 83-90%, a transparent conductive layer comprising 1-5%, an ion storage layer comprising 1-3%, an ion conductor layer comprising 1-5%, and an electrochromic layer comprising 1-5%.

[0009] The glass substrate is low-iron ultra-clear glass;

[0010] The transparent conductive layer is tightly bonded to the glass substrate to form a transparent electrode;

[0011] The ion storage layer is located between the transparent conductive layer and the ion conductor layer;

[0012] The electrochromic layer is located on the other side of the ion conductor layer.

[0013] Furthermore, by mass fraction, the transparent conductive layer comprises:

[0014] Zinc oxide 90-99%, aluminum 1-10%, gallium 0.1-1%, indium 0.1-0.5%, titanium 0.05-0.2%, and zirconium 0.05-0.2%.

[0015] Furthermore, the method for preparing the transparent conductive layer is as follows:

[0016] Zinc oxide, aluminum, gallium, indium, titanium, and zirconium powders are placed in a planetary ball mill and milled at 350-450 r / min for 5-7 hours by mass fraction. The milling media are zirconium oxide balls with a diameter of 6-8 mm and the ball-to-material ratio is 6:1-7:1.

[0017] The ball-milled powder is transferred to a vacuum sintering furnace and sintered at 850-950℃ for 3-5 hours, with the heating rate controlled at 6-8℃ / min and the temperature reduced at 3-5℃ / min after the holding time.

[0018] The sintered material is pulverized again and mixed with polyvinylpyrrolidone and ethanol. The mixture is then ultrasonically dispersed at a frequency of 45-55 kHz for 40-50 min to obtain a transparent conductive layer slurry.

[0019] Using physical vapor deposition (PVD), a transparent conductive layer slurry is uniformly deposited on the glass substrate under a vacuum of 2-4 × 10⁻³ Pa and a deposition temperature of 220-280 °C at a deposition rate of 0.8-1.2 μm / min. The substrate is then annealed at 420-480 °C for 1.5-2.5 h at a heating rate of 4-6 °C / min under nitrogen protection at a flow rate of 25-30 L / min to eliminate internal stress during the deposition process, thus obtaining the transparent conductive layer.

[0020] Furthermore, the amount of polyvinylpyrrolidone added is 3-5% of the mass of the pulverized powder; the amount of ethanol added is 10-12 times the mass of the pulverized powder.

[0021] Furthermore, by mass fraction, the ion storage layer comprises:

[0022] Polyaniline 60-70%, sulfuric acid dopant 15-30%, organic sulfonic acid dopant 5-10%, crosslinking agent 5-10%, solvent 1-5%;

[0023] The organic sulfonic acid dopant is p-toluenesulfonic acid, the crosslinking agent is composed of glutaraldehyde and divinylbenzene in a mass ratio of 4:1-3:1, and the solvent is composed of N-methylpyrrolidone and γ-butyrolactone in a mass ratio of 3:1-2:1.

[0024] Furthermore, the method for preparing the ion storage layer is as follows:

[0025] By mass fraction, polyaniline, sulfuric acid dopant, organic sulfonic acid dopant, glutaraldehyde, divinylbenzene, N-methylpyrrolidone, and γ-butyrolactone are placed in a three-necked flask and stirred at 220-280 r / min for 7-9 h at a temperature of 65-75℃. Nitrogen gas is introduced for protection during stirring at a flow rate of 12-18 L / min to form an ion storage layer solution.

[0026] Using slot coating technology, the ion storage layer solution is uniformly coated onto the transparent conductive layer at a rotation speed of 1200-1400 r / min, with a coating thickness of 1.2-1.8 μm. The coating is then cured at a temperature of 85-95℃ for 3-5 h with a heating rate of 3-5℃ / min to form the ion storage layer.

[0027] Furthermore, by mass fraction, the ion-conducting layer comprises:

[0028] The composition includes 40-60% ionic liquid, 20-40% polymer matrix, 5-15% plasticizer, 1-5% stabilizer, and 0.5-3% nanofiller.

[0029] Furthermore, the ionic liquid is composed of imidazole ionic liquid and quaternary ammonium salt ionic liquid in a mass ratio of 4:1-3:1; the polymer matrix is ​​obtained by modifying polyvinylidene fluoride-hexafluoropropylene copolymer with 6-10% polyethylene glycol by mass; the plasticizer is composed of ethylene carbonate and dibutyl phthalate in a mass ratio of 3:1-2:1; the stabilizer is composed of diphenylphosphine and hindered phenolic antioxidant in a mass ratio of 6:1-5:1; and the nanofiller is composed of alumina nanoparticles and titanium dioxide nanoparticles in a mass ratio of 9:1-7:1.

[0030] Furthermore, by mass fraction, the electrochromic layer comprises:

[0031] Bismuth vanadate 30-45%, conductive additive 12-20%, stabilizer 14-22%, binder 20-30%;

[0032] The conductive additive is composed of carbon nanotubes and graphene nanosheets in a mass ratio of 3:1 to 4:1.

[0033] The stabilizer is composed of triethyl phosphate and cyclodextrin derivative in a mass ratio of 3:1 to 2:1;

[0034] The adhesive is composed of polyvinylidene fluoride and ethylene-vinyl acetate copolymer in a mass ratio of 3:1 to 2:1.

[0035] Furthermore, the method for preparing the electrochromic layer is as follows:

[0036] Bismuth vanadate, carbon nanotubes, graphene nanosheets, triethyl phosphate, cyclodextrin derivatives, polyvinylidene fluoride, and ethylene-vinyl acetate copolymer are placed in a ball mill by mass fraction and ball-milled at a speed of 450-550 r / min for 4-6 h. The ball mill jar is a polyurethane-lined ball mill jar, and the ball milling media are stainless steel balls with a diameter of 4-6 mm. The ball-to-material ratio is 5:1-6:1 to obtain ball-milled powder.

[0037] Add 7-9 times the mass of the ball-milled powder of N,N-dimethylformamide and ultrasonically disperse at a frequency of 55-65kHz for 40-50min to obtain an electrochromic layer slurry.

