Electrochromic device, manufacturing method therefor, and electronic device

Abstract

Disclosed in the present disclosure are an electrochromic device, a manufacturing method therefor, and an electronic device. The electrochromic device comprises: a first conductive layer and a second conductive layer which are stacked; an edge sealant; and an enclosed cavity, the enclosed cavity comprising an electrochromic material inside. The edge sealant comprises: a sealant body; a first flow front portion; and a second flow front portion.

Description

Electrochromic device, preparation method thereof and electronic device

[0001] Priority information

[0002] The present disclosure claims the priority and benefit of the patent publication with the publication number 202411017588.1, filed on July 26, 2024, with the State Intellectual Property Office of China, and the patent publication with the publication number 202411206916.2, filed on August 29, 2024, with the State Intellectual Property Office of China, and incorporates the full text thereof herein by reference. TECHNICAL FIELD

[0003] The present disclosure relates to the technical field of electrochromic devices, in particular to an electrochromic device, a preparation method thereof and an electronic device. BACKGROUND

[0004] An electrochromic device is a device capable of changing its color through an electrochemical process. The built-in electrochromic layer thereof will undergo an oxidation-reduction reaction under the action of an electric field, thereby changing its optical properties and exhibiting different colors. However, under the condition of being powered on, the electrochromic material is prone to the phenomenon of gathering at the cathode and anode, especially at the edge of the frame glue, and the edge color difference often occurs, and even the color layering phenomenon occurs, and the power-off recovery time is slow.

[0005] Therefore, the current electrochromic device still needs to be researched.

[0006] DISCLOSURE

[0007] The present disclosure aims to at least partially solve one of the technical problems in the related art. To this end, one object of the present disclosure is to provide an electrochromic device, a preparation method thereof and an electronic device, which has strong color change uniformity and fast response rate, and is not prone to edge color difference phenomenon, and has excellent overall performance.

[0008] The first aspect of the present disclosure provides an electrochromic device, comprising:

[0009] a first conductive layer and a second conductive layer arranged in a stack;

[0010] a frame glue, the frame glue being located between the first conductive layer and the second conductive layer and surrounding the first conductive layer and the second conductive layer to form a sealed cavity, and the sealed cavity comprising an electrochromic material;

[0011] The frame glue comprises:

[0012] a glue body;

[0013] a first flow cast part, the first flow cast part being located on a side surface of the glue body facing the sealed cavity and connected with the first conductive layer.

[0014] a second flow cast portion located on a side surface of the adhesive body facing the sealed cavity and connected with the second conductive layer;

[0015] In the direction of the adhesive body facing the sealed cavity, the extension length of the first flow cast portion is X, and the extension length of the second flow cast portion is Y, and the difference between X and Y is not greater than 60 μm.

[0016] According to the electrochromic device of the present disclosure, the difference between the extension length X of the first flow cast portion and the extension length Y of the second flow cast portion meets the above condition, which is beneficial to the uniform distribution of the electric field in the device in the on-state, thereby promoting the uniform oxidation and reduction of the electrochromic material in the reaction process and improving the phenomenon of color difference or even delamination at the edge of the electrochromic device. After power-off, the color residue in the electrochromic layer can quickly recover to the initial state, and the response rate is fast.

[0017] According to the electrochromic device of the present disclosure, the electrochromic device can further have the following additional technical features:

[0018] According to the electrochromic device of the present disclosure, the extension length of the first flow cast portion is 0.1 μm to 100 μm.

[0019] And / or, the extension length of the second flow cast portion is 0.1 μm to 100 μm.

[0020] According to the electrochromic device of the present disclosure, the difference between X and Y is not greater than 20 μm.

[0021] According to the electrochromic device of the present disclosure, the distance between the first conductive layer and the second conductive layer is 50 μm to 120 μm.

[0022] According to the electrochromic device of the present disclosure, the material forming the sealing frame adhesive includes an adhesive liquid, and the adhesive liquid meets at least one of the following conditions:

[0023] The viscosity of the adhesive liquid is 10,000 mpa·s to 150,000 mpa·s.

[0024] The thixotropic index of the adhesive liquid is 1 to 8.

[0025] The curing energy of the adhesive liquid is 1,000 mj / cm 2 to 20,000 mj / cm 2 .

[0026] The adhesive liquid contains gap balls, and the thickness of the gap balls is 50 μm to 120 μm.

[0027] According to the electrochromic device of the present disclosure, the material forming the sealing frame adhesive includes an adhesive liquid, and the adhesive liquid meets at least one of the following conditions:

[0028] The viscosity of the adhesive is 30,000 mPa·s to 80,000 mPa·s;

[0029] The thixotropic index of the adhesive is 3 to 6;

[0030] The curing energy of the adhesive is 5000 mJ / cm. 2 ~10000mj / cm 2 .

[0031] According to embodiments of this disclosure, the material of the gap ball includes at least one selected from glass, ceramic, calcium barate, polystyrene, polymethyl methacrylate, and talc.

[0032] According to embodiments of this disclosure, the first conductive layer is electrically connected to the positive electrode plate, and the second conductive layer is electrically connected to the negative electrode plate;

[0033] The dyne value of the first conductive layer is A, and the dyne value of the second conductive layer is B, wherein A and B satisfy at least one of the following conditions:

[0034] AB is -30 to 30;

[0035] A is 30-60;

[0036] B is 30-60.

[0037] According to embodiments of this disclosure, AB is -2 to 18;

[0038] Alternatively, AB can be 4 to 10.

[0039] According to embodiments of this disclosure, the sealed cavity includes at least two electrochromic materials.

[0040] According to embodiments of this disclosure, the electrochromic material may include an electrochromic liquid, wherein the water content and oxygen content of the electrochromic liquid are both no more than 15 ppm. The low water and oxygen content in the electrochromic liquid according to embodiments of this disclosure reduces side reactions between oxygen and water and the components in the electrochromic liquid, thus improving the stability of the electrochromic liquid and slowing down its aging rate. Therefore, electrochromic devices containing this electrochromic liquid exhibit strong color-changing performance, long service life, and can maintain stable operation for extended periods even under high temperature and humidity or large temperature variations, demonstrating excellent overall performance.

[0041] According to embodiments of this disclosure, the electrochromic liquid does not contain antioxidants or dehydrating agents.

[0042] According to embodiments of this disclosure, the electrochromic liquid comprises: an anodic color-changing material, a cathodic color-changing material, an electrolyte, and a solvent.

[0043] According to embodiments of the present disclosure, the electrochromic solution further includes: an oxide of an anodic coloring material and a hydrate of a cathodic coloring material.

[0044] According to embodiments of the present disclosure, the content of the oxide of the anodic coloring material is not greater than 50 ppm;

[0045] and / or, the content of the hydrate of the cathodic coloring material is not greater than 50 ppm.

[0046] According to embodiments of the present disclosure, the content of the oxide of the anodic coloring material is not greater than 10 ppm; and / or, the content of the hydrate of the cathodic coloring material is not greater than 10 ppm.

[0047] According to embodiments of the present disclosure, the anodic coloring material includes: at least one of nickel oxide, iridium oxide, phenazine compound, polyaniline, polypyrrole, Prussian blue, thiophene compound, phthalocyanine compound, tungsten trioxide, molybdenum trioxide, phenothiazine compound, methylene blue, viologen, methyl viologen, ethyl viologen, phenyl viologen, and propyl viologen.

[0048] According to embodiments of the present disclosure, the cathodic coloring material includes: at least one of tungsten trioxide, molybdenum trioxide, phenylenediamine, nickel oxide, manganese dioxide, iridium oxide, polyaniline, Prussian blue, polypyrrole, manganese dioxide, methyl viologen, ethyl viologen, phenyl viologen, propyl viologen, 1,1'-disubstituted-4,4'-bipyridine, and 1,1'-diheptyl-4,4'-bipyridine tetrafluoroborate.

[0049] According to embodiments of the present disclosure, the electrolyte includes one or more of tetrabutylammonium bromide, tetrabutylammonium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis-trifluoromethylsulfonylimide, polyethylene oxide, polypropylene oxide, and polymethyl methacrylate.

[0050] According to embodiments of the present disclosure, the solvent includes at least one of propylene carbonate, toluene, xylene, butyrolactone, 2-acetylbutyrolactone, γ-valerolactone, ethylene carbonate, propylene carbonate, sulfolane, 3-methylsulfolane, dimethylacetamide, dimethylformamide, acetonitrile, glutaronitrile, 2-methylglutaronitrile, 3-hydroxypropionitrile, tetraethylene glycol dimethyl ether, dimethyl sulfoxide, ethoxyethanol, and cyclopentanone.

[0051] According to embodiments of the present disclosure, the first conductive layer is provided with a first substrate on a side away from the second conductive layer;

[0052] The second conductive layer is provided with a second substrate on a side away from the first conductive layer.

[0053] A second aspect of the present disclosure provides a method for preparing the electrochromic device of the first aspect of the present disclosure. According to an embodiment of the present disclosure, the method comprises:

[0054] applying the sealant between the first conductive layer and the second conductive layer to form a closed cavity around the first conductive layer and the second conductive layer with the sealant;

[0055] filling the electrochromic material into the closed cavity, and resealing the closed cavity to obtain the electrochromic device.

[0056] According to an embodiment of the present disclosure, the applying the sealant between the first conductive layer and the second conductive layer comprises:

[0057] applying the adhesive liquid on the first surface of the first conductive layer to form an adhesive layer, and reserving a filling opening on the adhesive layer;

[0058] turning over the first conductive layer to make the first surface face downward;

[0059] attaching the second conductive layer to the side of the first conductive layer with the adhesive layer, and performing a curing treatment to form the sealant around the first conductive layer and the second conductive layer.

[0060] According to an embodiment of the present disclosure, the curing treatment comprises a normal temperature curing treatment, an ultraviolet light curing treatment, or an ultraviolet and heat double curing treatment.

[0061] According to an embodiment of the present disclosure, the first conductive layer and the second conductive layer are subjected to a cleaning treatment before the sealant is applied between the first conductive layer and the second conductive layer.

[0062] A third aspect of the present disclosure provides an electronic device. According to an embodiment of the present disclosure, the electronic device comprises the electrochromic device of the first aspect of the present disclosure.

[0063] Additional aspects and advantages of the present disclosure will be in part apparent and in part pointed out hereinafter. BRIEF DESCRIPTION OF DRAWINGS

[0064] The above and / or additional aspects and advantages of the present disclosure will become apparent and be readily appreciated from the following description, including the appended drawings.

[0065] FIG. 1 shows a schematic structural diagram of an electrochromic device according to an embodiment of the present disclosure;

[0066] FIG. 2 shows a schematic structural diagram of an electrochromic device according to an embodiment of the present disclosure;

[0067] Figure 3 shows an edge color difference mechanism diagram of an electrochromic device according to an embodiment of the present disclosure;

[0068] Figure 4 shows a flow chart of a method for preparing an electrochromic device according to an embodiment of the present disclosure;

[0069] Figure 5 shows a flow chart of applying a sealant according to an embodiment of the present disclosure;

[0070] Figure 6 shows performance test results of an electrochromic device prepared using a modified polyacrylate provided in Example 22-3 of the present disclosure;

[0071] Figure 7 shows a structural schematic diagram of an electrochromic device according to an embodiment of the present disclosure;

[0072] Figure 8 shows a top view of a partial structure of an electrochromic device according to an embodiment of the present disclosure;

[0073] Figure 9 shows a structural schematic diagram of a first substrate and a first conductive layer according to an embodiment of the present disclosure;

[0074] Figure 10 shows a structural schematic diagram of a patterning structure according to an embodiment of the present disclosure;

[0075] Figure 11 shows a structural schematic diagram of an edge portion, a patterning structure, a first resistance regulating path, and a second resistance regulating path according to an embodiment of the present disclosure;

[0076] Figure 12 shows a structural schematic diagram of a first resistance regulating path and a second resistance regulating path according to an embodiment of the present disclosure;

[0077] Figure 13 shows a structural schematic diagram of a positive electrode sheet and a negative electrode sheet according to an embodiment of the present disclosure;

[0078] Figure 14 shows a flow chart of a method for preparing an electrochromic device according to an embodiment of the present disclosure;

[0079] Figure 15 shows a structural schematic diagram of a positive electrode sheet and a negative electrode sheet according to Example 47-3 of the present disclosure.

[0080] Figure 16 shows a flow chart of a method for preparing an electrochromic solution according to an embodiment of the present disclosure;

[0081] Figure 17 shows a structural schematic diagram of a system for preparing an electrochromic solution according to an embodiment of the present disclosure;

[0082] Figure 18 shows a structural schematic diagram of an electrochromic device according to an embodiment of the present disclosure;

[0083] Figure 19 shows a structural schematic diagram of an anode glass according to an embodiment of the present disclosure;

[0084] Figure 20 shows a structural schematic diagram of a cathode glass according to an embodiment of the present disclosure;

[0085] Figure 21 shows a schematic diagram of a conductive thin film material structure according to one embodiment of the present disclosure;

[0086] Figure 22 shows a reflection layer XPS elemental ratio plot according to Example 1-1 of the present disclosure;

[0087] Figure 23 shows a schematic diagram of a conductive thin film material structure according to Comparative Example 2-1 of the present disclosure;

[0088] Figure 24 shows a schematic diagram of an electrochromic device structure according to another embodiment of the present disclosure;

[0089] Figure 25 shows a perspective view of an electrochromic device according to one embodiment of the present disclosure;

[0090] Figure 26 shows a flow diagram of a method of making an electrochromic device according to one embodiment of the present disclosure.

[0091] 10: electrochromic device; 100: first conductive layer; 110: main body part; 111: center part; 112: patterned structure; 120: edge part; 130: first resistance regulation path; 140: second resistance regulation path; 150: first encapsulant; 160: second encapsulant; 170: spacing area; 200: second conductive layer; 300: sealant; 310: sealant body; 320: first flow-casting part; 330: second flow-casting part; 400: closed cavity; 500: first substrate; 600: second substrate; 200P: electrochromic layer; 300P: second conductive layer; 400P: insulating structure; 500P: first conductive coating; 600P: second conductive coating; 700: first substrate; 800A: positive electrode sheet; 800B: negative electrode sheet; 810: first part; 820: second part; 830: third part; 810A: first part adhesive layer; 820A: second part back surface; 830A: third part adhesive layer; 900: second substrate; a and b: cutting sites; c: first included angle; d: second included angle; M: first through hole; N: second through hole; 10A: system for preparing electrochromic device; 100A: heating unit; 200A: condensing unit; 300A: mixing unit; 110A: temperature acquisition module; 120A: stirring module; 210A: vacuum forming unit; 220A: air pressure acquisition module; 230A: temperature acquisition module; 400A: transfer storage device; 500A: finished product storage device; 10B: electrochromic device; 100B: first conductive layer; 200B: second conductive layer; 300B: sealant; 310: main adhesive layer; 320: moisture curing layer; 330: hydrophobic layer; 400B: closed cavity; 500B: first substrate; 600B: second substrate; 10-1: conductive film material; 100-1: transparent substrate; 200-1: reflective layer; 300-1: bonding transition layer; 400-1: protective layer. DETAILED DESCRIPTION

[0092] Embodiments of the present disclosure are described in detail below. The embodiments described below are examples for explaining the present disclosure and should not be understood as limiting the present disclosure.

