Preparation method of sandwich type all-solid-state inorganic electrochromic glass

Abstract

The invention relates to the technical field of electrochromic materials and glass preparation, in particular to a preparation method of sandwich type all-solid-state inorganic electrochromic glass which is formed by sequentially compounding a tempered glass layer, a film layer and an electrochromic film layer pile. The thickness of the tempered glass layer is 4 mm, and the film layer is a PVB film and is 0.76 mm thick. The electrochromic film layer stack takes sodium-calcium non-tempered glass with the thickness of 3mm as a substrate, and an anti-ion diffusion layer, a first conductive layer, a first resistive layer, a negative electrode color changing layer, a second resistive layer, a positive electrode color changing layer, a third resistive layer, a second conductive layer and an outermost protective layer are sequentially arranged on the surface of the substrate from inside to outside; the anti-ion diffusion layer is a silicon dioxide layer, and the thickness is 200 nm. According to the preparation method of the sandwich type all-solid-state inorganic electrochromic glass provided by the invention, through precise design of each film layer structure of the glass and gradient optimization of a preparation process, the comprehensive performance of a product is synergistically improved, and many problems in the prior art are effectively solved.

Description

Technical Field

[0001] This invention relates to the field of electrochromic materials and glass preparation technology, specifically to a method for preparing laminated all-solid-state inorganic electrochromic glass. Background Technology

[0002] Electrochromic glass, with its ability to adjust visible light transmittance, has shown significant application value in fields such as building energy conservation, transportation vehicles, and display devices. Among them, laminated all-solid-state inorganic electrochromic glass has become a research and application hotspot in this field due to its high structural safety and the absence of liquid electrolyte leakage risk.

[0003] In existing technologies, the fabrication process of laminated all-solid-state inorganic electrochromic glass still has many technical shortcomings, which restrict the improvement of the overall performance of the product. Some fabrication schemes lack anti-ion diffusion structures or adopt a single structural design, allowing impurity ions in the substrate to easily migrate to the color-changing layer, damaging the microstructure of the color-changing layer and causing a significant decrease in the glass's recyclability. The conductive layer often adopts a single coating layer structure, which has insufficient electrical conductivity and cannot provide sufficient impetus for rapid ion migration, resulting in a slow color-changing response speed.

[0004] Meanwhile, traditional color-changing layers are mostly designed with a single component, resulting in weak ion insertion and extraction capabilities and poor visible light transmittance adjustment. The structural design of the protective layer and anti-ion diffusion layer lacks specificity, leading to poor weather resistance of the glass, insufficient adhesion between film layers, and a tendency for film peeling. Furthermore, improper parameter control and film selection in the lamination process can easily result in residual air bubbles inside the glass, stress cracking, and compromised structural stability and safety.

[0005] The existing process lacks synergy in the design of each layer structure, making it difficult to balance core performance such as response speed, cycle stability, and weather resistance, and thus cannot meet the high performance requirements of practical applications. Therefore, there is an urgent need for a method to prepare sandwich-type all-solid-state inorganic electrochromic glass that optimizes the structure of each layer and the preparation process. Summary of the Invention

[0006] The primary objective of this invention is to provide a method for preparing laminated all-solid-state inorganic electrochromic glass.

[0007] A further objective of this invention is to provide a laminated all-solid-state inorganic electrochromic glass, comprising a tempered glass layer, a film layer, and an electrochromic film layer stacked sequentially; the tempered glass layer has a thickness of 4 mm, the film layer is a PVB film with a thickness of 0.76 mm; the electrochromic film layer stack uses a 3 mm thick soda-lime non-tempered glass as a substrate, and the substrate surface is sequentially disposed from the inside out as follows: an anti-ion diffusion layer, a first conductive layer, a first resistive layer, a negative electrode color-changing layer, a second resistive layer, a positive electrode color-changing layer, a third resistive layer, a second conductive layer, and an outermost protective layer; the anti-ion diffusion layer is a silicon dioxide layer with a thickness of 200 nm; the first conductive layer is an ITO layer. The first resistive layer is a silicon dioxide layer with a thickness of 50 nm; the negative electrode color-changing layer is a tungsten-molybdenum oxide layer, wherein the mass percentage of tungsten oxide is 80% and the mass percentage of molybdenum oxide is 20%, with a thickness of 500 nm; the second resistive layer is a tungsten oxide layer with a thickness of 40 nm; the positive electrode color-changing layer is a lithium-ion-containing tungsten-nickel oxide layer, wherein the mass percentage of nickel oxide is 70%, the mass percentage of tungsten oxide is 20%, and the lithium ion doping amount is 10%, with a thickness of 400 nm; the third resistive layer is a silicon nitride layer with a thickness of 60 nm; the second conductive layer is an aluminum-doped zinc oxide layer with a thickness of 280 nm; and the outermost protective layer is a silicon nitride layer with a thickness of 150 nm.