[0038] Using spraying or screen printing techniques, the electrochromic layer paste is uniformly coated onto the ion conductor layer. The spraying pressure is 0.4-0.6 MPa, the screen printing mesh is 220-280 mesh, and the coating is dried and cured at 105-115℃ for 4-6 hours with a heating rate of 3-5℃ / min to form the electrochromic layer.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] This invention, through optimization of the materials in each layer, enables electrochromic laminated energy-saving glass to possess excellent weather resistance, even under extreme temperatures (-40°C to 80°C), high humidity (95% RH), and strong ultraviolet radiation (irradiance of 1000 W / m²). 2 Under harsh environmental conditions such as 1000 hours of accelerated aging test, the electrochromic performance decay rate is less than 5%, and it can always maintain stable electrochromic performance, effectively avoiding performance degradation or failure caused by external environmental factors.

[0041] The ion storage layer is an organic conductive polymer system. Organic sulfonic acid dopants can increase the conductivity of polyaniline by 20-30%, broadening the potential window for ion storage and release to 0.2-0.3V. Divinylbenzene and glutaraldehyde work synergistically to form a tightly cross-linked network, increasing the tensile strength of the ion storage layer by 30-40% and reducing the elongation at break by no more than 10%, ensuring stable mechanical properties during long-term electrochromic cycling. γ-Butyrolactone can improve solution volatility and coating performance, promote uniform dispersion of each component, form a high-quality ion storage layer, and ensure rapid and stable storage and release of ions under the action of an electric field.

[0042] In the ion conductor layer, imidazole and quaternary ammonium salt ion liquids synergistically construct a highly efficient ion transport channel with a wide potential range, increasing the ion migration rate by 25-35%. The polyethylene glycol-modified polymer matrix enhances the compatibility with the ion liquid, reducing the system viscosity by 15-25% and improving the flexibility and processing performance of the ion conductor layer. Dibutyl phthalate further optimizes the processing performance of the polymer matrix, lowering the glass transition temperature by 5-10℃, facilitating coating and molding. Hindered phenolic antioxidants enhance the antioxidant properties of the stabilizer, ensuring that the weight loss rate of the ion conductor layer does not exceed 2% after aging at 150℃ for 1000 hours. Titanium dioxide nanoparticles improve the dispersibility of the nanofiller, enhancing the mechanical strength and conductivity of the ion conductor layer, increasing conductivity by 10-15%, and providing more effective pathways for ion migration. Attached Figure Description

[0043] The accompanying drawings are provided to further illustrate the present invention and, together with the embodiments thereof, are used to explain the present invention, but do not constitute a limitation thereof.

[0044] Figure 1 These are performance test tables and graphs of embodiments and comparative examples of the present invention. Detailed Implementation

[0045] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0046] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other. The present invention will now be described in detail with reference to specific embodiments.

[0047] The sources of some components in the examples and comparative examples are as follows:

[0048] Polyvinylidene fluoride-hexafluoropropylene copolymer, CAS No. 25038-71-5, purchased from Dongguan Fluoropon Anticorrosion Materials Co., Ltd.

[0049] Polyethylene glycol, CAS No. 25322-68-3, was purchased from Guangzhou Aobosheng Chemical Co., Ltd.

[0050] Polyaniline, CAS No. 25233-30-1, purchased from Hubei Shineng Chemical Technology Co., Ltd.

[0051] Sulfuric acid dopant (98% sulfuric acid), CAS No. 7664-93-9, purchased from Henan Dongke Chemical Products Sales Co., Ltd.

[0052] p-Toluenesulfonic acid, CAS No. 104-15-4, purchased from Langfang Qianyao Technology Co., Ltd.

[0053] Glutaraldehyde (50% aqueous solution), CAS No. 111-30-8, purchased from Guangzhou Xinhong Trading Co., Ltd.

[0054] Divinylbenzene, CAS No. 1321-74-0, was purchased from Zhengzhou Alpha Chemical Co., Ltd.

[0055] N-Methylpyrrolidone, CAS No. 872-50-4, purchased from Tianjin Yongda Chemical Reagent Co., Ltd.

[0056] γ-Butyrolactone, CAS No. 96-48-0, purchased from Wuhan Yuancheng Technology Development Co., Ltd.;

[0057] Ionic liquids (composed of imidazole ionic liquid [1-butyl-3-methylimidazolium hexafluorophosphate, CAS No. 174501-64-5] and quaternary ammonium salt ionic liquid [tetrabutylammonium bromide, CAS No. 1643-19-2] in a mass ratio of 3:2), wherein the imidazole ionic liquid was purchased from Wuhan Yuancheng Technology Development Co., Ltd., and the quaternary ammonium salt ionic liquid was purchased from a chemical reagent factory in Henan Province;

[0058] Ethylene carbonate, CAS No. 96-49-1, purchased from Linzhou Keneng Materials Technology Co., Ltd.

[0059] Dibutyl phthalate, CAS No. 84-74-2, purchased from Guangdong Daxiao Chemical Co., Ltd.

[0060] Diphenylphosphodiphenyl ester, CAS No. 26444-49-5, was purchased from Wuhan Shuer Biotechnology Co., Ltd.

[0061] Hindered phenolic antioxidant (antioxidant 1010, CAS No. 6683-19-8), purchased from Guangzhou Wanggang Trading Co., Ltd.

[0062] Alumina nanoparticles, CAS No. 1344-28-1, were purchased from Foshan Guohu Nanomaterials Co., Ltd.

[0063] Titanium dioxide nanoparticles, CAS No. 13463-67-7, were purchased from Guangzhou Hualisen Trading Co., Ltd.

[0064] Bismuth vanadate, CAS No. 14059-33-7, was purchased from Kohler Pigment Co., Ltd. in Xiangtan City.

[0065] Carbon nanotubes, CAS No. 308068-56-6, purchased from Shenzhen Huachuang Magnetics Co., Ltd.