[0093] It should be noted that the terms "first", "second" are used only for the purpose of description and should not be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features. Further, in the description of the present disclosure, the meaning of "a plurality of" is two or more, unless otherwise specified.

[0094] The endpoints and any values ​​of the ranges disclosed in this disclosure are not limited to the precise ranges or values, and such ranges or values ​​should be understood to include values ​​close to such ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this disclosure.

[0095] In this disclosure, the terms “comprising” or “including” are open-ended expressions, meaning that they include the contents specified in this disclosure but do not exclude other contents.

[0096] Electrochromic devices typically consist of two conductive layers and an electrochromic layer between them, with the electrochromic layer sealed by an adhesive sealant around its edges. Due to the high reactivity of the electrochromic material, it readily undergoes redox reactions during the application of an electric current, generating reactive free radical intermediates, thus causing a color change. For liquid or semi-solid electrochromic layers (obtained by curing a liquid electrochromic material electrolyte), ions migrate under an electric field, easily accumulating at the anode and cathode, especially at the edges of the sealant, often resulting in discoloration or even color layering. This phenomenon is exacerbated during prolonged operation. Furthermore, the recovery time after power failure is slow.

[0097] Traditionally, the solution to the aforementioned technical problem has been to add anti-delamination agents to the electrolyte, such as polymethyl methacrylate and various ionic polymers. However, after the device has been operating for an extended period, such as 10 minutes, 30 minutes, 1 hour, 3 hours, or even 8 hours, the severity of the phenomenon continues to increase, posing a serious safety hazard to devices that operate for extended periods overnight.

[0098] Therefore, the first aspect of this disclosure provides an electrochromic device 10, comprising: a first conductive layer 100 and a second conductive layer 200 stacked together; a sealing adhesive 300; and a sealed cavity 400, wherein the sealed cavity 400 includes an electrochromic material; the sealing adhesive 300 comprises: an adhesive body 310, a first casting portion 320, and a second casting portion 330. Specifically, the sealing adhesive 300 is located between the first conductive layer 100 and the second conductive layer 200 and surrounds the first conductive layer 100 and the second conductive layer 200 to form the sealed cavity 400; the first casting portion 320 is located on the side surface of the adhesive body 310 facing the sealed cavity 400 and is connected to the first conductive layer 100; the second casting portion 330 is located on the side surface of the adhesive body 310 facing the sealed cavity 400 and is connected to the second conductive layer 200.

[0099] The principle and advantages of the electrochromic device design disclosed herein are explained below with reference to Figures 2 and 3:

[0100] Figure 2 is an enlarged view of the area of the sealant in Figure 1. In the dispensing process, the sealant will inevitably flow to one or both sides due to the effects of gravity and surface tension. In this disclosure, the area formed by the flow of the sealant is referred to as the "flow area". The flow area connected to the first conductive layer is referred to as the "first flow area", and the corresponding width is denoted as X. The extension length of the first flow area in the direction of the sealant body towards the sealed cavity is X. The flow area connected to the second conductive layer is referred to as the "second flow area", and the corresponding width is denoted as Y. The extension length of the second flow area in the direction of the sealant body towards the sealed cavity is Y.

[0101] For example, the sealed cavity contains two electrochromic materials. One of the electrochromic materials is referred to as the "cathode material", denoted as A 2+ , and the other is referred to as the "anode material", denoted as B. As shown in Figure 3, when the device is in the powered state, the cathode material A 2+ and the anode material B are converted into the colored state A + and B + , respectively, under the action of the electric field, and form a composite color. When the power is cut off, the excited electrochromic materials A + and B + will collide with each other to quickly gain or lose electrons, and return to the initial A 2+ and B, presenting a colorless state. Since the sealant is insulating, when X and Y have a certain difference (i.e. in the asymmetric state), for example, when X is less than Y, as shown in Figure 3, the cathode will have a larger insulating area than the anode, forming an asymmetric electric field, so that the current density at the edge of the sealant of the cathode is higher than that of the anode, the concentration of A + at the edge of the sealant is higher than that of B + , and the high-concentration A + at the edge of the sealant will gradually diffuse to the inside of the sealant (the area where Y is located), while B + is uniformly distributed at the conductive layer, i.e. there is an uneven electric field. After the electric field is eliminated by cutting off the power, A + diffused to the inside of the sealant cannot collide with B + in time, resulting in color retention. At this time, B + is uniformly distributed, and the residual color is light, mainly with the color of A + retained. Similarly, if X is greater than Y, the color retention phenomenon of B + will occur.

[0102] As can be seen from the above, the difference between X and Y will significantly affect the uniformity of the electric field distribution, and in turn affect the color change uniformity and response rate. The smaller the difference between the two, the more uniform the electric field distribution, the better the color change uniformity, the less likely to appear edge color difference phenomenon, and the higher the response rate. Among them, when the difference is not greater than 60 μm, the diffusion distance of ions is shorter, which helps to uniformly distribute the electric field, improves the color change uniformity and response rate, and is less likely to appear edge color difference phenomenon. After power off, it can quickly recover to the initial state. In some embodiments, the difference between X and Y can be 0 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, etc. In some embodiments, the difference between X and Y is not greater than 20 μm. In some embodiments, the difference between X and Y is not greater than 10 μm.

[0103] It should be noted that the term "the difference between X and Y" can be understood as the absolute value of X-Y, that is, a positive value.

[0104] According to embodiments of the present disclosure, the extension length of the first flow cast part 320 is 0.1 μm-100 μm. In some embodiments, the extension length of the first flow cast part 320 is 0.1 μm, 10 μm, 20 μm, 40 μm, 50 μm, 60 μm, 80 μm, 100 μm, etc. Thus, not only can the uniformity of the electric field be optimized, the electric field uniformity and the migration speed of ions and electrons in the electrochromic process can be improved, the color change uniformity and response rate can be improved, and the recovery time after power off can be fast; the size of the electrochromic region can also be brought to a better level, providing a better visual experience, while reducing the influence of the first flow cast part on light absorption and reflection, and improving the optical properties of the device. In addition, the extension length of the flow cast part can be controlled by parameters such as the properties of the adhesive and the properties of the conductive layer, and the controllability is strong, which helps to improve the production yield.

[0105] According to embodiments of the present disclosure, the extension length of the second flow cast part 330 is 0.1 μm-100 μm. In some embodiments, the extension length of the second flow cast part 330 is 0.1 μm, 10 μm, 20 μm, 40 μm, 50 μm, 60 μm, 80 μm, 100 μm, etc. Thus, not only can the uniformity of the electric field be optimized, the electric field uniformity and the migration speed of ions and electrons in the electrochromic process can be improved, the color change uniformity and response rate can be improved; the size of the electrochromic region can also be brought to a better level, providing a better visual experience, while reducing the influence of the first flow cast part on light absorption and reflection, and improving the optical properties of the device. In addition, the extension length of the flow cast part can be controlled by parameters such as the properties of the adhesive and the properties of the conductive layer, and the controllability is strong, which helps to improve the production yield.

[0106] According to embodiments of the present disclosure, the distance between the first conductive layer 100 and the second conductive layer 200 is 50 μm to 120 μm. In some embodiments, the distance between the first conductive layer 100 and the second conductive layer 200 is 50 μm, 60 μm, 80 μm, 100 μm, 120 μm, etc.

[0107] As shown in FIGS. 2 and 3, the distance between the first conductive layer 100 and the second conductive layer 200 is the width of the sealed cavity 400, i.e., the width of the electrochromic layer, denoted as Z. Reducing the value of Z can reduce the collision distance of A + and B + , thereby shortening the diffusion time and reducing the time for which the color difference phenomenon exists. In addition, reducing the value of Z can reduce the amount of electrolyte containing electrochromic material that is injected, reduce the color contrast of the device, and increase the concentration of electrochromic material, which will cause a series of process problems. When the value of Z is 50 μm to 120 μm, the color uniformity and response rate can be effectively improved, the edge color difference phenomenon can be reduced, and the device can quickly return to the initial state after power-off.

[0108] The material forming the sealant of the present disclosure can include an adhesive liquid, and by controlling the viscosity, thixotropic index, and curing energy of the adhesive liquid, etc., the structure of the sealant can be controlled so that at least one of the values of X, Y, and Z satisfies the above conditions.

[0109] According to embodiments of the present disclosure, the viscosity of the adhesive liquid is 10,000 mpa·s to 150,000 mpa·s. In some embodiments, the viscosity of the adhesive liquid is 10,000 mpa·s, 30,000 mpa·s, 50,000 mpa·s, 70,000 mpa·s, 100,000 mpa·s, 120,000 mpa·s, 150,000 mpa·s, etc., and preferably the viscosity is 30,000 mpa·s to 80,000 mpa·s. The viscosity of the adhesive liquid can be measured by conventional instruments and methods such as a viscometer. Due to the effect of gravity, increasing the viscosity of the adhesive liquid can shorten the casting width of the adhesive liquid, which helps to shorten the difference between X and Y, and the more symmetrical the structure of the sealant, the more uniform the electric field distribution. In addition, increasing the viscosity of the adhesive liquid can easily reduce the adhesion of the adhesive liquid, thereby reducing its sealing performance and affecting the waterproof and dustproof performance of the device. When the viscosity of the adhesive liquid satisfies the above conditions, the color uniformity and response rate can be effectively improved, the edge color difference phenomenon can be reduced, and the device can quickly return to the initial state after power-off, and the viscosity of the adhesive liquid is preferably high, so that the sealing performance of the device is strong.

[0110] According to embodiments of the present disclosure, the thixotropic index of the adhesive liquid is 1-8. Illustratively, the thixotropic index of the adhesive liquid is 1, 2, 3, 4, 5, 6, 7, 8, etc., and in some embodiments, the thixotropic index of the adhesive liquid is 3-6, which can be measured by conventional instruments and methods such as viscometer, rheometer, and thixotropy tester, etc. Due to the effect of gravity, increasing the thixotropic index of the adhesive liquid can shorten the casting width of the adhesive liquid, which helps to shorten the difference between X and Y, and the more symmetrical the sealant structure is, the more uniform the electric field distribution is; in addition, increasing the thixotropic index of the adhesive liquid can easily reduce the adhesive force of the adhesive liquid, thereby reducing its sealing performance, affecting the waterproof, dustproof and other properties of the device. The thixotropic index of the adhesive liquid meets the above conditions, which can effectively improve the color change uniformity and response rate, reduce the edge color difference phenomenon, and quickly recover to the initial state after power off, and the viscosity of the adhesive liquid is better, so that the sealing performance of the device is strong.

[0111] It should be noted that the present disclosure can control the viscosity, thixotropic index and curing energy of the adhesive liquid by adjusting the types and contents of components in the adhesive liquid, and the specific types and contents can be reasonably selected and optimized based on the composition of the adhesive liquid disclosed in the art. Illustratively, the adhesive liquid contains at least one of polyacrylic acid resin, polyurethane acrylic acid resin, polyepoxy acrylic acid resin, polypropylene resin, polybutylene resin, polyurethane resin, cationic epoxy resin, modified epoxy acrylic acid resin, fluorine modified epoxy resin, silane modified epoxy resin and silicone rubber modified epoxy resin. In some embodiments, the adhesive liquid includes at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, fumed silica, 4,4'-bis(hydroxyhexafluoroisopropyl) benzene glycidyl ether, resorcinol diglycidyl ether, trioctyl trimellitate, talc, plastic balls, γ-glycidyl ether oxypropyl trimethoxysilane, diphenyl iodonium hexafluoroantimonate and 4-chlorobenzophenone. In other embodiments, the adhesive liquid includes 1-50 parts by weight of bisphenol A type epoxy resin, 1-50 parts by weight of bisphenol F type epoxy resin, 1-50 parts by weight of fumed silica, 0.1-20 parts by weight of 4,4'-bis(hydroxyhexafluoroisopropyl) benzene glycidyl ether, 1-50 parts by weight of resorcinol diglycidyl ether, 1-50 parts by weight of trioctyl trimellitate, 1-50 parts by weight of talc, 0.01-10 parts by weight of plastic balls, 1-50 parts by weight of γ-glycidyl ether oxypropyl trimethoxysilane, 0.1-50 parts by weight of diphenyl iodonium hexafluoroantimonate and 1-50 parts by weight of 4-chlorobenzophenone.

[0112] According to embodiments of the present disclosure, the adhesive liquid contains gap balls with a thickness of 50-120 μm. In some embodiments, the thickness of the gap balls is 50 μm, 60 μm, 80 μm, 100 μm, 120 μm, etc. The gap balls are placed in the adhesive liquid, and the distance between the first conductive layer and the second conductive layer, i.e., the Z value, is controlled by controlling the size of the gap balls. The gap balls can be made of materials that are not easy to deform and not easy to react with the functional materials of the device, such as glass, ceramic, calcium barium acid, polystyrene, polymethyl methacrylate, talc, etc. The thickness of the gap balls meets the above conditions, which can effectively improve the uniformity of color change and response rate, reduce the edge color difference phenomenon, and quickly recover to the initial state after power-off; at the same time, the device color contrast is appropriate, and the color change performance is excellent.

[0113] According to embodiments of the present disclosure, the curing energy of the adhesive liquid is 1000 mj / cm 2 , 2000 mj / cm 2 , 5000 mj / cm 2 , 8000 mj / cm 2 , 10000 mj / cm 2 , 12000 mj / cm 2 , 15000 mj / cm 2 , 18000 mj / cm 2 , 20000 mj / cm 2 , etc., preferably 5000 mj / cm 2 -10000 mj / cm 2 , which can be measured in combination with UV energy. In the present disclosure, the "curing energy" refers to the total energy required for the adhesive liquid to completely cure, and the higher the curing energy, the higher the energy required to be applied to completely cure the adhesive liquid, and too high energy is easy to cause serious flow phenomenon and increase the difference between X and Y. The curing energy of the adhesive liquid meets the above conditions, which can reduce the occurrence of flow phenomenon and reduce the difference between X and Y; and the viscosity of the adhesive liquid is appropriate, which can be quickly cured to improve the sealing performance of the device.