[0008] Preferably, the first conductive layer is a composite structure of an ITO layer and a silver metal mesh, with a silver metal mesh line width of 10 μm and a mesh spacing of 1000 μm; the second conductive layer is a composite structure of an aluminum-doped zinc oxide layer and a copper-clad silver metal mesh, with a copper-clad silver metal mesh line width of 10 μm and a mesh spacing of 1000 μm.

[0009] Preferably, the negative electrode color-changing layer is a tungsten oxide-molybdenum-titanium ternary doped layer, wherein tungsten oxide accounts for 75% by mass, molybdenum oxide accounts for 20% by mass, and titanium oxide accounts for 5% by mass, with a thickness of 500 nm; the positive electrode color-changing layer is a lithium-ion-containing tungsten oxide-nickel-tantalum ternary doped layer, wherein nickel oxide accounts for 65% by mass, tungsten oxide accounts for 25% by mass, tantalum oxide accounts for 5% by mass, lithium ion doping amount is 5%, and the thickness is 400 nm.

[0010] Preferably, the anti-ion diffusion layer is a three-layer composite structure consisting of a silicon dioxide layer, a silicon nitride layer, and a silicon aluminum oxide layer stacked sequentially, with a total thickness of 200 nm; the outermost protective layer is a composite structure consisting of a silicon nitride aluminum oxide layer and a waterproof membrane, with the silicon nitride aluminum oxide layer having a thickness of 150 nm and the waterproof membrane having a thickness of 50 nm.

[0011] Preferably, the film layer is an SGP-PVB composite film with a total thickness of 0.76 mm, or a POE-PVB composite film with a total thickness of 0.76 mm.

[0012] A method for preparing the aforementioned laminated all-solid-state inorganic electrochromic glass includes the following steps: (1) Substrate treatment: Sodium-calcium non-tempered glass with a thickness of 3mm is cleaned by ultrasonic cleaning with a power of 800W for 15min, dried at 120℃ for 20min, activated by plasma with a power of 500W for 3min, and placed in the coating chamber for later use. (2) Preparation of anti-ion diffusion layer: CVD technology was used to prepare a silicon dioxide layer on the substrate surface by introducing argon gas at a flow rate of 20 sccm, the coating temperature was 400℃, the chamber pressure was 0.5 Pa, the coating time was 30 min, and an anti-ion diffusion layer with a thickness of 200 nm was obtained. (3) Preparation of the first conductive layer: PVD sputtering technology was used to sputter ITO target material with argon gas at a flow rate of 25 sccm, coating temperature of 250℃, target power of 150W, and coating time of 40min to obtain a first conductive layer with a thickness of 300nm. (4) Preparation of the first resistive layer: PVD sputtering technology was used to sputter silicon dioxide target material with argon gas at a flow rate of 20 sccm, the coating temperature was 100℃, the target power was 80W, and the coating time was 10min to obtain a first resistive layer with a thickness of 50nm. (5) Preparation of negative electrode color-changing layer: PVD sputtering technology was used to sputter tungsten oxide molybdenum target material at a flow rate of 22 sccm, the coating temperature was 250℃, the target power was 120W, the coating time was 60min, and a negative electrode color-changing layer with a thickness of 500nm was obtained. (6) Preparation of the second resistive layer: PVD sputtering technology was used to sputter tungsten oxide target material at a flow rate of 20 sccm, the coating temperature was 100℃, the target power was 70W, the coating time was 8min, and a second resistive layer with a thickness of 40nm was obtained. (7) Preparation of positive electrode color-changing layer: PVD sputtering technology was used to sputter lithium-ion-containing tungsten nickel oxide target material with argon gas at a flow rate of 22 sccm, the coating temperature was 100℃, the target power was 100W, the coating time was 50min, and a positive electrode color-changing layer with a thickness of 400nm was obtained. (8) Preparation of the third resistive layer: PVD sputtering technology was used to sputter silicon nitride target material at a flow rate of 20 sccm, the coating temperature was 100℃, the target power was 90W, the coating time was 12min, and a third resistive layer with a thickness of 60nm was obtained. (9) Preparation of the second conductive layer: PVD sputtering technology was used to sputter aluminum-doped zinc oxide target material at a flow rate of 25 sccm, the coating temperature was 250℃, the target power was 140W, the coating time was 35min, and a second conductive layer with a thickness of 280nm was obtained. (10) Preparation of the outermost protective layer: PVD sputtering technology was used to sputter silicon nitride target material with argon gas at a flow rate of 20 sccm, the coating temperature was 200℃, the target power was 100W, the coating time was 25min, and the outermost protective layer with a thickness of 150nm was obtained. (11) Film stacking: The substrate with the above film layer is cooled to room temperature in the coating chamber to form an electrochromic film stack; (12) Laminated composite: 4mm thick tempered glass, 0.76mm thick PVB film and electrochromic film are stacked in sequence, placed in a laminator and vacuumed to 0.8Pa and held for 10min. The temperature is raised to 120℃ and held at 0.8MPa for 30min. The product is then naturally cooled to room temperature.