[0066] Graphene nanosheets, CAS No. 1034343-98-0, purchased from Qingdao Yanhai Carbon Materials Co., Ltd.

[0067] Triethyl phosphate, CAS No. 78-40-0, was purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0068] Cyclodextrin derivative (hydroxypropyl-β-cyclodextrin, CAS No. 128446-35-5) was purchased from Hubei Dixing Chemical Manufacturing Co., Ltd.

[0069] Ethylene-vinyl acetate copolymer, CAS No. 24937-78-8, purchased from Guangzhou Daixun Trading Co., Ltd.

[0070] Siloxane coatings, Shandong Bojie Medical Environmental Protection Engineering Co., Ltd.;

[0071] ITO material, purchased from Shenzhen Bangkai Adhesive Products Co., Ltd.

[0072] Acrylic coating, purchased from Shandong Bojie Medical Environmental Protection Engineering Co., Ltd.

[0073] Polyurethane coating, purchased from Shandong Bojie Medical Environmental Protection Engineering Co., Ltd.

[0074] Silicone rubber coating, purchased from Shandong Bojie Medical Environmental Protection Engineering Co., Ltd.

[0075] Preparation of the transparent conductive layer: Weighed zinc oxide, aluminum, gallium, indium, titanium, and zirconium powders were placed in a planetary ball mill. Zirconia balls with a diameter of 6 mm were used as the milling media, and the ball-to-material ratio was set to 6.5:1. The mill was run at 400 r / min for 6 hours, with a 10-minute stop every hour to prevent overheating and agglomeration. The material was also agitated to ensure uniform dispersion of each element. After milling, the powder was transferred to a vacuum sintering furnace and sintered at 900℃ for 4 hours, with a heating rate controlled at 7℃ / min. After holding at this temperature, the powder was cooled at a rate of 4℃ / min to allow for sufficient reaction and the formation of a stable doped structure. The sintered material was then pulverized again and mixed with 4% polyvinylpyrrolidone dispersant and 11 times the powder mass of ethanol solvent. The mixture was ultrasonically dispersed at 50 kHz for 45 minutes to obtain a uniform transparent conductive layer slurry. Physical vapor deposition (PVD) was then performed under a vacuum of 3 × 10⁻⁶ ppm. -3 Under conditions of Pa and a deposition temperature of 250℃, the transparent conductive layer slurry was uniformly deposited on a glass substrate at a deposition rate controlled at 1 μm / min. After deposition, annealing was performed at 450℃ for 2 h with a heating rate of 5℃ / min and a nitrogen protective atmosphere at a flow rate of 28 L / min to eliminate internal stress during the deposition process, improve the adhesion and stability of the transparent conductive layer to the glass substrate, and thus obtain a high-quality transparent conductive layer.

[0076] Preparation of the ion storage layer: Weighed polyaniline, sulfuric acid dopant, p-toluenesulfonic acid, glutaraldehyde, divinylbenzene, N-methylpyrrolidone, and γ-butyrolactone were placed in a three-necked flask. An anchor-type stirrer was installed, and the mixture was stirred at 250 r / min for 8 h at 70 °C. Nitrogen gas was continuously purged during stirring at a flow rate of 15 L / min to ensure complete dissolution and reaction of all components, forming a homogeneous ion storage layer solution. Using spin coating technology, the ion storage layer solution was uniformly coated onto a transparent conductive layer at a speed of 1300 r / min, with the coating thickness controlled at 1.5 μm. After coating, the layer was cured at 90 °C for 4 h at a heating rate of 4 °C / min to allow the solvent to evaporate completely, forming a dense ion storage layer. The ion diffusion coefficient of the ion storage layer was tested using an electrochemical workstation, and the results showed that its ion diffusion coefficient was 5 × 10⁻⁶. -8 cm 2 / s indicates good ion storage and release performance.

[0077] Preparation of the ion conductor layer: Weighed ionic liquid, modified polyvinylidene fluoride-hexafluoropropylene copolymer, ethylene carbonate, dibutyl phthalate, diphenylphosphamide, hindered phenolic antioxidant, alumina nanoparticles, and titanium dioxide nanoparticles were placed in a high-speed mixer with serrated blades and stirred at 900 r / min for 5 h. During stirring, a vacuum of 65 kPa was applied to ensure initial homogeneity of the components. The mixture was then transferred to a twin-screw extruder and melt-blended at 200 °C with a screw speed of 130 r / min and an aspect ratio of 35:1. The extrudate was granulated and pulverized to obtain the ion conductor layer material. The ion conductor layer material was uniformly coated onto the ion storage layer using a hot-pressing method at 135 °C, a pressure of 7 MPa, and a holding time of 7 min to form a stable ion conductor layer. The ionic conductivity of the ion conductor layer was tested using AC impedance spectroscopy. At a frequency of 100 Hz, the ionic conductivity was 5 mS / cm, indicating excellent ion conduction performance.

[0078] Preparation of the electrochromic layer: Weighed bismuth vanadate, carbon nanotubes, graphene nanosheets, triethyl phosphate, cyclodextrin derivatives, polyvinylidene fluoride, and ethylene-vinyl acetate copolymer were placed in a ball mill. A polyurethane-lined ball mill jar was used, with 5mm diameter stainless steel balls as the milling media. The ball-to-material ratio was 5.5:1. The mixture was ball-milled at 500 rpm for 5 hours to ensure uniform mixing of all components. Eight times the mass of the powder was added as N,N-dimethylformamide solvent, and the mixture was ultrasonically dispersed at 60 kHz for 45 minutes to obtain a uniform electrochromic layer slurry. The electrochromic layer was then applied using a spraying technique. The slurry was uniformly coated on the ion conductor layer under a spraying pressure of 0.5 MPa and dried and cured at 110°C for 5 hours at a heating rate of 4°C / min to allow the solvent to evaporate and the components to bind tightly, forming a high-performance electrochromic layer. The color-changing performance of the electrochromic layer was tested using a spectrophotometer. When a voltage of 3V was applied, its transmittance at a wavelength of 550nm decreased from 80% to 20%, and the color-changing response time was 5 seconds. After 10,000 cycles of color-changing testing, the transmittance change rate was within 10%, indicating good electrochromic performance and high cycle stability.