[0114] According to embodiments of the present disclosure, the first conductive layer is electrically connected with the positive electrode tab, and the second conductive layer is electrically connected with the negative electrode tab; the dyne value of the first conductive layer is A, and the dyne value of the second conductive layer is B. In some embodiments, A-B is -30-30, for example, -30, -20, -10, -5, -2, 0, 4, 6, 8, 10, 14, 20, 30, etc. In some embodiments, A-B is -2-18. In some embodiments, A-B is 4-10. The dyne value is a parameter for measuring the energy state of the solid surface, which is usually used to characterize the hydrophilicity or hydrophobicity of the material surface. The dyne value is determined by measuring the contact angle of the liquid on the solid surface, which is related to the surface tension. Exemplarily, the dyne value can be measured by a dyne pen. In the present disclosure, reducing the dyne value of the first / second conductive layer can reduce the casting distance of the adhesive liquid, and can reduce the difference between X and Y. Reducing the dyne value of the first / second conductive layer can easily lead to the difficulty in forming a strong bond with the frame sealant, thereby affecting the sealing performance. The dyne values of the first conductive layer and the second conductive layer meet the above conditions, which can make the X value and the Y value and the difference between the two meet the above conditions, which is helpful for uniform distribution of electric field, improves the uniformity of color change distribution and response rate, and is not easy to appear edge color difference phenomenon, and can quickly recover to the initial state after power off, and has strong sealing performance. In some embodiments, A-B is -2-18, and in some embodiments, A-B is 4-10, thereby reducing the spreading of the adhesive liquid to the surrounding caused by gravity to reduce the difference between X and Y.

[0115] According to embodiments of the present disclosure, the dyne value of the first conductive layer 100 is 30-60, for example, 30, 34, 40, 46, 50, 56, 60, etc., and the dyne value of the second conductive layer 200 is 30-60, for example, 30, 34, 40, 46, 50, 56, 60, etc. In this way, the first conductive layer and the second conductive layer can form a strong bond with the frame sealant, have strong sealing performance, and can also help the electric field to be uniformly distributed, improve the uniformity of color change distribution and response rate, and not easy to appear edge color difference phenomenon, and can quickly recover to the initial state after power off.

[0116] Generally, cleaning treatment is required before using the first conductive layer 100 and the second conductive layer 200. The dyne value can be adjusted by adjusting the pH value of the cleaning agent for the first conductive layer 100 and the second conductive layer 200. Specifically, the side of the first conductive layer 100 away from the second conductive layer 200 is provided with a first substrate 500, and the side of the second conductive layer 200 away from the first conductive layer 100 is provided with a second substrate 600. Before use, the first conductive layer 100 and the second conductive layer 200 are cleaned with a cleaning agent having a specific pH value, so as to have a required dyne value.

[0117] According to an embodiment of the present disclosure, the closed cavity 400 includes at least two electrochromic materials. The use of multiple electrochromic materials can provide a wider color change range, thereby achieving more diverse color display or adjustment effects, strong contrast, and more vivid color changes.

[0118] According to an embodiment of the present disclosure, the electrochromic device 10 further includes a positive electrode sheet and a negative electrode sheet, which are located on the first conductive layer or the second conductive layer, or the positive electrode sheet is located on one of the first conductive layer and the second conductive layer, and the negative electrode sheet is located on the other one of the first conductive layer and the second conductive layer.

[0119] According to an embodiment of the present disclosure, the electrochromic material can be an electrochromic liquid. The current electrochromic liquid has the problem of easy aging, mainly because the liquid component of the electrochromic liquid is easy to carry a small amount of water and oxygen when introduced. This part of water is easy to produce hydration crystals with the salt in the electrolyte or be electrolyzed to produce hydrogen and oxygen. This part of oxygen is easy to produce side reactions with the anode and cathode materials in the electrolyte solution, thereby affecting the electrochromic performance and service life of the device.

[0120] The existing method for reducing the water and oxygen content in the electrochromic liquid mainly adds an antioxidant or a water removal agent when the solution is prepared. However, this method has the following disadvantages: first, the presence of the antioxidant increases the overall cost of the product, and second, the antioxidant is easy to react with the components in the electrochromic liquid, thereby limiting its use.

[0121] In some embodiments, the water content and oxygen content of the electrochromic liquid are each not greater than 15 ppm.

[0122] The electrochromic liquid of the present disclosure can have extremely low water and oxygen content even without adding an antioxidant or a water removal agent, thereby reducing the phenomenon of side reactions between oxygen and water and the components in the electrochromic liquid, helping to improve the stability of the electrochromic liquid and slow down the aging speed of the electrochromic liquid. In this way, the color change performance of the electrochromic device can be improved, and the service life can be prolonged. The off-on cycle life under room temperature conditions can reach 100,000 groups, and the cycle life under high temperature and high humidity and cold and hot cycle conditions can reach 480 h. Thus, the device can still operate stably for a long time even in high temperature and high humidity or large temperature difference environments, and the overall performance is excellent. In addition, since it is not necessary to add an antioxidant and a water removal agent, the overall production cost of the device is reduced, and more color change systems can be adapted without paying too much attention to the side reactions between the antioxidant and the water removal agent and other components in the electrochromic liquid.

[0123] In the present disclosure, the term "water and oxygen content" refers to the water content and the oxygen content, and the water content and the oxygen content of the electrochromic liquid are based on the volume of the electrochromic liquid.

[0124] In some embodiments, the water content and the oxygen content in the electrochromic liquid are independently 0.1 ppm, 0.2 ppm, 0.3 ppm, 0.4 ppm, 0.5 ppm, 1 ppm, 2 ppm, 3 ppm, 5 ppm, 7 ppm, 9 ppm, 10 ppm, 12 ppm, 14 ppm, 15 ppm, respectively.

[0125] According to embodiments of the present disclosure, the electrochromic liquid comprises an anodic coloring material, a cathodic coloring material, an electrolyte, and a solvent.

[0126] According to embodiments of the present disclosure, the electrochromic liquid further comprises an oxide of the anodic coloring material and a hydrate of the cathodic coloring material. Due to the presence of a small amount of water and oxygen in the electrochromic liquid, water is prone to react with the cathodic coloring material to form a hydrate of the cathodic coloring material, and oxygen is prone to react with the anodic coloring material to form an oxide of the anodic coloring material. The oxide and the hydrate are usually colored substances, and the device exhibits a different color region in the absence of electricity. The process is irreversible, which will cause the device to be unable to function normally, and thus affect the color changing performance and service life of the electrochromic device.

[0127] According to embodiments of the present disclosure, the content of the oxide of the anodic coloring material is not more than 50 ppm, for example, 0.1 ppm, 1 ppm, 3 ppm, 5 ppm, 7 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, preferably not more than 10 ppm. The oxide of the anodic coloring material meets the above conditions, which can reduce the phenomenon that the device exhibits a different color region in the absence of electricity, so as to further improve the color changing performance and service life of the electrochromic device.

[0128] According to embodiments of the present disclosure, the content of the hydrate of the cathodic coloring material is not more than 50 ppm, for example, 0.1 ppm, 1 ppm, 3 ppm, 5 ppm, 7 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, preferably not more than 10 ppm. The hydrate of the cathodic coloring material meets the above conditions, which can reduce the phenomenon that the device exhibits a different color region in the absence of electricity, so as to further improve the color changing performance and service life of the electrochromic device.

[0129] According to embodiments of the disclosure, the anodic color-changing material includes at least one of nickel oxide, iridium oxide, phenazine-based compounds, polyaniline, polypyrrole, Prussian blue, thiophene-based compounds, phthalocyanine-based compounds, tungsten trioxide, molybdenum trioxide, phenothiazine-based compounds, methylene blue, viologen, methyl viologen, ethyl viologen, phenyl viologen, and propyl viologen.

[0130] According to embodiments of the disclosure, the cathodic color-changing material includes at least one of tungsten trioxide, molybdenum trioxide, phenylenediamine, nickel oxide, manganese dioxide, iridium oxide, polyaniline, Prussian blue, polypyrrole, manganese dioxide, methyl viologen, ethyl viologen, phenyl viologen, propyl viologen, 1,1'-disubstituted-4,4'-bipyridine, and 1,1'-diheptyl-4,4'-bipyridine tetrafluoroborate.

[0131] According to embodiments of the disclosure, the electrolyte includes one or more of tetrabutylammonium bromide, tetrabutylammonium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis(trifluoromethylsulfonyl)imide, polyethylene oxide, polypropylene oxide, and polymethyl methacrylate.

[0132] According to embodiments of the disclosure, the solvent includes at least one of propylene carbonate, toluene, xylene, butyrolactone, 2-acetylbutyrolactone, γ-valerolactone, ethylene carbonate, propylene carbonate, sulfolane, 3-methylsulfolane, dimethylacetamide, dimethylformamide, acetonitrile, glutaronitrile, 2-methylglutaronitrile, 3-hydroxypropanenitrile, tetraethylene glycol dimethyl ether, dimethyl sulfoxide, ethoxyethanol, and cyclopentanone.

[0133] In some embodiments, the electrochromic solution includes 5,10-dimethylphenazine, 1,1'-diheptyl-4,4'-bipyridine tetrafluoroborate, lithium tetrafluoroborate, and propylene carbonate.

[0134] The existing methods for reducing the content of impurities such as water and oxygen in a chemical solution include stripping removal, stripping method, membrane separation technology, etc. However, each of the above purification methods has its own disadvantages: the stripping removal refers to using water vapor to fill the solution to be purified, and the water vapor can displace the substances easily soluble in water in the solution, but this method itself will introduce additional water into the system, and subsequent water removal is required; the stripping method is similar to the stripping removal, the main difference is that the stripping method uses other gases (such as argon) instead of water vapor, but this also easily introduces other chemical substances, thereby increasing the difficulty of subsequent purification; the membrane separation technology can selectively filter water and oxygen, but the use process is relatively complex, the experimental conditions are relatively harsh, and it is not suitable for small-scale purification preparation.

[0135] Therefore, the present disclosure further provides a method for preparing the electrochromic liquid described above. According to an embodiment of the present disclosure, referring to FIG. 16, the method comprises: S100A heating treatment: heating the solvent to be treated to produce gas; S200A condensation treatment: condensing the gas to collect the resulting condensate to obtain the target solvent; S300A mixing treatment: mixing the anodic color material, the cathodic color material, the electrolyte, and the target solvent to obtain the electrochromic liquid.

[0136] The solvent to be treated is heated to evaporate into gas, while water and oxygen remain in the liquid. Subsequently, the solvent-containing gas is reduced to liquid after flowing through the condensation treatment, and the water and oxygen in the solvent are effectively removed, thereby obtaining the purified target solvent with low water content and low oxygen content.

[0137] According to an embodiment of the present disclosure, the temperature of the S100A heating treatment is 80-120°C, for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 105°C, or 120°C. The pressure of the S100 heating treatment is 0.01-0.05 kPa, for example, 0.01 kPa, 0.02 kPa, 0.03 kPa, 0.04 kPa, or 0.05 kPa. During the heating treatment, the reaction environment is subjected to vacuum treatment. The pressure meeting the above conditions helps to reduce the boiling point of the solvent, so that it can be effectively evaporated at the heating temperature meeting the above conditions. Although water and oxygen can also be evaporated into gas under the above temperature and pressure conditions, water and oxygen will be preferentially removed by vacuum, and the solvent will also be more easily condensed into a condensate. Thus, effective separation of the solvent and water / oxygen can be achieved. In addition, the pressure and temperature meeting the above conditions can reduce the decomposition of the solvent, reduce energy consumption and production cost. Thus, it is helpful to obtain electrochromic devices with high quality and high stability, and to improve their performance and service life.

[0138] It can be understood that the "reaction environment" described above refers to the environment in the reaction chamber of the reaction vessel containing the solvent to be treated.

[0139] According to an embodiment of the present disclosure, the temperature of the S200A condensation treatment is at least 10°C lower than the boiling point of the solvent in the solvent to be treated, for example, 10°C, 12°C, 14°C, 15°C, 16°C, 18°C, or 20°C. Thus, it is beneficial to condense the evaporated solvent gas into a solvent liquid, while water vapor and oxygen are not easily condensed and are removed by vacuum treatment, thereby achieving effective separation.

[0140] According to an embodiment of the present disclosure, the method for preparing the electrochromic liquid further comprises: recycling the condensed liquid for the heating treatment and the condensing treatment to obtain the target solvent; wherein the number of cycles is 1-5, for example, 1, 2, 3, 4 or 5. The condensed liquid is subjected to the heating treatment, the generated gas is subjected to the condensing treatment, and the condensed liquid is obtained again. The above process is regarded as a cycle. Through multiple cycles, the solvent can be more fully separated from oxygen and water, so as to reduce the water and oxygen content in the solvent, and at the same time, the waste of resources or the evaporation and decomposition of the solvent caused by excessive cycles are reduced.

[0141] According to an embodiment of the present disclosure, the method for preparing the electrochromic liquid comprises: subjecting the solvent to be treated to a heating treatment at a temperature of 95-105°C and a pressure of 0.01-0.02 kPa, subjecting the generated gas to a condensing treatment by a condenser, the temperature of the condensing treatment being 14-16°C, and collecting the condensed liquid; and repeating the heating treatment and the condensing treatment for the condensed liquid for 1-3 times to obtain the target solvent. In this way, the water and oxygen content in the solvent can be reduced, the yield can be improved, and the decomposition of the solvent can be reduced, which is especially suitable for propylene carbonate.

[0142] According to an embodiment of the present disclosure, the S300A mixing treatment is performed in an environment with a water content and an oxygen content of not more than 0.1 ppm. In this way, the water and oxygen in the environment are reduced from entering the solvent and the electrochromic liquid, so as to slow down the aging of the electrochromic liquid and improve the color-changing performance and service life of the electrochromic device.

[0143] In order to control the stability of the water and oxygen content in the production process and prevent the water and oxygen in the external air from affecting the device, all production processes related to the electrochromic liquid and the device need to use corresponding isolation means, for example, the production machine is placed in a vacuum container or an isolation container for corresponding production.

[0144] The present disclosure also provides a system for preparing the electrochromic liquid described above, which can implement the method for preparing the electrochromic liquid described above. According to an embodiment of the present disclosure, referring to FIG. 17, the system 10A comprises:

[0145] a heating unit 100A, which is used for subjecting the solvent to be treated to a heating treatment to generate gas;

[0146] a condensing unit 200A, which is connected with the heating unit 100A and is used for subjecting the gas to a condensing treatment to collect the obtained condensed liquid and obtain the target solvent;

[0147] a mixing unit 300A, which is used for mixing the anodic color-changing material, the cathodic color-changing material, the electrolyte and the target solvent to obtain the electrochromic liquid.

[0148] According to an embodiment of the present disclosure, the heating unit 100A can comprise a first temperature acquisition module 110A for monitoring the temperature of the solvent to be treated. The heating unit 100A can further comprise a stirring module 120A for stirring the solvent to be treated, so as to make the temperature uniform, facilitate rapid heating and evaporation, and improve the preparation efficiency.

[0149] According to an embodiment of the present disclosure, the system 10A further comprises a vacuum forming unit 210A connected to the condensing unit 200A, for reducing the pressure inside the system and increasing the vacuum degree. The system 10A further comprises a gas pressure acquisition module 220A connected to the condensing unit 200A, for monitoring the pressure of the gas flowing through the area of the condensing unit 200A. The device 10A can further comprise a second temperature acquisition module 230A for monitoring the temperature of the condensing unit 200A. When the pressure drops to the preset pressure, the condensing unit starts to condense, and the condensing temperature is set to be at least 10°C lower than the boiling point of the solvent in the solvent to be treated. The solvent heated and vaporized in the form of steam reaches the condensing unit through the pipeline and is condensed to liquid state.