[0013] Preferably, after step (3), PVD sputtering technology is used to introduce argon gas at a flow rate of 20 sccm to sputter silver metal mesh on the surface of the ITO layer. The sputtering temperature is 250℃, the target power is 80W, and the sputtering time is 5min to obtain a silver metal mesh with a line width of 10μm and a mesh spacing of 1000μm, which forms the first conductive layer with the ITO layer. After step (9), copper-clad silver metal mesh is prepared on the surface of the aluminum-doped zinc oxide layer by screen printing. The line width is 10μm and the mesh spacing is 1000μm. After printing, it is dried at 100℃ for 20min and cured to form the second conductive layer with the aluminum-doped zinc oxide layer.

[0014] Preferably, in step (5), the sputtering target is replaced with a ternary doped target of tungsten oxide, molybdenum and titanium oxide, while the coating process parameters remain unchanged; in step (7), the sputtering target is replaced with a ternary doped target of lithium-ion tungsten oxide, nickel and tantalum oxide, while the coating process parameters remain unchanged.

[0015] Preferably, in step (2), CVD technology is used to introduce argon gas at a flow rate of 20 sccm to prepare a silicon dioxide layer, a silicon nitride layer, and a silicon aluminum oxide layer in sequence. The chamber pressure is 0.5 Pa. The silicon dioxide layer is coated at a temperature of 400℃ for 10 min, the silicon nitride layer is coated at a temperature of 350℃ for 10 min, and the silicon aluminum oxide layer is coated at a temperature of 300℃ for 10 min to obtain a composite anti-ion diffusion layer with a total thickness of 200 nm. In step (10), PVD sputtering technology is first used to introduce argon gas at a flow rate of 20 sccm to sputter a silicon nitride aluminum oxide composite target material. The coating temperature is 200℃, the target power is 100W, and the coating time is 25 min to obtain a silicon nitride aluminum oxide layer with a thickness of 150 nm. Then, a waterproof membrane is coated on its surface using a doctor blade coating technology at a coating speed of 5 m / min. After drying at 120℃ for 15 min, a waterproof membrane with a thickness of 50 nm is obtained, which constitutes the outermost protective layer of the composite.

[0016] Preferably, in step (12), the PVB film is replaced with a POE-PVB composite film with a total thickness of 0.76 mm. After stacking, it is first placed in a pre-press machine and pre-pressed at 80°C and 0.3 MPa for 15 min. Then, it is placed in an autoclave and vacuumed to a vacuum degree of 0.5 Pa and held for 20 min. The temperature is raised to 140°C and held at 1.2 MPa for 50 min. Finally, it is gradually cooled from 140°C to room temperature at a cooling rate of 5°C / min. Alternatively, the PVB film is replaced with an SGP-PVB composite film with a total thickness of 0.76 mm. After stacking, it is placed in an autoclave and vacuumed to a vacuum degree of 0.8 Pa and held for 15 min. The temperature is raised to 130°C and held at 1.0 MPa for 40 min. Finally, it is cooled to room temperature.

[0017] Compared with the prior art, the beneficial effects of the present invention are: 1. The method for preparing sandwich-type all-solid-state inorganic electrochromic glass provided by the present invention achieves a synergistic improvement in the overall performance of the product through precise design of the structure of each film layer of the glass and gradient optimization of the preparation process, effectively solving many problems in the prior art.

[0018] 2. By setting a special anti-ion diffusion layer, the present invention can effectively block the migration of impurity ions in the substrate to the color-changing layer, avoid the damage of impurity ions to the structure of the color-changing layer, and fundamentally ensure the performance stability of the color-changing layer.

[0019] 3. The conductive layer of this invention adopts a composite structure design of a coating layer and a metal mesh, which significantly improves the electrical conduction efficiency, provides favorable conditions for rapid ion migration, and significantly improves the color-changing response characteristics of the glass. The positive and negative electrode color-changing layers adopt a multi-element doping modification design, which enhances the ion insertion and extraction capabilities, improves the adjustment effect of visible light transmittance, and makes the light control performance of the glass even better.

[0020] 4. The present invention also designs the anti-ion diffusion layer and the protective layer as a multi-layer composite structure, which enhances the ion blocking effect and weather protection capability, improves the adhesion between the film layers, and effectively avoids the problem of film layer peeling.

[0021] 5. In addition, the sandwich composite process improves the adhesion performance between the film and the film layer stack and the tempered glass by optimizing the selection of film and process parameters, effectively avoiding the problems of residual bubbles and stress cracking, and improving the structural stability and safety of the glass.