[0079] More specifically, the glass substrate possesses high transparency, low impurity content, and good thermal stability; its coefficient of thermal expansion varies within ±5×10⁻⁶ temperature ranges from -40℃ to 80℃. -6 Within / ℃, it ensures tight bonding with each functional layer under different temperature environments without causing significant stress deformation, thus maintaining the integrity of the overall glass structure;

[0080] The transparent conductive layer is an aluminum-doped zinc oxide material with multiple dopants. The introduction of titanium can refine the zinc oxide grains to an average particle size of 20-30 nm, enhance the stability of the crystal structure, and improve the corrosion resistance of the material in acidic, alkaline, and humid environments. Zirconium optimizes the electron migration path, increasing the electron mobility by 15-25%, thereby significantly enhancing the electrical conductivity and environmental adaptability of the material, ensuring that it provides an efficient electron transport channel for the electrochromic process under complex external conditions.

[0081] The ion storage layer is an organic conductive polymer system. Organic sulfonic acid dopants can increase the conductivity of polyaniline by 20-30%, widening the potential window for ion storage and release to 0.2-0.3V. Divinylbenzene and glutaraldehyde work synergistically to form a tightly cross-linked network, increasing the tensile strength of the ion storage layer by 30-40% and reducing the elongation at break by no more than 10%, ensuring stable mechanical properties during long-term electrochromic cycling. γ-Butyrolactone improves solution volatility and coating performance, promotes uniform dispersion of components, and forms a high-quality ion storage layer, ensuring rapid and stable storage and release of ions under the action of an electric field.

[0082] Imidazole and quaternary ammonium salt ionic liquids synergistically construct a highly efficient ion transport channel with a wide potential range in the ion conductor layer, increasing the ion migration rate by 25-35%. The polyethylene glycol-modified polymer matrix enhances the compatibility with the ionic liquid, reducing the system viscosity by 15-25% and improving the flexibility and processing performance of the ion conductor layer. Dibutyl phthalate further optimizes the processing performance of the polymer matrix, lowering the glass transition temperature by 5-10℃, facilitating coating and molding. Hindered phenolic antioxidants enhance the antioxidant properties of the stabilizer, ensuring that the weight loss rate of the ion conductor layer does not exceed 2% after aging at 150℃ for 1000 hours. Titanium dioxide nanoparticles improve the dispersibility of the nanofiller, enhancing the mechanical strength and conductivity of the ion conductor layer, increasing conductivity by 10-15%, and providing more effective pathways for ion migration.

[0083] In the electrochromic layer, graphene nanosheets and carbon nanotubes construct a three-dimensional conductive network, increasing the conductivity of the electrochromic layer by 30-40%, accelerating ion migration, and shortening the color-changing response time to 5-8 seconds. Cyclodextrin derivatives form supramolecular structures with other components, improving the chemical stability of the electrochromic layer. After 1000 cycles of color-changing testing, the optical performance degradation rate does not exceed 5%. Ethylene-vinyl acetate copolymer improves the flexibility and adhesion of the binder, ensuring that the components of the electrochromic layer are tightly bonded. Under different humidity environments (20%-90%RH), the change rate of the bonding strength does not exceed 8%, maintaining a uniform and stable structure and ensuring stable electrochromic performance.

[0084] The transparent conductive layer is tightly bonded to the glass substrate to form a transparent electrode, with an interfacial bonding strength of not less than 30 MPa, ensuring no delamination during long-term use and temperature changes; the ion storage layer is located between the transparent conductive layer and the ion conductor layer, forming a stable ion transport and storage structure; the electrochromic layer is located on the other side of the ion conductor layer, achieving efficient electrochromic function under the action of an electric field.

[0085] Example 1

[0086] Glass substrate: Low-iron ultra-clear glass with a thickness of 5mm is selected as the glass substrate, and its transmittance in the wavelength range of 380-780nm is tested to be 92%.

[0087] Transparent conductive layer material: Accurately weigh the powder raw materials according to the mass fraction of 95% zinc oxide, 4% aluminum, 0.5% gallium, 0.5% indium, 0.1% titanium, and 0.1% zirconium; among which, the purity of zinc oxide powder is 99.9%, the particle size of aluminum powder is controlled within 1-3μm, and the particle size of gallium, indium, titanium, and zirconium powders are all within the range of 0.5-1μm.

[0088] Ion storage layer material: Weigh out 65% polyaniline, 18% sulfuric acid dopant, 7% p-toluenesulfonic acid, 9% glutaraldehyde, 4% divinylbenzene, 4% N-methylpyrrolidone, and 2% γ-butyrolactone. The molecular weight of polyaniline is approximately 50,000-80,000 g / mol, the concentration of sulfuric acid dopant is 98%, the purity of p-toluenesulfonic acid is 99%, the mass fraction of glutaraldehyde is 50%, the purity of divinylbenzene is 98%, and the purity of both N-methylpyrrolidone and γ-butyrolactone is above 99%.

[0089] Ion conductor layer material: 50% ionic liquid (composed of imidazole ionic liquid and quaternary ammonium salt ionic liquid in a mass ratio of 4:1), 25% polyvinylidene fluoride-hexafluoropropylene copolymer (modified with 8% polyethylene glycol by mass), 9% ethylene carbonate, 4% dibutyl phthalate, 4% diphenylphosphamide, 0.8% hindered phenolic antioxidant, 4% alumina nanoparticles, and 0.2% titanium dioxide nanoparticles. The purity of both the imidazole ionic liquid and the quaternary ammonium salt ionic liquid is above 99%. The molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer is approximately 400,000-600,000 g / mol. The purity of ethylene carbonate, dibutyl phthalate, diphenylphosphamide, and hindered phenolic antioxidant all reach 99%. The average particle size of the alumina nanoparticles is 50 nm, and the average particle size of the titanium dioxide nanoparticles is 30 nm.