[0150] In some embodiments, in the vacuum forming unit, if a vacuum pump is needed to form a vacuum system, a rotary vane vacuum pump, a diaphragm vacuum pump or a liquid ring vacuum pump can be selected. Preferably, a diaphragm vacuum pump is selected, which is a dry pump without lubrication and has excellent chemical resistance.

[0151] According to an embodiment of the present disclosure, the system 10A further comprises a transfer storage device 400A and a finished product storage device 500A, the transfer storage device 400A being connected to the heating unit 100A and the condensing unit 200A respectively, and the finished product storage device 500A being connected to the transfer storage device 400A. The condensed solvent is sent to the transfer storage unit through the pipeline for storage, and when the transfer storage unit collects 80% of the volume of the initial solvent to be treated, it is re-transferred to the heating unit for secondary heating and condensing. The above process is repeated. After the cycle reaches the preset number of cycles, the target solvent after water and oxygen removal is obtained. The target solvent is transferred from the transfer storage unit to the finished product storage unit and stored under low vacuum, and the water and oxygen content in the storage environment is ≤0.1 ppm.

[0152] In some embodiments, the container materials of the heating unit 100A, the condensing unit 200A, the transfer storage device 300A and the finished product storage device 400A can be selected from high borosilicate glass, 304 stainless steel and silicon nitride ceramic. Preferably, high borosilicate glass is selected, which has the characteristics of chemical corrosion resistance and high light transmittance, facilitating observation of the internal reaction process.

[0153] The material for connecting the pipes between the various devices is selected from polytetrafluoroethylene pipe, UPVC pipe, and stainless steel hose, preferably stainless steel hose, which has the characteristics of corrosion resistance and high strength. When the pipe is transported, if a pump structure is needed to promote its flow, a peristaltic pump is preferred, which does not need to directly contact the liquid and has a simple structure.

[0154] The second aspect of the present disclosure provides a method for preparing the electrochromic device of the first aspect of the present disclosure. According to an embodiment of the present disclosure, referring to FIG. 4, the method comprises: S100 applying a sealant to form a sealed cavity; S200 filling an electrolyte and sealing. Each step will be described in detail below.

[0155] S100 applying a sealant to form a sealed cavity

[0156] In this step, the sealant is applied between the first conductive layer and the second conductive layer to form a sealed cavity around the first conductive layer and the second conductive layer.

[0157] According to an embodiment of the present disclosure, referring to FIG. 5, the step of applying a sealant between the first conductive layer and the second conductive layer comprises:

[0158] S110 applying an adhesive liquid and reserving a filling port

[0159] In this step, the adhesive liquid is applied to the first surface of the first conductive layer to form an adhesive layer, and a filling port is reserved on the adhesive layer.

[0160] In some embodiments, the adhesive liquid is applied by dispensing, and the structure of the sealant can be adjusted by changing the direction of the gravity acting on the adhesive liquid, i.e., the dispensing direction. The adhesive liquid on the lower surface of the upper glass is affected by both surface tension and gravity, and spreads outward to occur flow casting; while the adhesive liquid on the upper surface of the lower glass is affected by gravity, which causes the adhesive liquid to shrink and hinder the flow casting phenomenon. Therefore, dispensing on the upper glass and adhering by inverting on the lower glass can effectively reduce the difference between X and Y.

[0161] S120 turning over, adhering and curing

[0162] In this step, the first conductive layer is turned over to make the first surface face downward, the second conductive layer is adhered to the side of the first conductive layer provided with the adhesive layer, and then curing treatment is performed to form the sealant around the first conductive layer and the second conductive layer.

[0163] The curing treatment of the present disclosure can be heating curing, room temperature curing, moisture curing, ultraviolet light curing, and ultraviolet heating double curing, etc. Since the viscosity of the adhesive liquid is prone to change under the condition of heating curing, the casting distance and wettability will have uncontrollable phenomena, and it is not easy to accurately control the difference between X and Y. Therefore, the preferred curing treatment of the present disclosure is room temperature curing, ultraviolet light curing, ultraviolet heating double curing, etc., and more preferably ultraviolet light curing and ultraviolet heating double curing. Among them, the ultraviolet heating double curing method combines ultraviolet light curing and heating curing, which can first perform ultraviolet light curing to play a shaping role and reduce viscosity changes, and then perform heating curing.

[0164] According to the embodiments of the present disclosure, the adhesive liquid treated by ultraviolet light curing contains at least one of polyacrylic resin, polyurethane acrylic resin, polyepoxy acrylic resin, polypropylene resin, polybutylene resin, and polyurethane resin, etc. The adhesive liquid treated by ultraviolet heating double curing contains at least one of cationic epoxy resin, modified epoxy acrylic resin, fluorine-modified epoxy resin, silane-modified epoxy resin, and silicone rubber-modified epoxy resin, etc.

[0165] According to the embodiments of the present disclosure, the first conductive layer and the second conductive layer are subjected to cleaning treatment before the sealant is applied between the first conductive layer and the second conductive layer. In this way, by using cleaning agents with different pH values, the dini value of the first / second conductive layer can be controlled.

[0166] The present disclosure can use a plasma cleaning machine to clean the glass after washing. The plasma cleaning machine includes a spark type plasma cleaning machine or a box type plasma cleaning machine, and the plasma equipment energy parameter is 500W-6000W. The gas used can be air, nitrogen, or argon, etc.

[0167] It should be noted that the cleaning agent used in the present disclosure is a reagent commonly used in the field of electrochromic devices to clean substrates plated with conductive layers. The specific composition is not strictly limited and can be flexibly selected according to the actual situation. By controlling the addition ratio of one or more acidic or basic components, the pH value of the cleaning agent can be adjusted to make the cleaned conductive layer have a specific dini value. For example, for a cleaning agent containing potassium hydroxide, different pH values of the cleaning agent can be obtained by controlling the amount of potassium hydroxide added.

[0168] S200 filling electrolyte, sealing

[0169] In this step, an electrolyte containing the electrochromic material is filled into the sealed cavity, and the sealed cavity is sealed again to obtain the electrochromic device. When the sealed cavity is formed in the previous step, a glue filling port is reserved, through which the electrolyte is filled into the sealed cavity, and then the sealed cavity is sealed by the packaging member to obtain the electrochromic device.

[0170] In some embodiments, the encapsulant can be an ultraviolet-cured sealant, which can be sealed to the glue port by ultraviolet curing treatment.

[0171] According to embodiments of the present disclosure, the electrolyte can include an anodic coloring material, a cathodic coloring material, an electrolyte, and a solvent.

[0172] A third aspect of the present disclosure provides an electronic device. According to embodiments of the present disclosure, the electronic device includes the electrochromic device of the first aspect. Thus, the electronic device of the present disclosure has good color change uniformity and fast response rate.

[0173] According to embodiments of the present disclosure, the electronic device includes a display, an anti-dazzle rearview mirror, a light-adjustable curtain, a light-adjustable glass window, light-adjustable color-changing glasses, electronic paper, etc.

[0174] It should be noted that the features and advantages described above for the electrochromic device of the first aspect also apply to the method of preparing the electrochromic device and the electronic device, which will not be described here again.

[0175] The anodic and cathodic electrochromic materials contained in the liquid electrochromic electrolyte may have electrophoresis phenomenon under the action of an electric field, causing the device to be layered in color, slow recovery, and poor performance. The prior art includes directly dissolving a polymer electrolyte in an organic solvent, adding a polymer monomer in a solution for polymerization, adding a polymer monomer in a solution for partial polymerization to form a prepolymer for secondary polymerization, etc. The prepared polymer electrolyte includes polyacrylate, polyacrylate isocyanate, or polyacrylate salt, etc. The above polymer electrolyte has high viscosity in the electrochromic electrolyte, which can reduce the migration rate of the electrochromic material in a non-uniform electric field, and delay the layering effect. In addition, the acrylate ion has a certain negative charge, which has a mutual bonding effect on the positive intermediate formed after the oxidation and reduction of the electrochromic material, such as the cation radical intermediate of the viologen derivative, phenazine, and phenothiazine.

[0176] However, the dissociation ability of polyacrylate salt (such as polyacrylate ammonium) in an organic solvent (such as propylene carbonate) is weak, which hinders the complexation with the positive intermediate, and thus the delay effect on the migration of the color-changing positive intermediate ion is still insufficient.

[0177] A fourth aspect of embodiments of the present disclosure provides a modified polyacrylate, the structural formula of which is shown in Formula 1:

[0178] wherein R1 is selected from any one of C1-C3 alkyl and H, and R2 is selected from any one of C1-C8 alkyl and C1-C8 terminal hydroxyl. 18 alkyl and C1-C8 terminal hydroxyl.

[0179] R3 is selected from any one of C1-C3 alkyl and H; R4 is selected from any one of C1-C 18 alkylene, C6-C 30 arylene, CF2, CHF, C2F4 and single bond; 18 R5 is selected from any one of C1-C

[0180] R6 is selected from any one of C1-C3 alkyl and H; R7 is selected from any one of C1-C 18 alkylene, C6-C 30 arylene, CF2, CHF, C2F4 and single bond;

[0181] R8, R9, R 10 and R 11 are each independently selected from any one of C1-C 18 alkyl and C1-C8 functional group with hydroxyl as the end group;

[0182] X is selected from N or P;

[0183] n, m and p each represent the degree of polymerization.

[0184] In the embodiments of the present disclosure, R8, R9, R 10 and R 11 are four groups connected to X respectively. Further, the C1-C 18 alkyl includes C1-C 18 branched alkyl or C1-C 18 linear alkyl.

[0185] The modified polyacrylate provided by the embodiments of the present disclosure is a sulfonate modified polyacrylate. By introducing alkyl sulfonate, aryl sulfonate or fluorine-containing sulfonate with stronger polarity and better low-temperature dissociation effect into the acrylate structure, the dissociation ability of the ionic polymer electrolyte is improved while the high solubility of the polyacrylate is retained. The complexation with the positive intermediate of the color-changing material is stronger, and the anti-delamination effect is better. Therefore, the modified polyacrylate provided by the embodiments of the present disclosure can be used as an ionic polymer electrolyte in a liquid-state electrochromic electrolyte, and can achieve a good anti-delamination effect.

[0186] In addition, as the size of the electrochromic device increases, the large-size electrochromic device is more likely to delaminate during long-time energization, or the electrochromic device is more likely to delaminate under low-temperature conditions. For example, the large-size electrochromic device still delaminates after more than 3 h of continuous energization, and the delamination is aggravated after 8 h. In addition, the electrochromic device is more likely to fade slowly under the cycle of on-off working conditions at a low temperature of -30°C, and the migrated color-changing material continuously accumulates to cause the device to fail.

[0187] The modified polyacrylate provided in the embodiments of the present disclosure can be suitable for large-size electrochromic devices and can be suitable for low-temperature working environments. For example, the electrochromic device (30 cm x 10 cm) using the modified polyacrylate as a polymer electrolyte has the advantages of no delamination for 12 h of continuous energization at room temperature and 14 D of cycle working at a low temperature of -30°C.

[0188] In some embodiments, the modified polyacrylate has a molecular weight of 100,000 Da to 500,000 Da, and / or n, m, and p are each independently a natural number of 5 to 3,000.

[0189] The modified polyacrylate has a molecular weight of 100,000 Da to 500,000 Da. In specific examples, the modified polyacrylate has a molecular weight of 100,000 Da, 150,000 Da, 200,000 Da, 250,000 Da, 300,000 Da, 350,000 Da, 400,000 Da, 450,000 Da, or 500,000 Da, etc.

[0190] n, m, and p are each independently a natural number of 5 to 3,000, i.e., n is a natural number of 5 to 3,000, m is a natural number of 5 to 3,000, and p is a natural number of 5 to 3,000, each independently. In specific examples, n is 5, 100, 500, 1,000, 1,500, 2,000, 2,500, or 3,000, etc. In specific examples, m is 5, 100, 500, 1,000, 1,500, 2,000, 2,500, or 3,000, etc. In specific examples, p is 5, 100, 500, 1,000, 1,500, 2,000, 2,500, or 3,000, etc.

[0191] In the embodiments of the present disclosure, by reasonably setting the polymerization degree or the molecular weight range, the anti-delamination effect is improved, and the response speed of the electrolyte color change is ensured. If the polymerization degree or the molecular weight is too high, the solubility of the prepared modified polyacrylate is reduced, the anti-delamination effect is reduced, and the viscosity is too large, which causes the liquid electrolyte to fade too slowly. If the polymerization degree or the molecular weight is too low, the viscosity of the modified polyacrylate is too small, and the anti-delamination effect is reduced.

[0192] In some embodiments, the modified polyacrylate has a molecular weight of 100,000 Da to 450,000 Da, n is a natural number of 500 to 3,000, m is a natural number of 5 to 700, and p is a natural number of 5 to 700.

[0193] Further, the modified polyacrylate has a molecular weight of 150,000 Da to 370,000 Da.

[0194] The embodiments of the present disclosure further provide respective values of the molecular weight or n, m and p of the modified polyacrylate, which are conducive to obtaining better anti-delamination effect.

[0195] In some embodiments, R4 is selected from a single bond or a C6-C 30 arylene group, and R7 is selected from a single bond or a C6-C 30 arylene group. The modified polyacrylate provided by the embodiments of the present disclosure is used in a liquid electrochromic electrolyte, and can achieve better anti-delamination effect.

[0196] In specific examples, the modified polyacrylate has a structural formula as shown in any one of Formula 1-1 to Formula 1-8.

[0197] In the embodiments of the present disclosure, the modified polyacrylate has a structural formula as shown in any one of Formula 1-1 to Formula 1-8. These modified polyacrylate polymers exhibit better anti-delamination effect when applied in a liquid electrochromic electrolyte.

[0198] The fifth aspect of the embodiments of the present disclosure provides a preparation method of the modified polyacrylate described above, which comprises: preparing the modified polyacrylate by copolymerization of a polyacrylate monomer, a sulfonate monomer and a sulfonic acid ester monomer; the sulfonate monomer comprises at least one of a quaternary ammonium sulfonate and a quaternary phosphonium sulfonate.

[0199] The modified polyacrylate obtained has a structural formula as shown in Formula 1:

[0200] wherein R1 is selected from any one of C1-C3 alkyl and H, R2 is selected from any one of C1-C 18 alkyl and C1-C8 terminal hydroxyl group;

[0201] R3 is selected from any one of C1-C3 alkyl and H, R4 is selected from any one of C1-C 18 alkylene group, C6-C 30 arylene group, CF2, CHF, C2F4 and a single bond, and R5 is selected from any one of C1-C 18 alkyl group.