[0022] 6. The preparation process of this invention is standardized and controllable, and the design of each layer structure has good synergy. It can stably prepare high-performance sandwich-type all-solid-state inorganic electrochromic glass, which is suitable for practical application needs in multiple fields and has significant technical and practical value. Detailed Implementation

[0023] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example 1:

[0024] Substrate selection: Sodium-calcium non-tempered glass with a thickness of 3mm was selected as the substrate. It was ultrasonically cleaned with a power of 800W for 15 minutes, dried at 120℃ for 20 minutes, and then activated with plasma with a power of 500W for 3 minutes. It was then placed in the coating chamber for later use. Preparation of anti-ion diffusion layer: CVD technology was used, with argon gas introduced as a protective gas at a flow rate of 20 sccm to prepare a silicon dioxide layer on the substrate surface. The coating temperature was 400℃, the chamber pressure was 0.5 Pa, the coating time was 30 min, and the film thickness was 200 nm. Preparation of the first conductive layer: Using PVD sputtering technology, argon gas flow rate of 25 sccm was introduced, and ITO target material was sputtered on the surface of the anti-ion diffusion layer. The coating temperature was 250℃, the target power was 150W, the coating time was 40min, and the film thickness was 300nm, thus forming the first conductive layer. Preparation of the first resistive layer: PVD sputtering technology was used, with an argon gas flow rate of 20 sccm, sputtering of silicon dioxide target material, coating temperature of 100℃, target power of 80W, coating time of 10 min, and film thickness of 50 nm. Preparation of negative electrode color-changing layer: PVD sputtering technology was used, with argon gas flow rate of 22 sccm, sputtering tungsten oxide molybdenum target material, tungsten oxide mass ratio of 80% and molybdenum oxide mass ratio of 20%, coating temperature of 250℃, target power of 120W, coating time of 60min, and film thickness of 500nm. Preparation of the second resistive layer: PVD sputtering technology was used, with an argon gas flow rate of 20 sccm, sputtering tungsten oxide target material, a coating temperature of 100℃, a target power of 70W, a coating time of 8 min, and a film thickness of 40 nm. Preparation of positive electrode color-changing layer: PVD sputtering technology was used, with argon gas flow rate of 22 sccm, sputtering tungsten-nickel oxide target containing lithium metal ions, with nickel oxide mass ratio of 70%, tungsten oxide mass ratio of 20%, lithium ion doping amount of 10%, coating temperature of 100℃, target power of 100W, coating time of 50min, and film thickness of 400nm. Preparation of the third resistive layer: PVD sputtering technology was used, with an argon gas flow rate of 20 sccm, sputtering silicon nitride target material, coating temperature of 100℃, target power of 90W, coating time of 12min, and film thickness of 60nm. Preparation of the second conductive layer: PVD sputtering technology was used, with an argon gas flow rate of 25 sccm, aluminum-doped zinc oxide target was sputtered, the coating temperature was 250℃, the target power was 140W, the coating time was 35min, and the film thickness was 280nm to form the second conductive layer. The outermost protective layer was prepared by PVD sputtering technology, with an argon gas flow rate of 20 sccm, sputtering silicon nitride target material, a coating temperature of 200℃, a target power of 100W, a coating time of 25 min, and a film thickness of 150 nm. Electrochromic film stack formation: All the film layers on the above substrate constitute an electrochromic film stack, which is taken out after being cooled to room temperature in a chamber; Laminated composite: 4mm thick tempered glass, 0.76mm thick PVB film, and electrochromic film are stacked sequentially and placed in a laminator. First, a vacuum is drawn to a vacuum degree of 0.8Pa and maintained for 10 minutes. Then, the temperature is heated to 120℃ and held at 0.8MPa for 30 minutes. After the film is completely melted and the air bubbles are expelled, it is allowed to cool naturally to room temperature to obtain laminated all-solid-state inorganic electrochromic glass. Example 2:

[0025] Based on Example 1, this embodiment optimizes the conductive layer structure by using a conductive layer assembly consisting of a coating layer and a metal mesh to improve electrical conductivity and color change responsiveness. The remaining preparation processes, raw materials, and specific parameters are consistent with those in Example 1.

[0026] Substrate and preceding film preparation: Same as steps 1 to 4 of Example 1, to complete the preparation of substrate, anti-ion diffusion layer and first conductive layer; Preparation of the first conductive layer assembly: PVD sputtering technology was used on the surface of the ITO layer, with argon gas flow rate of 20 sccm, sputtering silver metal mesh with a metal mesh line width of 10 μm and a mesh spacing of 1000 μm, sputtering temperature of 250℃, target power of 80W, sputtering time of 5 min, to form the first conductive layer assembly with the underlying ITO. Intermediate film preparation: Same as steps 5 to 8 in Example 1, to complete the preparation of the first resistive layer to the third resistive layer; Preparation of the second conductive layer assembly: After sputtering aluminum-doped zinc oxide on the surface of the third resistive layer using PVD technology, a copper-clad silver metal mesh is prepared by screen printing. The metal mesh has a line width of 10 μm and a mesh spacing of 1000 μm. After printing, it is dried at 100℃ for 20 min to cure, forming the second conductive layer assembly with the bottom aluminum-doped zinc oxide. Protective layer and sandwich composite: Same as steps 10 to 12 in Example 1, complete the preparation of the outermost protective layer and sandwich composite to obtain the finished product. Example 3:

[0027] Based on Example 2, this embodiment modifies the positive and negative electrode color-changing layers with multi-element doping to enhance ion insertion and extraction capabilities. Combined with the optimized conductive layer assembly, it improves the difference in transmittance between coloring and fading, and extends the number of cycles. The remaining preparation processes, raw materials, and specific parameters are the same as in Example 2.