[0090] Electrochromic layer material: 40% bismuth vanadate, 13% carbon nanotubes, 4% graphene nanosheets, 17% triethyl phosphate, 6% cyclodextrin derivatives, 20% polyvinylidene fluoride, and 8% ethylene-vinyl acetate copolymer. The crystallinity of bismuth vanadate is above 90%, the diameter of the carbon nanotubes is 10-20 nm and the length is 5-10 μm, the number of graphene nanosheets is 3-5 layers, the purity of triethyl phosphate is 99%, the degree of substitution of the cyclodextrin derivative is 0.5-0.8, the molecular weight of polyvinylidene fluoride is approximately 300,000-500,000 g / mol, and the vinyl acetate content of the ethylene-vinyl acetate copolymer is 18%-25%, ensuring excellent performance of the electrochromic layer material.

[0091] Protective layer material: Siloxane coating is selected as the protective layer material, with a solid content of 40%-50% and a viscosity between 1000-1500 mPa·s.

[0092] Example 2:

[0093] Glass substrate: Low-iron ultra-white glass with a thickness of 4mm is selected, which has a light transmittance of 93% in the wavelength range of 380-780nm.

[0094] Transparent conductive layer material: Weigh out powder raw materials of 90% zinc oxide, 8% aluminum, 1% gallium, 1% indium, 0.2% titanium, and 0.2% zirconium. The purity and particle size requirements of each raw material are the same as in Example 1.

[0095] Ion storage layer material: Prepare 70% polyaniline, 15% sulfuric acid dopant, 10% p-toluenesulfonic acid, 8% glutaraldehyde, 5% divinylbenzene, 4% N-methylpyrrolidone, and 3% γ-butyrolactone. The specifications of each reagent are the same as in Example 1.

[0096] The ion conductor layer material consists of 40% ionic liquid (composed of imidazole ionic liquid and quaternary ammonium salt ionic liquid in a mass ratio of 3:1), 30% polyvinylidene fluoride-hexafluoropropylene copolymer (containing 10% polyethylene glycol modification), 10% ethylene carbonate, 5% dibutyl phthalate, 4% diphenylphosphamide, 0.7% hindered phenolic antioxidant, 4% alumina nanoparticles, and 0.3% titanium dioxide nanoparticles. The parameters of each material are similar to those in Example 1.

[0097] Electrochromic layer material: Weigh out 35% bismuth vanadate, 18% carbon nanotubes, 5% graphene nanosheets, 20% triethyl phosphate, 7% cyclodextrin derivative, 15% polyvinylidene fluoride, and 10% ethylene-vinyl acetate copolymer. The material properties are the same as in Example 1.

[0098] Protective layer material: The same siloxane coating as in Example 1 is used.

[0099] Example 3:

[0100] Glass substrate: 6mm thick low-iron ultra-white glass with a transmittance of 91% in the wavelength range of 380-780nm.

[0101] Transparent conductive layer material: Weigh out powder raw materials of 99% zinc oxide, 1% aluminum, 0.1% gallium, 0.1% indium, 0.05% titanium, and 0.05% zirconium. The quality requirements of each raw material are the same as those in the above embodiments.

[0102] Ion storage layer material: Prepare 60% polyaniline, 30% sulfuric acid dopant, 5% p-toluenesulfonic acid, 5% glutaraldehyde, 3% divinylbenzene, 5% N-methylpyrrolidone, and 1% γ-butyrolactone. The purity and other parameters of each reagent are in accordance with the settings of Example 1.

[0103] The ion conductor layer material consists of 60% ionic liquid (composed of imidazole ionic liquid and quaternary ammonium salt ionic liquid in a mass ratio of 5:2), 20% polyvinylidene fluoride-hexafluoropropylene copolymer (containing 6% polyethylene glycol modification), 15% ethylene carbonate, 3% dibutyl phthalate, 1% diphenylphosphamide, 0.5% hindered phenolic antioxidant, 4% alumina nanoparticles, and 0.5% titanium dioxide nanoparticles. The material properties are the same as in Example 1.

[0104] Electrochromic layer material: 45% bismuth vanadate, 12% carbon nanotubes, 3% graphene nanosheets, 14% triethyl phosphate, 5% cyclodextrin derivative, 21% polyvinylidene fluoride, and 9% ethylene-vinyl acetate copolymer were weighed. The properties of the material were consistent with those in Example 1.

[0105] Protective layer material: The siloxane coating from Example 1 is selected.

[0106] Comparative Example 1:

[0107] Glass substrate: The same 5mm low-iron ultra-clear glass as in Example 1 is used.

[0108] Transparent conductive layer material: Ordinary magnetron sputtered ITO material is prepared to replace the aluminum-doped zinc oxide material of the present invention.

[0109] Ion storage layer material: the same organic conductive polymer material as in Example 1, consisting of 65% polyaniline, 18% sulfuric acid dopant, 7% p-toluenesulfonic acid, 9% glutaraldehyde, 4% divinylbenzene, 4% N-methylpyrrolidone, and 2% γ-butyrolactone.

[0110] Ion conductor layer material: Same as the ion conductor layer material in Example 1, comprising 50% ionic liquid (imidazolium ionic liquid and quaternary ammonium salt ionic liquid in a mass ratio of 4:1), 25% polyvinylidene fluoride-hexafluoropropylene copolymer (modified with 8% polyethylene glycol by mass), 9% ethylene carbonate, 4% dibutyl phthalate, 4% diphenylphosphamide, 0.8% hindered phenolic antioxidant, 4% alumina nanoparticles, and 0.2% titanium dioxide nanoparticles.

[0111] Electrochromic layer material: The same material as in Example 1 is used, but the binder is changed to PVB, 40% bismuth vanadate, 13% carbon nanotubes, 4% graphene nanosheets, 17% triethyl phosphate, 6% cyclodextrin derivative, 20% PVB, and 8% ethylene-vinyl acetate copolymer.

[0112] Protective layer material: ordinary acrylic coating with a solid content of 30%-40% and a viscosity between 800-1200 mPa·s.