[0202] R6 is selected from any one of C1-C3 alkyl and H, and R7 is selected from any one of C1-C18 Alkylene, C6-C 30 Any one of the aryl group, CF2, CHF, C2F4 and a single bond;

[0203] R8, R9, R 10 and R 11 Each independently selected from C1-C 18 It can be any one of the alkyl group and the C1-C8 terminal group which is a hydroxyl group;

[0204] X is selected from N or P;

[0205] n, m, and p each represent the degree of aggregation.

[0206] The modified polyacrylate prepared in this embodiment, as an ionic polymer electrolyte, can achieve good anti-delamination effect when used in liquid electrochromic electrolytes; moreover, the modified polyacrylate is suitable for large-size electrochromic devices and can be used in low-temperature operating environments.

[0207] The preparation method provided in this disclosure has a simple synthesis route, low cost, and is easy to operate.

[0208] In some embodiments, the molar ratio of the polyacrylate monomer, sulfonate monomer and sulfonate monomer is 1:0.001-0.5:0.001-0.5. In specific examples, the molar ratios of polyacrylate monomer, sulfonate monomer, and sulfonate monomer are 1:0.001:0.001, 1:0.005:0.001, 1:0.01:0.001, 1:0.05:0.001, 1:0.1:0.001, 1:0.2:0.001, 1:0.3:0.001, 1:0.4:0.001, 1:0.5:0.001, 1:0.001:0.005, 1:0.001:0.01, 1:0.001:0.05, 1:0.001:0.1, 1:0.001:0.2, 1:0.001:0.3, 1:0.001:0.4, or 1:0.001:0.5, etc.

[0209] In this embodiment, by setting the ratio of polyacrylate monomer, sulfonate monomer, and sulfonate monomer, and adding an appropriate amount of sulfonate monomer, the resulting modified polyacrylate maintains high solubility in the electrochromic electrolyte solvent, thereby improving the anti-stratification effect. Since the sulfonic acid groups in the sulfonate monomer have hydrophilic and oleophobic properties, if the added sulfonate monomer is too high, it may reduce the solubility of the modified polyacrylate and affect the anti-stratification effect.

[0210] In some embodiments, the sulfonate monomer comprises at least one of an alpha-alkenyl sulfonate monomer and a vinyl benzene sulfonate monomer; and / or, the sulfonate ester monomer comprises at least one of an alpha-alkenyl sulfonate ester monomer and a vinyl benzene sulfonate ester monomer; wherein, the alpha-alkenyl sulfonate monomer has a structural formula as shown in Formula 2:

[0211] The vinyl benzene sulfonate monomer has a structural formula as shown in Formula 3:

[0212] The modified polyacrylate prepared by the preparation method of the embodiments of the present disclosure is shown in Formula 1, wherein, R1 and R2 are from the functional groups of the acrylate monomer, R3, R4 and R5 are from the functional groups of the alpha-alkenyl sulfonate ester monomer or the vinyl benzene sulfonate ester monomer, and R6 and R7 are from the functional groups of the alpha-alkenyl sulfonate monomer or the vinyl benzene sulfonate monomer.

[0213] In some embodiments, the preparation method of the modified polyacrylate comprises: copolymerizing the acrylate monomer, the alpha-alkenyl sulfonate monomer and the alpha-alkenyl sulfonate ester monomer to prepare the modified polyacrylate, and the reaction formula is shown in Formula I:

[0214] The preparation method provided by the embodiments of the present disclosure has a simple synthesis route, low cost and convenient operation; and the sulfonate modified polyacrylate prepared by the preparation method exhibits good anti-delamination effect.

[0215] In some embodiments, the initiation mode of the copolymerization reaction comprises chemical initiator initiation and physical initiation.

[0216] Further, the initiator used in the chemical initiator initiation comprises at least one of azobisisobutyronitrile, dibenzoyl peroxide and benzophenone.

[0217] In the embodiments of the present disclosure, the chemical initiator is used as the free radical polymerization initiator, which is beneficial to effectively obtain the required modified polyacrylate.

[0218] In some embodiments, the molar ratio of the acrylate monomer to the chemical initiator is 1:0.001-0.01. In specific examples, the molar ratio of the acrylate monomer to the chemical initiator is 1:0.001, 1:0.002, 1:0.003, 1:0.004, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009 or 1:0.01, etc.

[0219] By controlling the addition of an appropriate amount of chemical initiator, the modified polyacrylate with an appropriate molecular weight can be synthesized, and the anti-delamination effect is improved.

[0220] In some embodiments, the physical initiation includes radiation initiation and heating initiation. Among them, the way of radiation initiation includes microwave initiation and electron beam initiation.

[0221] In some embodiments, the temperature of the copolymerization reaction is 70-100°C.

[0222] In some embodiments, the temperature of the copolymerization reaction is 70-100°C, which is conducive to improving the efficiency of the copolymerization reaction. Too high a temperature will cause the initiator to decompose too quickly, increase the chain termination reaction speed, and result in a decrease in the degree of polymerization. In specific examples, the copolymerization reaction temperature is 70°C, 80°C, 90°C, or 100°C.

[0223] In some embodiments, the temperature of the copolymerization reaction is 75-85°C.

[0224] In some embodiments, the temperature of the copolymerization reaction is 70-100°C, which is conducive to quickly obtaining the desired degree of polymerization of the modified polyacrylate.

[0225] In some embodiments, the copolymerization reaction time is 0.5-24h. Further, the copolymerization reaction time is 1-12h.

[0226] In some embodiments, after the copolymerization reaction is completed, the desired modified polyacrylate is obtained through purification treatment.

[0227] In some embodiments, the copolymerization reaction time is 0.5-24h. Further, the copolymerization reaction time is 1-12h.

[0228] In some embodiments, the purification treatment includes adding anhydrous ethanol to precipitate the solid product, then using a washing solvent to wash the unreacted monomer, residual initiator, and reaction solvent, and finally drying.

[0229] In some embodiments, the washing solvent includes an organic solvent. Further, the organic solvent includes at least one of anhydrous ethanol, petroleum ether, n-hexane, diethyl ether, acetone, acetonitrile, toluene, tetrahydrofuran, chloroform, and dichloromethane.

[0230] In some embodiments, the method for preparing the α-alkenyl sulfonate monomer includes one of the following (1)-(3) methods:

[0231] (1) reacting sodium α-alkenyl sulfonate with a quaternary ammonium salt or a quaternary phosphonium salt to obtain an α-alkenyl sulfonate monomer;

[0232] (2) reacting silver α-alkenyl sulfonate with a quaternary ammonium salt or a quaternary phosphonium salt to obtain an α-alkenyl sulfonate monomer;

[0233] (3) reacting an α-alkenyl sulfonate ester with a trialkylamine or a trialkyl phosphine to obtain an α-alkenyl sulfonate monomer.

[0234] In some embodiments, the method for preparing the alpha-olefin sulfonate monomer comprises:

[0235] reacting the sodium alpha-olefin sulfonate with a quaternary ammonium salt or a quaternary phosphonium salt to obtain the alpha-olefin sulfonate monomer, and the reaction formula is shown in Formula II:

[0236] The method for preparing the alpha-olefin sulfonate monomer provided by the embodiments of the present disclosure is to perform ion exchange reaction of the sodium alpha-olefin sulfonate with the quaternary ammonium salt or the quaternary phosphonium salt, and the synthetic route is simple and the preparation cost is low.

[0237] In some embodiments, the coordinating anion of the quaternary ammonium salt or the quaternary phosphonium salt comprises at least one of F - , Cl - , Br - , ClO4 - , BF4 - , PF6 - , and CF3SO3 - .

[0238] In some embodiments, the molar ratio of the sodium alpha-olefin sulfonate to the quaternary ammonium salt or the quaternary phosphonium salt is 2:1-1:2. In specific examples, the molar ratio of the sodium alpha-olefin sulfonate to the quaternary ammonium salt or the quaternary phosphonium salt is 2:1, 1.5:1, 1:1, 1:1.5, or 2:1, etc. The embodiments of the present disclosure set the molar ratio of the sodium alpha-olefin sulfonate to the quaternary ammonium salt or the quaternary phosphonium salt to be 2:1-1:2, which is conducive to improving the reaction efficiency and preparing the target product alpha-olefin sulfonate.

[0239] In some embodiments, the molar ratio of the sodium alpha-olefin sulfonate to the quaternary ammonium salt or the quaternary phosphonium salt is 1.5:1-1:1. In specific examples, the molar ratio of the sodium alpha-olefin sulfonate to the quaternary ammonium salt or the quaternary phosphonium salt is 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, or 1:1, etc.

[0240] In the embodiments of the present disclosure, the excess quaternary ammonium salt or quaternary phosphonium salt will be dissolved in the solvent together with the product, which cannot be filtered and purified, and the purification is difficult. Therefore, the excess sodium alpha-olefin sulfonate is added in the reaction, which can be removed by filtration, facilitating the purification and accelerating the reaction rate.

[0241] In some embodiments, the solvent used for the reaction of the sodium alpha-olefin sulfonate with the quaternary ammonium salt or the quaternary phosphonium salt comprises at least one of cyan-based organic solvents, amide-based organic solvents, sulfoxide-based organic solvents, ester-based organic solvents, ketone-based organic solvents, ether-based organic solvents, halogenated hydrocarbon-based organic solvents, and alcohol-based organic solvents.

[0242] In specific examples, the cyan-based organic solvent comprises acetonitrile.

[0243] In specific examples, the amide organic solvent includes at least one of dimethylformamide and dimethylacetamide.

[0244] In specific examples, the sulfoxide organic solvent includes dimethyl sulfoxide.

[0245] In specific examples, the ester organic solvent includes at least one of methyl acetate, ethyl acetate and butyl acetate.

[0246] In specific examples, the ketone organic solvent includes at least one of acetone and methyl ethyl ketone.

[0247] In specific examples, the ether organic solvent includes at least one of diethyl ether, isopropyl ether, cyclopentyl methyl ether, tetrahydrofuran and dioxane.

[0248] In specific examples, the halogenated hydrocarbon organic solvent includes at least one of chloroform, dichloromethane and 1,2-dichloroethane.

[0249] In specific examples, the alcohol organic solvent includes at least one of methanol, ethanol and isopropyl alcohol.

[0250] In some embodiments, the sodium a-alkenyl sulfonate is reacted with a quaternary ammonium salt or a quaternary phosphonium salt at a reaction temperature of 25°C to 120°C. In specific examples, the reaction temperature is 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C and 120°C, etc.

[0251] The reaction temperature is set to 25°C to 120°C in the embodiments of the present disclosure, which is conducive to improving the reaction efficiency and facilitating the later separation and purification. The distillation temperature of the filtrate after filtering the synthesized a-alkenyl sulfonate monomer should not be too high, because high temperature may cause the a-alkenyl functional group to polymerize, affecting the yield and purity.

[0252] In some embodiments, the reaction temperature is 25°C to 80°C.

[0253] This is conducive to improving the reaction efficiency and obtaining a-alkenyl sulfonate with higher purity.

[0254] In some embodiments, the reaction time is 1h to 24h. In some embodiments, the reaction time is 1h to 12h.

[0255] In some embodiments, the method for preparing a-alkenyl sulfonate monomer includes:

[0256] The a-alkenyl sulfonate is reacted with a trialkylamine or a trialkyl phosphine to obtain a-alkenyl sulfonate monomer, and the reaction formula is shown in Formula III:

[0257] The method for preparing the α-alkenyl sulfonate monomer provided by the embodiments of the present disclosure is simple in synthesis route and low in preparation cost.

[0258] In some embodiments, the reaction temperature is 25-200℃.

[0259] In the embodiments of the present disclosure, the α-alkenyl sulfonate ester is reacted with the trialkylamine or trialkylphosphine by heating, which is conducive to improving the reaction efficiency.

[0260] In some embodiments, the reaction temperature is 25-120℃.

[0261] In some embodiments, the molar ratio of the α-alkenyl sulfonate ester to the trialkylamine or trialkylphosphine is ≤1:1.

[0262] In the embodiments of the present disclosure, by adding the trialkylamine or trialkylphosphine in an amount equivalent to or in excess of the α-alkenyl sulfonate ester, the reaction efficiency is improved. The amount of the trialkylamine or trialkylphosphine added is at least equivalent to that of the α-alkenyl sulfonate ester; in some embodiments, the amount of the trialkylamine or trialkylphosphine added is in excess of that of the α-alkenyl sulfonate ester.

[0263] In some embodiments, the solvent used for the reaction of the α-alkenyl sulfonate ester with the trialkylamine or trialkylphosphine includes at least one of acetonitrile, anhydrous ethanol, acetone, chloroform, toluene and tetrahydrofuran.

[0264] In some embodiments, the post-treatment of the reaction can be performed by precipitation and washing using a solvent (the solvent includes at least one of diethyl ether, petroleum ether, anhydrous ethanol and acetonitrile) to remove the excess trialkylamine or trialkylphosphine. In some embodiments, the obtained α-alkenyl sulfonate ammonium or α-alkenyl sulfonate phosphonium monomer is subjected to solvent removal by heating under reduced pressure.

[0265] In some embodiments, the method for preparing the α-alkenyl sulfonate monomer includes:

[0266] The α-alkenyl sulfonate silver is reacted with the quaternary ammonium salt or quaternary phosphonium salt to obtain the α-alkenyl sulfonate monomer.

[0267] In the embodiments of the present disclosure, the α-alkenyl sulfonate silver is precipitated by being reacted with the quaternary ammonium salt or quaternary phosphonium salt, which is conducive to precipitating the silver salt, speeding up the reaction efficiency, facilitating the separation of the main product and reducing the difficulty of post-treatment.

[0268] In some embodiments, the α-alkenyl sulfonate silver is reacted with the quaternary ammonium salt or quaternary phosphonium salt to obtain the α-alkenyl sulfonate monomer, and the reaction formula is as shown in Formula IV:

[0269] In the embodiments of the present disclosure, the coordination anion used for the silver ion precipitation reaction includes halide ions such as F -F, Cl - Br - or I - .

[0270] The sixth aspect of the embodiments of the present disclosure provides an electrochromic electrolyte, comprising at least one of the modified polyacrylates described above, or comprising at least one of the modified polyacrylates obtained by the preparation method described above.

[0271] The embodiments of the present disclosure use the at least one modified polyacrylate described above as an electrochromic electrolyte, which is conducive to improving the anti-layering effect of the liquid electrochromic electrolyte, and can be applied to large-size liquid electrochromic devices and exhibit high anti-layering effect under low-temperature working conditions.

[0272] The seventh aspect of the embodiments of the present disclosure provides an electrochromic electrolyte, comprising the electrochromic electrolyte described above.

[0273] The embodiments of the present disclosure use the at least one modified polyacrylate described above as an electrochromic electrolyte, and the liquid electrochromic electrolyte provided exhibits good anti-layering effect, and can be applied to large-size liquid electrochromic devices and exhibit high anti-layering effect under low-temperature working conditions.