[0028] Substrate and preceding film preparation: Same as steps 1 to 3 in Example 2, to complete the preparation of substrate, anti-ion diffusion layer, first conductive layer assembly and first resistive layer; Preparation of negative electrode color-changing layer: PVD sputtering technology was used, with argon gas flow rate of 22 sccm, sputtering tungsten oxide, molybdenum oxide and titanium oxide ternary doped target material, with tungsten oxide mass ratio of 75%, molybdenum oxide mass ratio of 20%, titanium oxide mass ratio of 5%, coating temperature of 250℃, target power of 120W, coating time of 60min, and film thickness of 500nm. Preparation of intermediate resistive layer: Same as step 4 in Example 2, to complete the preparation of the second resistive layer; Preparation of positive electrode color-changing layer: PVD sputtering technology was used, with argon gas flow rate of 22 sccm, sputtering a ternary doped target material of tungsten oxide, nickel, and tantalum containing metallic lithium ions, with nickel oxide mass ratio of 65%, tungsten oxide mass ratio of 25%, tantalum oxide mass ratio of 5%, and lithium ion doping amount of 5%. The coating temperature was 100℃, the target power was 100W, the coating time was 50min, and the film thickness was 400nm. Subsequent film layer and sandwich composite: Same as steps 5 to 6 of Example 2, complete the preparation of the third resistive layer, the second conductive layer assembly, the protective layer and sandwich composite, to obtain the finished product. Example 4:

[0029] Based on Example 3, this embodiment changes the anti-ion diffusion layer to a multi-layer composite structure and the protective layer to a PVD coating plus waterproof membrane composite structure to enhance the ion barrier effect and improve weather resistance. The rest of the preparation process, raw materials and specific parameters are the same as in Example 3.

[0030] Substrate preparation: Same as step 1 in Example 3, complete the cleaning and activation of the sodium-calcium non-tempered glass; Preparation of the composite anti-ion diffusion layer: Using CVD technology, with an argon gas flow rate of 20 sccm, a silicon dioxide layer, a silicon nitride layer, and a silicon aluminum oxide layer were sequentially prepared to form a three-layer composite anti-ion diffusion layer with a total thickness of 200 nm. The silicon dioxide layer was deposited at a temperature of 400℃ for 10 min; the silicon nitride layer was deposited at a temperature of 350℃ for 10 min; and the silicon aluminum oxide layer was deposited at a temperature of 300℃ for 10 min. The chamber pressure was 0.5 Pa for all layers. Intermediate film preparation: Same as steps 2 to 5 of Example 3, to complete the preparation of the first conductive layer assembly, the first resistive layer, the multi-element doped positive and negative electrode color-changing layer, the second resistive layer, the third resistive layer, and the second conductive layer assembly; Preparation of the outermost protective layer of the composite: First, PVD technology was used to sputter silicon nitride aluminum oxide composite target material with an argon gas flow rate of 20 sccm, a coating temperature of 200℃, a target power of 100W, a coating time of 25 min, and a film thickness of 150 nm; then, a waterproof film was coated on the surface of the composite layer using blade coating technology at a coating speed of 5 m / min, and cured by drying at 120℃ for 15 min, with a waterproof film thickness of 50 nm. Laminated composite: Tempered glass with a thickness of 4 mm, SGP-PVB composite film with a total thickness of 0.76 mm, and electrochromic film layer are stacked in sequence, placed in an autoclave, evacuated to a vacuum degree of 0.8 Pa, maintained at vacuum for 15 min, heated to 130 °C, held at temperature and pressure for 40 min at a pressure of 1.0 MPa, and cooled to room temperature to obtain the finished product. Example 5:

[0031] Based on Example 4, this embodiment optimizes the sandwich composite process parameters, selects POE-PVB composite film to improve adhesion performance, avoids bubble residue and stress cracking, and further improves the stability and safety of the glass structure. The remaining preparation process, raw materials and specific parameters are the same as in Example 4.

[0032] Substrate and film stack preparation: Same as steps 1 to 4 of Example 4, complete the preparation of substrate, composite anti-ion diffusion layer, intermediate film layers and composite outermost protective layer to form electrochromic film stack. Laminated composite: 4mm thick tempered glass, 0.76mm thick POE-PVB composite film, and electrochromic film stack are sequentially stacked. First, the layers are placed in a pre-pressing machine at 80℃, 0.3MPa, and 15min to initially remove air bubbles. Then, the composite is placed in an autoclave, evacuated to 0.5Pa, and maintained at vacuum for 20min. It is then heated to 140℃ and held under pressure for 50min at 1.2MPa to ensure the film is completely melted and tightly bonded to the film stack and tempered glass. Finally, a gradient cooling method is used, gradually cooling from 140℃ to room temperature at a rate of 5℃ / min to prevent stress cracking of the glass due to excessive temperature difference, resulting in the finished product.

[0033] Comparative Example 1: The anti-ion diffusion layer is missing, but the rest of the preparation process, raw materials, and parameters are the same as in Example 1.