[0113] The preparation method is as follows:

[0114] The transparent conductive layer was deposited on a glass substrate using magnetron sputtering technology. The sputtering power was 150W, the sputtering time was 30min, and the deposition thickness was approximately 200nm. No annealing treatment was performed.

[0115] The preparation methods of the ion storage layer, ion conductor layer and electrochromic layer are similar to the corresponding steps in Example 1, but due to differences in material properties, the process parameters are slightly adjusted. The spin coating speed of the ion storage layer is 1100 r / min, the coating thickness is 1.4 μm, and it is cured at 90℃ for 3.5 h; the hot pressing temperature of the ion conductor layer is 130℃, the pressure is 6 MPa, and the holding time is 6 min; the spraying pressure of the electrochromic layer is 0.4 MPa, and it is dried and cured at 105℃ for 4.5 h.

[0116] The assembly and packaging process is carried out in a normal workshop environment. After the layers are assembled, ordinary acrylic paint is applied by brushing. The coating thickness is about 5μm, and it is dried and cured at 60℃ for 3 hours.

[0117] Comparative Example 2:

[0118] Glass substrate: Ordinary float glass with a thickness of 4mm is used, which has a light transmittance of 85% in the wavelength range of 380-780nm.

[0119] Transparent conductive layer material: Powdered raw materials of 92% zinc oxide, 6% aluminum, 0.8% gallium and 0.6% indium by mass fraction were weighed, but titanium and zirconium were not added. The purity and particle size requirements of each raw material were similar to those in Example 1.

[0120] Ion storage layer material: Weigh out 68% polyaniline, 22% sulfuric acid dopant, 8% glutaraldehyde, and 2% N-methylpyrrolidone. No organic sulfonic acid dopant or divinylbenzene was added, and the specifications of each reagent are somewhat different from those in Example 1. For example, the molecular weight of polyaniline is about 40,000-60,000 g / mol, and the concentration of sulfuric acid dopant is 95%.

[0121] Ion conductor layer material: 45% ionic liquid (imidazolium ionic liquid only), 32% unmodified polyvinylidene fluoride-hexafluoropropylene copolymer, 12% ethylene carbonate, 6% diphenylphosphine, and 5% alumina nanoparticles were prepared. Quaternary ammonium salt ionic liquid, polyethylene glycol, dibutyl phthalate, and titanium dioxide nanoparticles were not added. The parameters of each material are different from those in Example 1.

[0122] Electrochromic layer material: 38% bismuth vanadate, 16% carbon nanotubes, 20% triethyl phosphate, and 26% polyvinylidene fluoride were weighed out. No graphene nanosheets and cyclodextrin derivatives were added. The material properties are different from those in Example 1.

[0123] Protective layer material: A common polyurethane coating is used, with a solid content of 35%-45% and a viscosity between 900-1300 mPa·s.

[0124] Preparation method:

[0125] For the preparation of the transparent conductive layer, the powder was placed in a planetary ball mill and milled at 350 r / min for 4 h using 6 mm diameter zirconia balls at a ball-to-powder ratio of 5:1. Sintering was carried out at 850 °C for 3 h, with heating at 6 °C / min and cooling at 3 °C / min. After pulverization, the powder was mixed with 3% (w / w) polyvinylpyrrolidone and 9 times the powder weight of ethanol, and ultrasonically dispersed at 45 kHz for 40 min. The mixture was then subjected to physical vapor deposition under a vacuum of 2 × 10⁻⁶. -3 The deposition was carried out at 220°C with a deposition rate of 0.8 μm / min, followed by annealing at 420°C for 1.5 h, with a heating rate of 4°C / min and a nitrogen flow rate of 22 L / min.

[0126] The ion storage layer was stirred at 200 rpm for 6 h at 65 °C in a three-necked flask without nitrogen protection. A 1.2 μm thick layer was then coated by spin coating at 1000 rpm and cured at 85 °C for 3 h with a temperature increase of 3 °C / min.

[0127] The ion conductor layer was stirred in a high-speed mixer at 800 r / min for 4 h without vacuum. It was processed by a twin-screw extruder at 185℃, screw speed of 110 r / min, and length-to-diameter ratio of 30:1; and hot-pressed at 125℃, 5 MPa, and 5 min.

[0128] The electrochromic layer was ball-milled at 400 r / min for 4 h, with the same ball mill jar and ball-to-material ratio as in Example 1; 7 times the powder weight of N,N-dimethylformamide was added, and the mixture was ultrasonically dispersed at 50 kHz for 40 min. The spraying pressure was 0.35 MPa, and the mixture was dried and cured at 100 °C for 4 h, with a temperature increase of 3 °C / min.

[0129] Assembly and encapsulation are carried out in a standard workshop, with bonding accuracy controlled within ±0.05mm. Polyurethane coating is applied at a thickness of 6μm, a spraying distance of 18cm, and cured at 70℃ for 3.5h with a temperature increase rate of 3.5℃ / min.

[0130] Comparative Example 3:

[0131] Glass substrate: Low-iron ultra-white glass with a thickness of 6mm is selected, which has a light transmittance of 90% in the wavelength range of 380-780nm.

[0132] Transparent conductive layer material: Weigh out powder raw materials of 97% zinc oxide, 2% aluminum, 0.5% gallium and 0.5% indium, without adding titanium and zirconium elements, and the purity and particle size requirements of each raw material are similar to those in Example 1.

[0133] Ion storage layer material: 72% polyaniline, 16% sulfuric acid dopant, 8% p-toluenesulfonic acid, 4% glutaraldehyde, and 4% N-methylpyrrolidone were prepared. Divinylbenzene and γ-butyrolactone were not added. The specifications of each reagent differed from those in Example 1.

[0134] The ion conductor layer material consists of 55% ionic liquid (composed of imidazole ionic liquid and quaternary ammonium salt ionic liquid in a mass ratio of 3:2), 22% polyvinylidene fluoride-hexafluoropropylene copolymer (containing 5% polyethylene glycol modification), 10% ethylene carbonate, 6% dibutyl phthalate, 3% diphenylphosphamide, 0.7% hindered phenolic antioxidant, 4% alumina nanoparticles, and 0.3% titanium dioxide nanoparticles. The material properties are the same as in Example 1, but some proportions are different.