[0274] In some embodiments, the mass percentage content of the modified polyacrylate in the electrochromic electrolyte is 1wt%~10wt%. In specific examples, the mass percentage content of the modified polyacrylate in the electrochromic electrolyte is 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%, etc.

[0275] In the embodiments of the present disclosure, the amount of the modified polyacrylate in the electrochromic electrolyte will affect the anti-layering effect. If the content of the modified polyacrylate in the electrochromic electrolyte is too high, the viscosity of the electrochromic electrolyte will be too large, the overall bleaching response speed will be reduced, and at the same time, the solubility of the modified polyacrylate in the solvent will be reduced, and the anti-layering effect will be reduced.

[0276] In some embodiments, the mass percentage content of the modified polyacrylate in the electrochromic electrolyte is 1wt%~5wt%. The anti-layering effect of the electrochromic electrolyte is improved.

[0277] In some embodiments, the electrochromic electrolyte further comprises a solvent and an electrochromic material.

[0278] In some embodiments, the electrochromic material comprises a cathode color-changing material and an anode color-changing material.

[0279] In some embodiments, the cathodic color-changing material includes at least one of alkyl viologen and derivatives thereof, and the anion is tetrafluoroborate, perchlorate, hexafluorophosphate, or the like, such as methyl viologen ditetrafluoroborate, ethyl viologen di-perchlorate (36305-51-8), ethyl viologen dihexafluorophosphate (138926-07-5), heptyl viologen ditetrafluoroborate; and / or, the anodic color-changing material includes at least one of phenazine, phenothiazine, ferrocene and derivatives thereof, such as dihydrophenazine, 5,10-dimethylphenazine (15546-75-5), phenothiazine (92-84-2), 10-methylphenothiazine (1207-72-3), ferrocene, methylferrocene.

[0280] In some embodiments, the solvent includes at least one of ether or polyether solvents, alcohol solvents, nitrile solvents, ketone solvents, cyclic ester solvents, and carbonate solvents.

[0281] In some embodiments, the ether or polyether solvents include at least one of 3-methylsulfolane, dimethyl sulfoxide, dimethylformamide, tetraglyme, and polyethylene glycol; the alcohol solvents include ethoxyethanol; the nitrile solvents include at least one of acetonitrile, glutaronitrile, 3-hydroxypropionitrile, and 2-methylglutaronitrile; the ketone solvents include at least one of 2-acetylbutyrolactone and cyclopentanone; the cyclic ester solvents include at least one of β-propiolactone, γ-butyrolactone, and γ-valerolactone; and the carbonate solvents include at least one of acid propylene carbonate, ethylene carbonate, and propylene carbonate.

[0282] In some embodiments, the solvent is an anhydrous and oxygen-free solvent.

[0283] An eighth aspect of the embodiments of the present disclosure provides a preparation method of the electrochromic electrolyte, including:

[0284] Mixing the modified polyacrylate with raw materials including the color-changing material and the solvent to obtain the electrochromic electrolyte.

[0285] Alternatively, the polyacrylate monomer, the sulfonate monomer, and the sulfonate ester monomer are subjected to a copolymerization reaction, and then raw materials including the color-changing material and the solvent are added to obtain the electrochromic electrolyte.

[0286] The preparation method of the electrochromic electrolyte provided by the embodiments of the present disclosure can be: first, preparing the modified polyacrylate with high purity, and then mixing the modified polyacrylate with other raw materials of the electrolyte to obtain the electrochromic electrolyte, which is equivalent to a two-step method.

[0287] The preparation method of the electrochromic electrolyte provided by the embodiments of the present disclosure can also be: directly adding other raw materials of the electrolyte to the system after the copolymerization reaction is completed to obtain the electrochromic electrolyte, which is a one-pot method.

[0288] The one-pot method for preparing the electrochromic electrolyte does not need to purify, crystallize and resolubilize the sulfonate modified polyacrylate, and can directly prepare the electrolyte; and the use of anhydrous oxygen solvent can improve the free radical utilization rate of the initiator, make the polymerization condition more stable, and facilitate the control of the polymerization degree and the repeatability of the preparation process.

[0289] The ninth aspect of the embodiments of the present disclosure provides an electrochromic device comprising the electrolyte or the electrolyte prepared by the preparation method.

[0290] The electrochromic device provided by the embodiments of the present disclosure has high anti-delamination effect, can be applied to the generation of large-size devices, and can also be applied to low-temperature conditions.

[0291] In specific examples, the electrochromic device includes an automobile anti-dazzle rearview mirror, an aircraft porthole, a dimming glass, a display, a wearable device, or an energy storage device.

[0292] In some embodiments, under the condition of a 1.2V pulse voltage test, the current stable stage duration of the electrochromic device is above 8000s, and / or the 12h coloration aggregation is ≤5.6%. In specific examples, the current stable stage duration of the electrochromic device is 9000s, 10000s, 11000s, 12000s, 13000s, 14000s, 15000s, 16000s, 17000s, 18000s, 19000s, 20000s, 21000s, 22000s, 23000s, 24000s, 25000s, 26000s, 27000s, 28000s, 29000s, 30000s, 32000s, 35000s, 40000s, 45000s, 50000s, 54000s, 58000s, 60000s, or 65000s, etc. In specific examples, the 12h coloration aggregation is 1.3%, 1.5%, 1.8%, 2.1%, 2.2%, 2.8%, 3.1%, 3.2%, 3.5%, 4.0%, 4.2%, 4.5%, 5.0%, 5.1%, 5.3%, or 5.6%, etc.

[0293] The electrochromic device provided by the embodiments of the present disclosure has a high anti-layering effect. After a test condition of applying a 1.2V pulse power source to the electrochromic device, the electrochromic device maintains a stable current for more than 8000s, and the surface electrochromic device electrophoresis phenomenon is effectively inhibited; after the current is maintained stable, the current continues to rise, and the electrophoresis phenomenon appears. The greater the aggregation degree value, the greater the migration rate of the electrochromic material in a non-uniform electric field, and the more likely the layering; in the embodiments of the present disclosure, the 12h color aggregation degree is less than or equal to 5.6%, which indicates that the modified polyacrylate provided by the present disclosure can effectively slow down the migration rate of the electrochromic material in a non-uniform electric field, and achieve the technical effect of delaying layering.

[0294] The tenth aspect of the present disclosure provides an electrochromic device. According to the embodiments of the present disclosure, the electrochromic device comprises: a first conductive layer, an electrochromic layer and a second conductive layer which are arranged in a stack; the first conductive layer or the second conductive layer comprises: a main body part and an edge part, the main body part and the edge part are arranged in a spaced manner; an insulating structure, the insulating structure is arranged on the side of the first conductive layer or the second conductive layer facing the electrochromic layer, and the insulating structure and the edge part are respectively arranged on the two sides of the electrochromic layer and are not located on the same conductive layer; a first conductive coating, the first conductive coating is connected with one of the first conductive layer and the second conductive layer, and is connected with the other of the first conductive layer and the second conductive layer through the insulating structure; a second conductive coating, the second conductive coating is connected with the one of the first conductive layer and the second conductive layer which does not contain the edge part and the edge part respectively.

[0295] According to the electrochromic device of the embodiments of the present disclosure, the first conductive layer or the second conductive layer comprises the main body part and the edge part arranged in a spaced manner, so that the edge part, the second conductive coating and the first conductive layer or the second conductive layer are connected in parallel with each other, which can reduce the internal resistance of the device. In addition, the edge part and the second conductive coating are connected in parallel, which increases the effective area of the second conductive coating, makes the current line divergence effect better, and thus helps to reduce the internal resistance of the device, thereby reducing the overall resistance of the device and improving the coloration uniformity and the bleaching rate. Moreover, in the case of achieving the same internal resistance, the amount of the second conductive coating can be reduced, thereby saving the production cost.

[0296] According to the embodiments of the present disclosure, in the direction of the main body part towards the edge part, at least one of the following conditions is met: the width of the edge part is 0.05mm-2.7mm; the shortest distance between the main body part and the edge part is 0.3mm-2.9mm; the width of the edge part is M, the shortest distance between the main body part and the edge part is N, and the sum of M and N is 0.35mm-3mm.

[0297] According to an embodiment of the present disclosure, in a direction in which the main body portion is toward the edge portion, at least one of the following conditions is satisfied: the width of the edge portion is 0.1 mm to 2 mm; the shortest distance between the main body portion and the edge portion is 1 mm to 2.9 mm; the width of the edge portion is M, the shortest distance between the main body portion and the edge portion is N, and the sum of M and N is 2.5 mm to 3 mm.

[0298] According to an embodiment of the present disclosure, the electrochromic device has a resistance of 30 Ω to 150 Ω.

[0299] According to an embodiment of the present disclosure, the main body portion includes a center portion and a patterned structure located on a side of the center portion away from the edge portion, the patterned structure is electrically connected to the center portion, and the patterned structure includes a plurality of first through holes arranged at intervals.

[0300] According to an embodiment of the present disclosure, the patterned structure satisfies at least one of the following conditions: the aperture of the first through hole is 0.3 mm to 2.9 mm; the shortest distance from the edge of the first through hole to a side of the patterned structure away from the center portion is 0.05 mm to 2.7 mm; the aperture of the first through hole is P, the shortest distance from the edge of the first through hole to a side of the patterned structure away from the center portion is Q, and the sum of P and Q is 0.35 mm to 3 mm.

[0301] According to an embodiment of the present disclosure, the patterned structure satisfies at least one of the following conditions: the aperture of the first through hole is 1 mm to 2.9 mm; the shortest distance from the edge of the first through hole to a side of the patterned structure away from the center portion is 0.1 mm to 2 mm; the aperture of the first through hole is P, the shortest distance from the edge of the first through hole to a side of the patterned structure away from the center portion is Q, and the sum of P and Q is 2.5 mm to 3 mm.

[0302] According to an embodiment of the present disclosure, the first conductive layer or the second conductive layer containing the edge portion further comprises: a first resistance regulation path, one end of the first resistance regulation path being electrically connected to one end of the edge portion, and the other end of the first resistance regulation path being electrically connected to one end of the patterned structure; a second resistance regulation path, one end of the second resistance regulation path being electrically connected to the other end of the edge portion, and the other end of the second resistance regulation path being electrically connected to the other end of the patterned structure; a first resistance regulation path, one end of the first resistance regulation path being electrically connected to one end of the edge portion, and the other end of the first resistance regulation path being electrically connected to one end of the patterned structure; a second resistance regulation path, one end of the second resistance regulation path being electrically connected to the other end of the edge portion, and the other end of the second resistance regulation path being electrically connected to the other end of the patterned structure; the resistances of the edge portion and the patterned structure are each independently 4Ω-30Ω; and the parallel resistances of the first resistance regulation path and the second resistance regulation path are each independently 30Ω-1000Ω.

[0303] According to an embodiment of the present disclosure, at least one of the following conditions is met: the resistance difference between the first resistance regulation path and the second resistance regulation path is not greater than 20% of any one of the first resistance regulation path resistance value and the second resistance regulation path resistance value; the resistances of the first resistance regulation path and the second resistance regulation path are each independently 30Ω-1000Ω; the parallel resistances of the first resistance regulation path and the second resistance regulation path are each independently 45Ω-200Ω; and the resistances of the edge portion and the patterned structure are each independently 4Ω-10Ω.

[0304] According to an embodiment of the present disclosure, the resistances of the first resistance regulation path and the second resistance regulation path are each independently 90Ω-400Ω.

[0305] According to an embodiment of the present disclosure, a resistance member is arranged on the first resistance regulation path and / or the second resistance regulation path.

[0306] According to an embodiment of the present disclosure, in a direction perpendicular to the main body portion towards the edge portion, the length of the edge portion is A, and the length of the patterned structure is B; in the direction of the main body portion towards the edge portion, the length of the first resistance regulation path is C, and the length of the second resistance regulation path is D; A, B, C, and D satisfy: A+B≥50%×(A+B+C+D).

[0307] According to an embodiment of the present disclosure, the electrochromic device comprises: a first substrate disposed on a side of the first conductive layer away from the electrochromic layer; a positive electrode sheet and a negative electrode sheet, at least one of which comprises: a first portion in contact with the first conductive layer and the first substrate respectively and disposed along the thickness direction of the first substrate; a second portion intersecting the first portion and extending in a direction away from the first conductive layer; a third portion intersecting the first portion and extending in a direction away from the second portion, the third portion being in contact with the first substrate.

[0308] According to an embodiment of the present disclosure, a first included angle between the first portion and the second portion is 10°-135°; and / or, a second included angle between the first portion and the third portion is 70°-95°.

[0309] According to an embodiment of the present disclosure, a first included angle between the first portion and the second portion is 50°-90°; and / or, a second included angle between the first portion and the third portion is 80°-90°.

[0310] According to an embodiment of the present disclosure, in the direction of the first conductive layer towards the second conductive layer, the length of the first portion is 50%-100% of the thickness of the first substrate; and / or, a side of the first portion and the third portion towards the first conductive layer is provided with an adhesive layer.

[0311] According to an embodiment of the present disclosure, in the direction of the first conductive layer towards the second conductive layer, the length of the first portion is 0.1mm-3mm; and / or, in the direction of the main body portion towards the edge portion, the length of the second portion is 0.1mm-3mm; and / or, in the direction of the main body portion towards the edge portion, the length of the third portion is 10mm-20mm.

[0312] According to an embodiment of the present disclosure, at least one of the first portion, the second portion and the third portion is distributed with a plurality of second through holes.

[0313] According to an embodiment of the present disclosure, the aperture of the second through hole is 30 mesh-100 mesh.

[0314] According to an embodiment of the present disclosure, a gap region is included between the main body portion and the edge portion, and the electrochromic device further comprises: a first encapsulant and a second encapsulant, the first encapsulant and the second encapsulant being connected to two ends of the electrochromic layer respectively; a projection of the gap region towards the electrochromic layer coincides with one of the first encapsulant and the second encapsulant, and a projection of the edge portion towards the electrochromic layer does not completely coincide with the one of the first encapsulant and the second encapsulant; a projection of the patterned structure towards the electrochromic layer coincides with the other of the first encapsulant and the second encapsulant.

[0315] According to an embodiment of the present disclosure, at least one of the following conditions is met: one of the first conductive layer and the second conductive layer is a reflective conductive layer, and the other is a transparent conductive layer; the electrochromic layer comprises: an anodic coloring material, a cathodic coloring material, an electrolyte, and a solvent; the first conductive coating and the second conductive coating comprise a conductive metal.

[0316] According to an embodiment of the present disclosure, the electrochromic device further comprises: a second substrate, the second substrate being arranged on a side of the second conductive layer away from the electrochromic layer.

[0317] The electrochromic device of the tenth aspect of the present disclosure will be described in detail below.