[0034] Comparative Example 2: The conductive layer does not use a composite structure of a coating layer and a metal mesh, but is only a single ITO, aluminum-doped zinc oxide layer. The rest of the preparation process, raw materials and parameters are the same as in Example 2.

[0035] Comparative Example 3: The color-changing layers of the positive and negative electrodes are of a single composition. The negative electrode is only tungsten oxide and the positive electrode is only lithium-containing nickel oxide. There are no multi-component doping. The rest of the preparation process, raw materials and parameters are the same as those in Example 3.

[0036] Comparative Example 4: The anti-ion diffusion layer is a single silicon nitride layer, and the protective layer is only a single silicon dioxide PVD coating. There is no waterproof membrane coating. The rest of the preparation process, raw materials, and parameters are the same as in Example 4.

[0037] Comparative Example 5: The pre-pressing process and gradient cooling process were not used, and a single PVD film was selected. The rest of the preparation process, raw materials, and parameters were the same as in Example 5.

[0038] Performance testing: Test metrics and test methods: Visible light transmittance: The transmittance of visible light at 550 nm was measured using a spectrophotometer and recorded in both the colored and faded states. The difference in transmittance was then calculated. Color change response time: Using an electrochromic performance testing system, a DC voltage of ±2V was applied, and the coloring time from the faded state to the colored state and the fading time from the colored state to the faded state were recorded. Cyclic stability: Apply ±2V DC voltage and perform coloring and fading cycle tests, recording the number of cycles in which the transmittance difference remains no less than 80%; Ion diffusion barrier: The diffusion of sodium ions from the substrate to the color-changing layer was tested using X-ray photoelectron spectroscopy after the glass was placed at 60℃ and 90% humidity for 1000h. Weather resistance: The glass was placed in a xenon lamp aging test chamber and subjected to a 1000-hour xenon lamp aging test. The change rate of coloring and fading response time after aging was tested. Film adhesion: The adhesion between the outermost protective layer and the second conductive layer is tested using the cross-cut adhesion test method. The level is divided into 0 to 5, with level 0 being the best, indicating no film peeling.

[0039] The test results are shown in Table 1 below:

[0040] Results analysis: The test results show that the performance of each embodiment of the present invention exhibits a gradual optimization trend, with Embodiment 5 showing the best overall performance. Embodiment 1, as the basic solution, meets all basic usage standards, with a transmittance difference of 59.7%, a coloring time of 3.8s, a fading time of 4.2s, and a cycle stability of 1.2×10⁻⁶. 4In Example 2, the sodium ion diffusion rate was 0.85 at.%, the weather resistance was 8.5%, and the film adhesion was Grade 1. Compared with Comparative Example 1, the sodium ion diffusion rate was significantly reduced due to the addition of the anti-ion diffusion layer, and the cycle stability was improved by 15 times. This proves that the anti-ion diffusion layer can effectively block impurity ions and ensure the performance of the color-changing layer. After optimizing the overall structure of the conductive layer in Example 2, the coloring time was shortened to 2.9s, the fading time was shortened to 3.3s, and the transmittance difference was increased to 65.3%. Compared with Comparative Example 2, the conductivity efficiency was significantly improved, and the color-changing response speed was accelerated. This indicates that the conductive layer assembly of the coating layer and the metal mesh can effectively improve the electrical conductivity and provide a guarantee for rapid ion migration. After multi-element doping modification of the positive and negative electrode color-changing layers in Example 3, the transmittance difference was increased to 69.8%, and the cycle stability was increased to 4.8 × 10⁻⁶. 4 In Example 4, compared to Comparative Example 3, the ion insertion and extraction capabilities were enhanced, and the number of cycles increased by 2.4 times, demonstrating that multi-element doping can significantly improve the performance of the color-changing layer. After optimizing the composite anti-ion diffusion layer and composite protective layer in Example 4, the sodium ion diffusion rate decreased to 0.05 at.%, weather resistance increased to 3.1%, and film adhesion remained at level 0. Compared to Comparative Example 4, the ion blocking effect was improved by 80%, and weather resistance increased by 79.6%, indicating that the multilayer composite structure can enhance ion blocking and weather protection effects. In Example 5, after comprehensively optimizing the sandwich composite process, all performance aspects were further improved: coloring time 1.7s, fading time 1.9s, transmittance difference 74.7%, and cycle stability 7.2×10⁻⁶. 4 Secondly, the sodium ion diffusion rate was 0.04 at.%, and the weather resistance was 2.8%. Compared with Comparative Example 5, there were no residual bubbles, the structural stability was stronger, and the risk of stress cracking was reduced, proving that the pre-compression process, gradient cooling, and composite film can improve the bonding performance and structural safety. Each comparative example, lacking the corresponding core optimization features, showed significant performance shortcomings, further verifying the necessity and synergistic effect of the various optimization schemes in this invention, ensuring that the preparation method of this invention can stably achieve the production of high-performance laminated all-solid-state inorganic electrochromic glass.

[0041] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention.