[0135] Electrochromic layer material: 42% bismuth vanadate, 14% carbon nanotubes, 4% graphene nanosheets, 18% triethyl phosphate, 4% cyclodextrin derivative, 18% polyvinylidene fluoride, and 10% ethylene-vinyl acetate copolymer were weighed. The various properties of the material are somewhat different from those in Example 1.

[0136] Protective layer material: A silicone rubber coating with a solid content of 40%-50% and a viscosity between 1100-1600 mPa·s is selected.

[0137] The preparation method is as follows:

[0138] The transparent conductive layer was prepared as follows: The powder was placed in a planetary ball mill and milled at 450 r / min for 7 h using 7 mm diameter zirconia balls as the milling media, with a ball-to-powder ratio of 7:1. Sintering was carried out at 950℃ for 5 h, with a heating rate of 8℃ / min and a cooling rate of 5℃ / min. After pulverization, the powder was mixed with 4.5% (w / w) polyvinylpyrrolidone and 12 times the powder mass of ethanol, and ultrasonically dispersed at 55 kHz for 50 min. Physical vapor deposition was performed under a vacuum of 4 × 10⁻³ Pa at 280℃ with a deposition rate of 1.2 μm / min, followed by annealing at 480℃ for 2.5 h with a heating rate of 6℃ / min and a nitrogen flow rate of 30 L / min.

[0139] The ion storage layer was stirred at 300 rpm for 9 h at 75 °C in a three-necked flask under nitrogen protection at a flow rate of 18 L / min. A 1.8 μm thick layer was then coated by spin coating at 1400 rpm and cured at 95 °C for 5 h with a temperature increase of 5 °C / min.

[0140] The ion conductor layer was stirred at 950 rpm for 6 hours in a high-speed mixer, and then evacuated to 70 kPa. It was then processed using a twin-screw extruder at 215℃, screw speed of 140 rpm, and a length-to-diameter ratio of 38:1. Finally, it was hot-pressed at 140℃, 8 MPa, for 9 minutes.

[0141] The electrochromic layer was ball-milled at 550 r / min for 6 h, with the same ball mill jar and ball-to-material ratio as in Example 1; 9 times the powder weight of N,N-dimethylformamide was added, and the mixture was ultrasonically dispersed at 65 kHz for 50 min. The spraying pressure was 0.6 MPa, and the mixture was dried and cured at 115 °C for 6 h with a temperature increase of 5 °C / min.

[0142] Assembly and encapsulation were carried out in a cleanroom with a cleanliness level of 5000, and the bonding accuracy was controlled within ±0.04mm. Silicone rubber coating was applied with a thickness of 8μm at a spraying distance of 22cm, and cured at 85℃ for 5h with a temperature increase of 5℃ / min.

[0143] The performance of the energy-saving glass provided in the above embodiments and comparative examples was tested.

[0144] Performance test data such as Figure 1 As shown.

[0145] As can be seen from the above, Examples 1-3 of the present invention exhibit superior performance advantages through carefully designed material formulations and rigorous preparation processes. Regarding the electrochromic response time, all examples complete the color-changing process within a short time (5-5.5 seconds), meeting the requirement for rapid adjustment of light transmittance. In contrast, the response time of Comparative Examples 1-3 is significantly longer (10-15 seconds), which will affect their timeliness and convenience in practical applications.

[0146] In terms of cycle life, the transmittance change rate of the embodiment can still be controlled within 11% after 10,000 cycles, ensuring long-term stable performance. In contrast, the transmittance change rate of the comparative embodiment exceeds 18% or even reaches 25% after a few fewer cycles (4,000-6,000 cycles), indicating poor durability and the need for frequent replacement, which increases the cost of use and maintenance difficulty.

[0147] Regarding the light transmittance of the glass, the glass in the embodiment maintains a high light transmittance (91%-93%) in the wavelength range of 380-780nm, ensuring good lighting effect and visual clarity, while the light transmittance of the comparative embodiment is relatively low (80%-88%), which may affect the indoor lighting environment and visual experience.

[0148] The superior waterproof performance and salt spray resistance further highlight the significant advantages of this invention. The embodiment exhibits excellent waterproof performance, with a water contact angle of 108°-112°, effectively preventing moisture intrusion. Furthermore, its electrochromic performance shows no significant decrease after 1000 hours of salt spray testing, demonstrating its ability to withstand harsh environmental conditions. In contrast, the comparative embodiment exhibits weaker waterproof performance, with a water contact angle of only 80°-92°. In salt spray testing, its electrochromic performance shows a significant decrease after 400-600 hours, making it difficult to maintain stable performance in complex environments and severely limiting its application range and service life.

[0149] Therefore, the electrochromic laminated energy-saving glass and its preparation method of the present invention have achieved significant results in solving the problem of performance degradation of electrochromic glass due to external factors. Compared with the comparative example, it has obvious advantages and higher practical value, and can better meet the market demand for high-performance energy-saving glass, and has broad application prospects in the construction field.

[0150] The embodiments described above are some, but not all, embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. Energy saving glass of electrochromic sandwich, characterized in that, Composed of the following ingredients by mass fraction: Glass substrate 83-90 parts, transparent conductive layer 1-5 parts, ion storage layer 1-3 parts, ion conductor layer 1-5 parts, electrochromic layer 1-5 parts; The glass substrate is low-iron ultra-white glass; The transparent conductive layer is closely combined with the glass substrate to form a transparent electrode; The ion storage layer is located between the transparent conductive layer and the ion conductor layer; The electrochromic layer is located on the other side of the ion conductor layer; The ion storage layer is composed of the following ingredients by mass fraction: polyaniline 60-70 parts, sulfuric acid dopant 15-30 parts, organic sulfonic acid dopant 5-10 parts, crosslinking agent 5-10 parts, solvent 1-5 parts; The organic sulfonic acid dopant is p-toluenesulfonic acid, the crosslinking agent is composed of glutaraldehyde and divinylbenzene in a mass ratio of 4:1-3:1, and the solvent is composed of N-methyl pyrrolidone and gamma-butyrolactone in a mass ratio of 3:1-2:

1.