[0318] FIG. 7 shows a schematic diagram of an electrochromic device structure of the present disclosure, the electrochromic device 10 comprising a first conductive layer 100, an electrochromic layer 300P, and a second conductive layer 200P arranged in a stack; an insulating structure 400P; a first conductive coating 500P; and a second conductive coating 600P. The advantages of the electrochromic device structure design of the present disclosure will be described in detail below in combination with FIG. 7:

[0319] According to an embodiment of the present disclosure, one of the first conductive layer 100 and the second conductive layer 200P is a transparent conductive layer, and the other is a reflective conductive layer. The transparent conductive layer has both transparency and conductivity, allowing light to pass through while providing the necessary electrical conductivity to drive color change. When the electrochromic device is in use, it is observed from the side of the transparent conductive layer. The reflective conductive layer is a conductive layer with light reflection performance, which can reflect more light when the electrochromic material changes color under the action of an electric field, making the color change more obvious. FIG. 7 shows a case where the first conductive layer 100 is a reflective conductive layer and the second conductive layer 200P is a transparent conductive layer, thereby obtaining a larger observation field of view, reducing the obstruction of the electrode sheet, and providing a better experience. In some embodiments, the first conductive layer 100 and the second conductive layer 200P can each comprise ITO, silver alloy, aluminum alloy, chromium metal, copper metal, gold, and a mixture containing one or more of the above substances, or a thin film structure stacked on each other.

[0320] According to an embodiment of the present disclosure, the first conductive layer 100 or the second conductive layer 200P comprises a main body part 110 and an edge part 120, which are arranged in intervals;

[0321] The insulating structure 400P is arranged on the side of the first conductive layer 100 or the second conductive layer 300P facing the electrochromic layer 200P, and the insulating structure 400P and the edge part 120 are arranged on both sides of the electrochromic layer 200P and not on the same conductive layer;

[0322] The first conductive coating 500P is connected to one of the first conductive layer 100 and the second conductive layer 200P, and connected to the other of the first conductive layer 100 and the second conductive layer 200P through the insulating structure 400P;

[0323] The second conductive coating 600P is connected to one of the first conductive layer 100 and the second conductive layer 200P which does not contain the edge part 120, and the edge part 120, respectively.

[0324] For example, in the processing of the electrochromic device, the edge conductive material is usually removed from the cutting site a to the edge to avoid short circuit. The electrochromic device of the present disclosure does not completely remove the conductive material at the edge of the first conductive layer, but retains a part of it, which is called the "edge part". That is, the main body part and the edge part are arranged in intervals on the first conductive layer. At the same time, the insulating structure is arranged on the side of the first / second conductive layer facing the electrochromic layer, and is symmetrically arranged on both sides of the electrochromic layer with the edge part to prevent short circuit. In this way, on the one hand, since the main body part and the edge part are arranged in intervals, the connection between the electrode sheet and the conductive layer is blocked, and the short circuit of the electrochromic device can still be effectively avoided. On the other hand, the main circuit of the device is negative electrode sheet-first conductive layer-electrochromic layer-second conductive layer-positive electrode sheet, and the first conductive coating is connected in parallel with the second conductive layer. By retaining the edge part on the first conductive layer, the edge part is connected in parallel with the first conductive coating and the second conductive layer, respectively (as shown in FIG. 8), thereby reducing the internal resistance of the circuit. On the other hand, the edge part and the second conductive coating are connected in parallel, which increases the effective area of the second conductive coating and makes the current line divergence effect better, thereby helping to further reduce the internal resistance of the device and effectively improve the color change uniformity and fading rate of the device. Moreover, the amount of the second conductive coating can be reduced to save production costs under the condition that the device has the same internal resistance. For the convenience of understanding, the area between the main body part and the edge part is called the "interval area", that is, the interval area is included between the main body part and the edge part.

[0325] It should be noted that the main body part and the edge part arranged at intervals can be located on the first conductive layer or the second conductive layer, and are preferably formed on the conductive layer with smaller resistance. For example, the main body part and the edge part are formed on the first conductive layer. The insulating structure can be located on the side of the first conductive layer facing the electrochromic layer or on the side of the second conductive layer facing the electrochromic layer. The insulating structure and the edge part are located on the two sides of the electrochromic layer and are not located on the same conductive layer, so as to prevent short circuit. For example, the edge part is arranged on the second conductive layer, and the negative electrode sheet, the first conductive coating, the first conductive layer, the second conductive coating, and the positive electrode sheet are in electrical communication. The two sides of the electrochromic layer include the upper and lower sides and the left and right sides of the electrochromic layer. For example, the insulating structure is located on the left side of the second conductive layer, and the edge part is located on the right side of the first conductive layer. Alternatively, the insulating structure is located on the left side of the first conductive layer, and the edge part is located on the right side of the second conductive layer. Alternatively, the edge part is located on the left side of the second conductive layer, and the insulating structure is located on the right side of the first conductive layer. Alternatively, the edge part is located on the left side of the first conductive layer, and the insulating structure is located on the right side of the second conductive layer.

[0326] According to embodiments of the present disclosure, in the direction of the main body part 110 towards the edge part 120, at least one of the following conditions is met:

[0327] The width of the edge part 120 is 0.05mm-2.7mm, for example, it can be 0.05mm, 0.1mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 2.7mm, etc. In some embodiments, the width of the edge part 120 is 0.1mm-2mm.

[0328] The shortest distance between the main body part 110 and the edge part 120 (i.e. the width of the interval region 170) is 0.3mm-2.9mm, for example, it can be 0.3mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 2.9mm, etc. In some embodiments, the shortest distance between the main body part 110 and the edge part 120 is 1mm-2.9mm.

[0329] The width of the main body part 110 is M, the shortest distance between the main body part 110 and the edge part 120 is N, and the sum of M and N (i.e. the sum of the widths of the edge part 110 and the interval region 170) is 0.35mm-3mm, for example, it can be 0.35mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, etc. In some embodiments, the sum of M and N is 2.5mm-3mm.

[0330] Increasing the width of the edge portion can reduce the internal resistance, shorten the bleaching time and improve the color change uniformity, but increasing the edge portion can easily cause the width of the interval region to be small, resulting in the light source not being easy to pass through the interval region to irradiate the frame glue, thereby causing the frame glue to be not easy to solidify. When the edge portion and the main body portion meet the above conditions, the space of the main body portion reserved in the first / second conductive layer is appropriate, the space utilization rate and efficiency of the electrochromic reaction are high, the edge portion is parallel to the conductive coating and the conductive layer, the resistance of the generated circuit is appropriate, which can effectively improve the uniformity of the electric field, the uniformity of the color change and the bleaching rate, can also reduce the short circuit phenomenon caused by too small resistance, and can also reduce the too long ultraviolet curing time of the frame glue caused by too small interval region width.

[0331] According to an embodiment of the present disclosure, the resistance of the electrochromic device 10 is 30Ω-150Ω, for example, can be 30Ω, 50Ω, 70Ω, 90Ω, 100Ω, 120Ω, 140Ω, 150Ω, etc. Thus, the electrochromic device with the above low resistance has better electric field uniformity, color change uniformity and bleaching rate.

[0332] According to an embodiment of the present disclosure, the first conductive coating 500P and the second conductive coating 600P include a conductive metal, for example, the first conductive coating and the second conductive coating include at least one of a conductive silver paste, a conductive aluminum paste and a conductive copper paste. Exemplarily, the first conductive coating and the second conductive coating include a conductive silver paste, thereby having higher conductivity and stability.

[0333] According to an embodiment of the present disclosure, referring to (A) in FIGS. 9 and 10, the main body portion 110 includes a center portion 111 and a patterned structure 112 located on the side of the center portion 111 away from the edge portion 120, the patterned structure 112 is electrically connected with the center portion 111, and the patterned structure 112 includes a plurality of first through holes M arranged at intervals.

[0334] For example, in FIGS. 7-10, the part of the conductive material from the cutting site b to the edge is removed to form a patterned structure, the conductive layer on both sides and the lower end of the first through hole is electrically connected with the first conductive coating, the first through hole can be filled with frame glue, or can be partially filled with frame glue, and the remaining part is filled with the first conductive coating. The first through hole can improve the light transmittance of the device, so that the light source passes through the first through hole of the patterned structure to irradiate the frame glue close to it, so that it is optically cured, and the adhesion of the sealing glue is improved.

[0335] Furthermore, the patterned structure is in parallel with the first conductive coating and the first / second conductive layer, which reduces the internal resistance of the entire circuit. Moreover, the patterned structure is in parallel with the first conductive coating, which increases the effective area of the first conductive coating, makes the current diverge better, and thus helps to reduce the internal resistance of the device. In addition, the amount of the first conductive coating can be reduced to save production costs while the device has the same internal resistance.

[0336] Furthermore, the point gluing process is performed during the assembly of each layer assembly, which is prone to overflow. The overflow can cause the conductive coating to fail to be electrically connected with the conductive layer, resulting in poor contact, uneven discoloration, and the like. Compared with the structure shown in (B) of FIG. 10, the area between the lower edge of the through-hole structure and the lower edge of the patterned structure increases the contact area of the conductive coating and the conductive layer. Therefore, even if the overflow occurs, the area where the conductive coating is connected with the conductive layer is relatively more, so as to obtain a higher point gluing yield.

[0337] According to embodiments of the present disclosure, the patterned structure satisfies at least one of the following conditions:

[0338] The first through-hole has a hole diameter of 0.3 mm to 2.9 mm, for example, 0.3 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 2.9 mm, or the like. In some embodiments, the first through-hole has a hole diameter of 1 mm to 2.9 mm.

[0339] The edge of the first through-hole is away from the side of the patterned structure that is away from the center part by a shortest distance of 0.05 mm to 2.7 mm, for example, 0.05 mm, 0.1 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 2.7 mm, or the like. In some embodiments, the edge of the first through-hole is away from the side of the patterned structure that is away from the center part by a shortest distance of 0.1 mm to 2 mm.

[0340] The first through-hole has a hole diameter of P, and the edge of the first through-hole is away from the side of the patterned structure that is away from the center part by a shortest distance of Q. The sum of P and Q is 0.35 mm to 3 mm, for example, 0.35 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, or the like. In some embodiments, the sum of P and Q is 2.5 mm to 3 mm.

[0341] In this way, the resistance of the patterned structure can be appropriately adjusted to maintain good conductive effect, shorten discoloration time, and improve discoloration uniformity. In addition, light can pass through the first through-hole to make the light-curing sealant near the first through-hole more easily cured by light, thereby improving the adhesion of the sealant.

[0342] It should be noted that the shape of the first through hole is not strictly limited, and can be square, circular, oval, triangular, trapezoidal or other polygonal shape, which can be flexibly selected according to actual conditions.

[0343] According to an embodiment of the present disclosure, the first conductive layer 100 or the second conductive layer 200P containing the edge part 120 further comprises:

[0344] A first resistance regulation path 130, one end of the first resistance regulation path 130 is electrically connected to one end of the edge part 120, and the other end of the first resistance regulation path 130 is electrically connected to one end of the patterned structure 112;

[0345] A second resistance regulation path 140, one end of the second resistance regulation path 140 is electrically connected to the other end of the edge part 120, and the other end of the second resistance regulation path 140 is electrically connected to the other end of the patterned structure 112;

[0346] The resistance of the edge part and the patterned structure is independently 4Ω-30Ω, for example, can be 4Ω, 6Ω, 8Ω, 10Ω, 15Ω, 20Ω, 25Ω, 30Ω, etc., in some embodiments, the resistance of the edge part and the patterned structure is independently 4Ω-10Ω;

[0347] The parallel resistance of the first resistance regulation path and the second resistance regulation path is independently 30Ω-1000Ω, for example, can be 30Ω, 50Ω, 80Ω, 100Ω, 200Ω, 400Ω, 500Ω, 600Ω, 800Ω, 1000Ω, etc., preferably 45Ω-200Ω.

[0348] As shown in FIG. 11, the edge part is connected in parallel with the first resistance regulation path, and the patterned structure is connected in parallel with the second resistance regulation path, and when the resistance of the first / second resistance regulation path, the edge part and the patterned structure meets the above conditions, when the device is powered on, the first / second resistance regulation path will not cause serious short circuit phenomenon because the resistance of the first / second resistance regulation path is greater than the resistance of the edge part and the patterned structure, the main circuit works normally, and the color change performance is good. After the device is powered off, part of the current will pass through the first resistance regulation path and the second resistance regulation path with appropriate resistance, which is equivalent to adding a discharge circuit, thereby accelerating the balance of residual charge, so that the color change material in the device can be more quickly restored to the initial state, and the fading rate of the device is improved.

[0349] In the present disclosure, the "resistance regulation path" can be replaced by "micro-short circuit path".

[0350] It should be noted that the first resistance regulating path and the second resistance regulating path can be formed on the conductive material directly on the first / second conductive layer, and the specific circuit shape is not strictly limited, and can be flexibly selected according to the required resistance value. FIG. 12 shows the first / second resistance regulating path with different patterns. The resistance member can also be externally connected on the first / second conductive layer to form the first / second resistance regulating path. Exemplarily, the setting mode of the resistance member includes coating a high-resistance conductive substance, pasting a metal conductive film, plating, connecting a resistance on the back of the substrate, welding a fixed resistance between the power supply wires, and controlling a fixed resistance in series in the mainboard. In addition, the circuit resistance can also be regulated by changing the insulation resistance of the insulating ink, the insulation resistance of the frame glue, and the resistance of the gap ball.

[0351] According to an embodiment of the present disclosure, the resistance difference between the first resistance regulating path 130 and the second resistance regulating path 140 is not greater than 20% of either one of the resistance values of the first resistance regulating path 130 and the second resistance regulating path 140. In this way, the phenomenon of uneven discoloration caused by the current preferentially passing through the side with smaller resistance after the device is powered on due to the too large resistance difference between the first resistance regulating path and the second resistance regulating path is avoided.

[0352] According to an embodiment of the present disclosure, the resistance of the first resistance regulating path 130 and the second resistance regulating path 140 is independently 30Ω-1000Ω, for example, can be 30Ω, 50Ω, 80Ω, 100Ω, 200Ω, 400Ω, 500Ω, 600Ω, 800Ω, 1000Ω, etc., and is preferably 90Ω-400Ω. In this way, the balance of residual charge can be accelerated, and the discoloration material in the device can be more quickly restored to the initial state, thereby improving the fading rate of the device.

[0353] According to an embodiment of the present disclosure, in a direction perpendicular to the main body part 110 towards the edge part 120, the length of the edge part 120 is A, and the length of the patterned structure 112 is B.

[0354] In the direction of the main body part 110 towards the edge part 120, the length of the first resistance regulating path 130 is C, and the length of the second resistance regulating path 140 is D.

[0355] A, B, C, and D satisfy: A+B≥50%×(A+B+C+D), and preferably satisfy: A+B≥80%×(A+B+C+D).

[0356] Therefore, the edge portion, the patterned structure, the first resistance regulation path and the second resistance regulation path meet the above conditions, which is conducive to improving the electric field uniformity, color change uniformity and fading rate of the device. This is because a certain voltage drop will occur when the current passes through the conductive layer from the electrode, and the voltage drop far from the electrode will be more obvious, and the color change material is difficult to be driven. Since the conductive coating covers the edge portion, the patterned structure, the first resistance regulation path and the second resistance regulation path, when the edge portion and the patterned structure meet the above conditions, the coverage length of the conductive coating can be increased, the overall resistance can be reduced, the voltage drop far from the electrode can be reduced, and the color change uniformity can be improved.