Claims

1. A laminated all-solid-state inorganic electrochromic glass, characterized in that, It is composed of a tempered glass layer, a film layer, and an electrochromic film layer stacked sequentially; the tempered glass layer is 4mm thick, the film layer is a PVB film with a thickness of 0.76mm; the electrochromic film stack uses a 3mm thick soda-lime non-tempered glass substrate, and the substrate surface is sequentially arranged from the inside to the outside as follows: an anti-ion diffusion layer, a first conductive layer, a first resistive layer, a negative electrode color-changing layer, a second resistive layer, a positive electrode color-changing layer, a third resistive layer, a second conductive layer, and an outermost protective layer; the anti-ion diffusion layer is a silicon dioxide layer with a thickness of 200nm; the first conductive layer is an ITO layer with a thickness of 300nm; the first resistive layer... The first layer is a silicon dioxide layer with a thickness of 50 nm; the negative electrode color-changing layer is a tungsten-molybdenum oxide layer, wherein tungsten oxide accounts for 80% by mass and molybdenum oxide accounts for 20% by mass, with a thickness of 500 nm; the second resistive layer is a tungsten oxide layer with a thickness of 40 nm; the positive electrode color-changing layer is a lithium-ion-containing tungsten-nickel oxide layer, wherein nickel oxide accounts for 70% by mass, tungsten oxide accounts for 20% by mass, and lithium ion doping is 10%, with a thickness of 400 nm; the third resistive layer is a silicon nitride layer with a thickness of 60 nm; the second conductive layer is an aluminum-doped zinc oxide layer with a thickness of 280 nm; and the outermost protective layer is a silicon nitride layer with a thickness of 150 nm.

2. The laminated all-solid-state inorganic electrochromic glass according to claim 1, characterized in that, The first conductive layer is a composite structure of an ITO layer and a silver metal mesh, with a silver metal mesh line width of 10 μm and a mesh spacing of 1000 μm; the second conductive layer is a composite structure of an aluminum-doped zinc oxide layer and a copper-clad silver metal mesh, with a copper-clad silver metal mesh line width of 10 μm and a mesh spacing of 1000 μm.

3. The laminated all-solid-state inorganic electrochromic glass according to claim 2, characterized in that, The negative electrode color-changing layer is a ternary doped layer of tungsten oxide, molybdenum oxide, and titanium oxide, wherein tungsten oxide accounts for 75% by mass, molybdenum oxide accounts for 20% by mass, titanium oxide accounts for 5% by mass, and the thickness is 500 nm; the positive electrode color-changing layer is a ternary doped layer of tungsten oxide, nickel oxide, and tantalum oxide containing lithium ions, wherein nickel oxide accounts for 65% by mass, tungsten oxide accounts for 25% by mass, tantalum oxide accounts for 5% by mass, lithium ion doping amount is 5%, and the thickness is 400 nm.

4. The laminated all-solid-state inorganic electrochromic glass according to claim 3, characterized in that, The anti-ion diffusion layer is a three-layer composite structure consisting of a silicon dioxide layer, a silicon nitride layer, and a silicon aluminum oxide layer stacked sequentially, with a total thickness of 200 nm; the outermost protective layer is a composite structure consisting of a silicon nitride aluminum oxide layer and a waterproof membrane, with the silicon nitride aluminum oxide layer having a thickness of 150 nm and the waterproof membrane having a thickness of 50 nm.

5. The laminated all-solid-state inorganic electrochromic glass according to claim 4, characterized in that, The film layer is an SGP-PVB composite film with a total thickness of 0.76 mm, or a POE-PVB composite film with a total thickness of 0.76 mm.