2. The energy saving glass of electrochromic sandwich according to claim 1, characterized in that, The transparent conductive layer is composed of the following ingredients by mass fraction: Zinc oxide 90-99 parts, aluminum 1-10 parts, gallium 0.1-1 part, indium 0.1-0.5 part, titanium 0.05-0.2 part, and zirconium 0.05-0.2 part.

3. The energy saving glass of electrochromic sandwich according to claim 2, characterized in that, The preparation method of the transparent conductive layer is: Put the zinc oxide, aluminum, gallium, indium, titanium, and zirconium powders into a planetary ball mill, and ball mill at a speed of 350-450 r / min for 5-7 h, wherein the ball milling medium is zirconia ball with a diameter of 6-8 mm, and the ball-to-material ratio is 6:1-7:1; Transfer the ball-milled powder to a vacuum sintering furnace, sinter at a temperature of 850-950℃ for 3-5 h, wherein the heating rate is controlled at 6-8℃ / min, and after the holding time, cool down at a rate of 3-5℃ / min; Grind the sintered material again, mix it with polyvinylpyrrolidone and ethanol, and ultrasonically disperse at a frequency of 45-55 kHz for 40-50 min to obtain a transparent conductive layer slurry; The transparent conductive layer paste is uniformly deposited on the glass substrate by physical vapor deposition technology under the conditions of vacuum degree of 2×10 -3 -4×10 -3 Pa, deposition temperature of 220-280℃, deposition rate of 0.8-1.2μm / min, annealing treatment at temperature of 420-480℃ for 1.5-2.5h, heating rate of 4-6℃ / min, and nitrogen protection with flow rate of 25-30L / min to eliminate internal stress in the deposition process, thereby obtaining the transparent conductive layer.

4. The energy saving glass of electrochromic sandwich according to claim 3, characterized in that, The addition amount of polyvinylpyrrolidone is 3-5% of the mass of the ground powder, and the addition amount of ethanol is 10-12 times the mass of the ground powder.

5. The energy saving glass of electrochromic sandwich according to claim 1, characterized in that, The preparation method of the ion storage layer is: Put the polyaniline, sulfuric acid dopant, organic sulfonic acid dopant, glutaraldehyde, divinylbenzene, N-methyl pyrrolidone, and gamma-butyrolactone into a three-necked flask, stir at a speed of 220-280 r / min at a temperature of 65-75℃ for 7-9 h, and protect with nitrogen gas during stirring at a flow rate of 12-18 L / min to form an ion storage layer solution; Use slit coating technology to uniformly coat the ion storage layer solution on the transparent conductive layer at a speed of 1200-1400 r / min, with a coating thickness of 1.2-1.8 μm, and perform solidification treatment at a temperature of 85-95℃ for 3-5 h at a heating rate of 3-5℃ / min to form the ion storage layer.

6. The energy saving glass of electrochromic sandwich according to claim 1, characterized in that, The ion conductor layer is composed of the following ingredients by mass fraction: ionic liquid 40-60 parts, polymer matrix 20-40 parts, plasticizer 5-15 parts, stabilizer 1-5 parts, and nano filler 0.5-3 parts.

7. The energy saving glass of electrochromic sandwich according to claim 6, characterized in that, The ionic liquid is composed of imidazole ionic liquid and quaternary ammonium salt ionic liquid in a mass ratio of 4:1-3:1, the polymer matrix is polyvinylidene fluoride-hexafluoropropylene copolymer modified by introducing 6-10% of polyethylene glycol in mass fraction, the plasticizer is composed of ethylene carbonate and dibutyl phthalate in a mass ratio of 3:1-2:1, the stabilizer is composed of diphenyl phosphate and hindered phenolic antioxidant in a mass ratio of 6:1-5:1, and the nano filler is composed of aluminum oxide nanoparticles and titanium dioxide nanoparticles in a mass ratio of 9:1-7:

1.

8. The energy saving glass of electrochromic sandwich according to claim 1, characterized in that, The electrochromic layer is composed of the following components in mass parts: 30-45 parts of bismuth vanadate, 12-20 parts of conductive additive, 14-22 parts of stabilizer, and 20-30 parts of binder; The conductive additive is composed of carbon nanotubes and graphene nanosheets in a mass ratio of 3:1-4:1; The stabilizer is composed of triethyl phosphate and cyclodextrin derivative in a mass ratio of 3:1-2:1; The binder is composed of polyvinylidene fluoride and ethylene-vinyl acetate copolymer in a mass ratio of 3:1-2:

1.

9. The energy saving glass of electrochromic sandwich according to claim 8, characterized in that, The preparation method of the electrochromic layer is as follows: Put the bismuth vanadate, carbon nanotubes, graphene nanosheets, triethyl phosphate, cyclodextrin derivative, polyvinylidene fluoride, and ethylene-vinyl acetate copolymer into a ball mill, and ball mill at a speed of 450-550 r / min for 4-6 h, the ball mill tank is a polyurethane-lined ball mill tank, the ball mill medium is a stainless steel ball with a diameter of 4-6 mm, and the ball-to-material ratio is 5:1-6:1 to obtain a ball milled powder; Add 7-9 times the mass of the ball milled powder of N,N-dimethylformamide, and ultrasonically disperse at a frequency of 55-65 kHz for 40-50 min to obtain an electrochromic layer slurry; Use spraying or screen printing technology to uniformly coat the electrochromic layer slurry on the ion conductor layer, the spraying pressure is 0.4-0.6 MPa, the screen printing mesh number is 220-280 meshes, and drying and curing treatment is carried out at a temperature of 105-115℃ for 4-6 h at a heating rate of 3-5℃ / min to form the electrochromic layer.

Images