6. A method for preparing a laminated all-solid-state inorganic electrochromic glass as described in claim 1, characterized in that, Includes the following steps: (1) Substrate treatment: Sodium-calcium non-tempered glass with a thickness of 3mm is cleaned by ultrasonic cleaning with a power of 800W for 15min, dried at 120℃ for 20min, activated by plasma with a power of 500W for 3min, and placed in the coating chamber for later use. (2) Preparation of anti-ion diffusion layer: CVD technology was used to prepare a silicon dioxide layer on the substrate surface by introducing argon gas at a flow rate of 20 sccm, the coating temperature was 400℃, the chamber pressure was 0.5 Pa, the coating time was 30 min, and an anti-ion diffusion layer with a thickness of 200 nm was obtained. (3) Preparation of the first conductive layer: PVD sputtering technology was used to sputter ITO target material with argon gas at a flow rate of 25 sccm, coating temperature of 250℃, target power of 150W, and coating time of 40min to obtain a first conductive layer with a thickness of 300nm. (4) Preparation of the first resistive layer: PVD sputtering technology was used to sputter silicon dioxide target material with argon gas at a flow rate of 20 sccm, the coating temperature was 100℃, the target power was 80W, and the coating time was 10min to obtain a first resistive layer with a thickness of 50nm. (5) Preparation of negative electrode color-changing layer: PVD sputtering technology was used to sputter tungsten oxide molybdenum target material at a flow rate of 22 sccm, the coating temperature was 250℃, the target power was 120W, the coating time was 60min, and a negative electrode color-changing layer with a thickness of 500nm was obtained. (6) Preparation of the second resistive layer: PVD sputtering technology was used to sputter tungsten oxide target material at a flow rate of 20 sccm, the coating temperature was 100℃, the target power was 70W, the coating time was 8min, and a second resistive layer with a thickness of 40nm was obtained. (7) Preparation of positive electrode color-changing layer: PVD sputtering technology was used to sputter lithium-ion-containing tungsten nickel oxide target material with argon gas at a flow rate of 22 sccm, the coating temperature was 100℃, the target power was 100W, the coating time was 50min, and a positive electrode color-changing layer with a thickness of 400nm was obtained. (8) Preparation of the third resistive layer: PVD sputtering technology was used to sputter silicon nitride target material at a flow rate of 20 sccm, the coating temperature was 100℃, the target power was 90W, the coating time was 12min, and a third resistive layer with a thickness of 60nm was obtained. (9) Preparation of the second conductive layer: PVD sputtering technology was used to sputter aluminum-doped zinc oxide target material at a flow rate of 25 sccm, the coating temperature was 250℃, the target power was 140W, the coating time was 35min, and a second conductive layer with a thickness of 280nm was obtained. (10) Preparation of the outermost protective layer: PVD sputtering technology was used to sputter silicon nitride target material with argon gas at a flow rate of 20 sccm, the coating temperature was 200℃, the target power was 100W, the coating time was 25min, and the outermost protective layer with a thickness of 150nm was obtained. (11) Film stacking: The substrate with the above film layer is cooled to room temperature in the coating chamber to form an electrochromic film stack; (12) Laminated composite: 4mm thick tempered glass, 0.76mm thick PVB film and electrochromic film are stacked in sequence, placed in a laminator and vacuumed to 0.8Pa and held for 10min. The temperature is raised to 120℃ and held at 0.8MPa for 30min. The product is then naturally cooled to room temperature.

7. The preparation method according to claim 6, characterized in that, After step (3), PVD sputtering technology was used to introduce argon gas at a flow rate of 20 sccm to sputter silver metal mesh on the surface of the ITO layer. The sputtering temperature was 250℃, the target power was 80W, and the sputtering time was 5min. A silver metal mesh with a line width of 10μm and a mesh spacing of 1000μm was obtained, which together with the ITO layer constituted the first conductive layer. After step (9), copper-clad silver metal mesh was prepared on the surface of the aluminum-doped zinc oxide layer by screen printing. The line width was 10μm and the mesh spacing was 1000μm. After printing, it was dried at 100℃ for 20min and cured to form the second conductive layer together with the aluminum-doped zinc oxide layer.

8. The preparation method according to claim 7, characterized in that, In step (5), the sputtering target is replaced with a ternary doped target of tungsten oxide, molybdenum and titanium oxide, while the coating process parameters remain unchanged; in step (7), the sputtering target is replaced with a ternary doped target of lithium-ion tungsten oxide, nickel and tantalum oxide, while the coating process parameters remain unchanged.

9. The preparation method according to claim 8, characterized in that, In step (2), CVD technology is used to introduce argon gas at a flow rate of 20 sccm to prepare a silicon dioxide layer, a silicon nitride layer, and a silicon aluminum oxide layer in sequence. The chamber pressure is 0.5 Pa. The silicon dioxide layer is coated at a temperature of 400℃ for 10 min, the silicon nitride layer is coated at a temperature of 350℃ for 10 min, and the silicon aluminum oxide layer is coated at a temperature of 300℃ for 10 min, resulting in a composite anti-ion diffusion layer with a total thickness of 200 nm. In step (10), PVD sputtering technology is first used to introduce argon gas at a flow rate of 20 sccm to sputter a silicon nitride aluminum oxide composite target material. The coating temperature is 200℃, the target power is 100 W, and the coating time is 25 min, resulting in a silicon nitride aluminum oxide layer with a thickness of 150 nm. Then, a waterproof membrane is coated on its surface using a doctor blade coating technology at a coating speed of 5 m / min. After drying at 120℃ for 15 min, a waterproof membrane with a thickness of 50 nm is obtained, which constitutes the outermost protective layer of the composite.

10. The preparation method according to claim 9, characterized in that, In step (12), the PVB film is replaced with a POE-PVB composite film with a total thickness of 0.76 mm. After stacking, it is first placed in a pre-press machine and pre-pressed at 80°C and 0.3 MPa for 15 min. Then it is placed in an autoclave and vacuumed to a vacuum degree of 0.5 Pa and held for 20 min. The temperature is raised to 140°C and held at 1.2 MPa for 50 min. Finally, it is gradually cooled from 140°C to room temperature at a cooling rate of 5°C / min. Alternatively, the PVB film is replaced with an SGP-PVB composite film with a total thickness of 0.76 mm. After stacking, it is placed in an autoclave and vacuumed to a vacuum degree of 0.8 Pa and held for 15 min. The temperature is raised to 130°C and held at 1.0 MPa for 40 min. Finally, it is cooled to room temperature.

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