[0357] According to an embodiment of the present disclosure, referring to FIGS. 7 and 13, the electrochromic device 10 further comprises:

[0358] a first substrate 700 disposed on a side of the first conductive layer 100 away from the electrochromic layer 300P;

[0359] a positive electrode sheet 800A and a negative electrode sheet 800B, at least one of the positive electrode sheet 800A and the negative electrode sheet 800B comprising:

[0360] a first portion 810 in contact with the first conductive layer 100 and the first substrate 700 respectively and disposed along the thickness direction of the first substrate 700;

[0361] a second portion 820 intersecting the first portion 810 and extending in a direction away from the first conductive layer 100;

[0362] a third portion 830 intersecting the first portion 810 and extending in a direction away from the second portion 820, the third portion 830 being in contact with the first substrate 700.

[0363] The first portion of the electrode sheet is in contact with the first conductive layer to play a conductive role. If the second portion extends towards the first conductive layer, it needs to be inserted into the gap between the double-layer conductive layer, although it can improve the structural strength of the circuit connection, but it is easy to cause abnormal dispensing and uneven thickness of the device in the production process, thereby causing the display uniformity of the device to decrease, and it is easy to cause problems such as scratching of the conductive layer and overflow of the frame sealant. Therefore, the electrode sheet is designed in a structure similar to a “Z” type (for example, a “Z” type, a “B” type, a reverse “J” type), which is conducive to being attached to the first substrate, thereby stabilizing the structure, the second portion extends in a direction away from the first conductive layer, does not need to be inserted into the gap between the double-layer conductive layer, and can be fixed by an adhesive, which is conducive to improving the dispensing yield, making the thickness of the device more uniform, improving the display uniformity and production efficiency of the device, and avoiding problems such as uneven thickness of the device, overflow of the frame sealant and scratching of the conductive layer caused by warping, attachment and dispensing of the electrode sheet.

[0364] In some embodiments, the material of the electrode sheet is copper alloy, aluminum, iron, silver or other metals. In some embodiments, the material of the electrode sheet is copper plated with silver.

[0365] According to embodiments of the present disclosure, a plurality of second through holes N are distributed on the first part 810 and / or the second part 820. In this way, the first / second conductive coating is facilitated to penetrate through the second through holes, thereby improving the bonding strength of the electrode sheet and making it firmly adhere to the first substrate.

[0366] According to embodiments of the present disclosure, the first included angle c between the first part 810 and the second part 820 is 10°-135°, for example, it can be 10°, 30°, 50°, 80°, 100°, 120°, 135°, etc., and in some embodiments, the first included angle c is 50°-95°. In this way, the first part and the second part are closely attached to the first substrate to ensure good electrical connection and structural stability.

[0367] According to embodiments of the present disclosure, the second included angle d between the first part 810 and the third part 830 is 70°-95°, for example, it can be 70°, 75°, 80°, 85°, 90°, 95°, etc., and in some embodiments, the second included angle d is 80°-90°. In this way, the electrode sheet is closely attached to the surface of the substrate, reducing the phenomenon of warping and falling off due to the deformation and rebound of the metal after heating.

[0368] According to embodiments of the present disclosure, in the direction of the first conductive layer 100 towards the second conductive layer 200P, the length of the first part 810 is 50%-100% of the thickness of the first substrate 700, for example, it can be 50%, 60%, 70%, 80%, 90%, 100%, etc., preferably 70%-100%; in the direction of the main part 110 towards the edge part 120, the length of the first part 810 is 0.1mm-3mm, for example, it can be 0.1mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, etc.; the length of the second part 820 is 0.1mm-3mm, for example, it can be 0.1mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, etc.; the length of the third part 830 is 10mm-20mm, for example, 10mm, 12mm, 15mm, 18mm, 20mm, etc. In this way, the electrode sheet is stably attached and fixed to the first substrate, and can be in electrical communication with the first conductive layer, thereby achieving good conductive effect. Moreover, since the conductive coating will be in contact with the first part and the second part, the length of the above-mentioned first part and second part meets the above-mentioned condition, which increases the contact area with the conductive coating and improves the conductive effect.

[0369] According to embodiments of the present disclosure, the thickness of the positive electrode sheet 800A and the negative electrode sheet 800B is independently 30 μm-200 μm, for example, can be 30 μm, 50 μm, 80 μm, 100 μm, 150 μm, 200 μm, etc. Thus, the electrode sheet has better electrical conductivity and mechanical strength.

[0370] According to embodiments of the present disclosure, the hardness of the positive electrode sheet 800A and the negative electrode sheet 800B is independently 60 HV-150 HV, for example, can be 60 HV, 80 HV, 100 HV, 120 HV, 150 HV, etc. Thus, the electrode sheet has better mechanical strength, which helps to improve the durability and reliability of the device in long-term use.

[0371] According to embodiments of the present disclosure, referring to (B) shown in FIG. 13, the first part 810 and the third part 830 are provided with adhesive layers on the side of the first conductive layer 100, and the corresponding adhesive layers are referred to as the first part adhesive layer 810A and the third part adhesive layer 830A. Thus, in order to stably fix the electrode sheet, improve the tensile performance and environmental reliability of the electrode sheet, without inserting the electrode sheet into the gap between the double-layer conductive layer, avoiding the problems of uneven thickness of the device, scratching of the conductive layer, etc. The side of the second part 810 towards the first conductive layer 100 can be referred to as the second part back surface 820A, and the conductive coating can cover the second part and be bonded and fixed to the conductive layer or the insulating layer through the second through hole, increasing the contact area of the conductive coating and improving the conductivity.

[0372] In some embodiments, the adhesive layer comprises an adhesive, and the adhesive comprises at least one of high-temperature-resistant double-sided tape, acrylic glue, rubber glue, silicone, high-temperature-resistant pressure-sensitive adhesive, and epoxy resin. Since a high temperature of 300°C or higher is generated when the electrode sheet is welded with a wire, a high-temperature-resistant pressure-sensitive adhesive, high-temperature-resistant double-sided tape, and epoxy resin are preferred for ease of construction.

[0373] In some embodiments, the thickness of the adhesive is 5 μm-100 μm, preferably 30 μm-70 μm.

[0374] In some embodiments, the adhesive has a coating area of 50%-100% of the area of the plane, preferably 60%-90%.

[0375] According to embodiments of the present disclosure, the pore size of the second through hole N is 30 mesh-100 mesh, for example, can be 30 mesh, 50 mesh, 80 mesh, 100 mesh, etc. Thus, the electrode sheet has better electrical conductivity, and the bonding strength between the electrode sheet and the first substrate and the first / second conductive layer can be improved.

[0376] It should be noted that the shape of the second through hole is not strictly limited in the present disclosure, and can include but is not limited to regular or irregular shapes. Such structures can be achieved by drilling, stamping, laser engraving, printing, rolling, etc.

[0377] According to an embodiment of the present disclosure, the electrochromic device 10 further comprises: a first encapsulant 150 and a second encapsulant 160, which are respectively connected to two ends of the electrochromic layer 300P;

[0378] The normal projection of the spacing region towards the electrochromic layer 300P coincides with one of the first encapsulant 150 and the second encapsulant 160, and the normal projection of the edge portion 120 towards the electrochromic layer 300P does not completely coincide with one of the first encapsulant 150 and the second encapsulant 160;

[0379] The normal projection of the patterned structure 112 towards the electrochromic layer 300P coincides with the other of the first encapsulant 150 and the second encapsulant 160.

[0380] The frame adhesive can firmly bond the double-layer conductive layer and the electrochromic layer together, improving the structural stability of the overall device. The spacing region and the first through hole of the patterned structure can improve the light transmittance of the device, so that the light source passes through the spacing region and the first through hole of the patterned structure to enter the frame adhesive close to it, causing optical curing.

[0381] According to an embodiment of the present disclosure, the electrochromic layer 300P comprises: an anodic coloring material, a cathodic coloring material, an electrolyte, and a solvent.

[0382] According to an embodiment of the present disclosure, the electrochromic device 10 further comprises: a second substrate 900, which is arranged on the side of the second conductive layer 200P away from the electrochromic layer 300P.

[0383] Exemplarily, the first substrate 700 and the second substrate 900 of the present disclosure are each independently soda-lime glass or high borosilicate glass.

[0384] The eleventh aspect of the present disclosure provides a method for preparing the electrochromic device of the tenth aspect of the present disclosure. According to an embodiment of the present disclosure, the method comprises: removing part of the conductive material in the initial conductive layer to form the main body part and the edge part on the initial conductive layer, to obtain one of the first conductive layer and the second conductive layer; forming the insulating structure on the side of the other of the first conductive layer and the second conductive layer facing the main body part; assembling the first conductive layer or the second conductive layer comprising the main body part and the edge part and the first conductive layer or the second conductive layer provided with the insulating structure to obtain a pre-assembled part, the pre-assembled part being provided with a cavity; pouring electrochromic slurry into the cavity and sealing to form an electrochromic layer.

[0385] According to an embodiment of the present disclosure, the method for removing comprises at least one of electron beam bombardment, chemical etching, masking, plating, polishing and laser cutting.

[0386] According to an embodiment of the present disclosure, after the sealing, the positive electrode sheet and the negative electrode sheet are respectively adhered to the side of the first substrate away from the first conductive layer and the side in the thickness direction, and the first conductive coating and the second conductive coating are coated to obtain the electrochromic device.

[0387] The method for preparing the electrochromic device of the tenth aspect will be described in detail below.

[0388] Referring to FIG. 14, the method comprises:

[0389] S100 B forming a main body part, an edge part and an insulating structure

[0390] In this step, part of the conductive material in the initial conductive layer is removed to form the main body part and the edge part on the initial conductive layer, to obtain one of the first conductive layer and the second conductive layer; the insulating structure is formed on the side of the other of the first conductive layer and the second conductive layer facing the main body part. Exemplarily, when the first conductive layer comprises the main body part and the edge part, the insulating structure is formed on the second conductive layer; or, when the second conductive layer comprises the main body part and the edge part, the insulating structure is formed on the first conductive layer.

[0391] According to an embodiment of the present disclosure, the method for removing comprises at least one of electron beam bombardment, chemical etching, masking, plating, polishing and laser cutting, preferably electron beam bombardment or laser cutting.

[0392] S200 B assembling

[0393] In this step, the first conductive layer or the second conductive layer including the main body part and the edge part and the first conductive layer or the second conductive layer provided with the insulating structure are assembled to obtain a pre-assembled part, and the pre-assembled part is provided with a cavity. By assembling the first conductive layer and the second conductive layer and reserving the cavity, it is convenient for subsequent pouring of the electrochromic slurry.

[0394] S300B pouring electrochromic slurry, sealing

[0395] In this step, the electrochromic slurry is poured into the cavity and sealed.

[0396] According to an embodiment of the present disclosure, after the sealing, the positive electrode sheet and the negative electrode sheet are respectively adhered to the back surface and the side surface of the first substrate, and the first conductive coating and the second conductive coating are coated to obtain the electrochromic device.

[0397] The preparation method of the positive / negative electrode sheet of the present disclosure includes: processing the positive / negative electrode sheet into a planar shape by punching, cutting, laser engraving, wire cutting and the like, then bending it using a bending device, and finally printing an adhesive for fixation on the bonding surface a and the bonding surface b.

[0398] The present disclosure provides an electronic device. According to an embodiment of the present disclosure, the electronic device includes the electrochromic device of the eleventh aspect of the present disclosure. Thus, the electronic device of the present disclosure has good color change uniformity, fast color fading rate and strong performance stability.

[0399] According to an embodiment of the present disclosure, the electronic device includes a display, an anti-dazzle rearview mirror, a light-adjustable curtain, a light-adjustable glass window, light-adjustable color-changing glasses, electronic paper and the like.

[0400] It should be noted that the features and advantages described above for the electrochromic device of the tenth aspect also apply to the method of preparing the electrochromic device and the electronic device, which will not be described here.

[0401] In some embodiments of the present disclosure, an electrochromic device is also provided, as shown in FIG. 18, the electrochromic device 10B includes:

[0402] The first conductive layer 100B and the second conductive layer 200B are stacked and arranged;

[0403] The frame sealant 300B is arranged between the first conductive layer 100B and the second conductive layer 200B and surrounds the first conductive layer 100B and the second conductive layer 200B to form a closed cavity 400B, and the closed cavity 400B contains the electrochromic liquid described above or the electrochromic liquid obtained by the method of preparing the electrochromic liquid described above.

[0404] The electrochromic device of the present disclosure has excellent color change performance and service life, specifically, the electrochromic device has high contrast before and after being powered on and powered off, and strong color change uniformity, and after the power-off cycle test, the cold-heat cycle test or the high-temperature and high-humidity cycle test, at least one of conditions (a) and (b) is met: (a) contrast R≥65%; (b) chroma value a is -3.5≤a≤3.5, chroma value b is -3.5≤b≤3.5, and chroma value L is 80≤L≤90;

[0405] The power-off cycle test comprises: charging the electrochromic device with a voltage of 1.2V for 30 seconds and then powering off for 30 seconds, which is one cycle, and a total of not less than 40,000 cycles, not less than 60,000 cycles, not less than 80,000 cycles or not less than 100,000 cycles;

[0406] The cold-heat cycle test comprises: continuously powering the electrochromic device with a voltage of 1.2V, first increasing the ambient temperature to 80℃, maintaining the temperature for 1 hour, then decreasing the temperature to -20℃, and continuing to maintain for 1 hour, which is one cycle, and a total of not less than 360h or not less than 480h;

[0407] The high-temperature and high-humidity cycle test comprises: powering the electrochromic device with a voltage of 1.2V in an environment with a relative humidity of 80% and an ambient temperature of 80℃ for not less than 360h or not less than 480h.

[0408] It should be noted that in the case of multiple different test conditions in the above test methods, only any one test condition needs to be met.

[0409] In some embodiments, the first conductive layer 100B and the second conductive layer 200B can each be indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO) or a transparent metal mesh, which has good light transmittance and good electrical conductivity, and is conducive to improving the color change effect of the electrochromic device.

[0410] According to embodiments of the present disclosure, the electrochromic device 10B further comprises a first substrate 500B and a second substrate 600B, the first substrate 500B is arranged on the side of the first conductive layer 100B away from the second conductive layer 200B, and the second substrate 600B is arranged on the side of the second conductive layer 200B away from the first conductive layer 100B. Exemplarily, the first substrate is an anode glass (Fig. 19), and the second substrate is a cathode glass (Fig. 20).

[0411] In some embodiments, the first substrate 500B and the second substrate 600B can each be glass, which has high transparency and good water vapor transmission resistance.

[0412] According to an embodiment of the present disclosure, the first conductive layer 100B comprises a transparent conductive layer, referring to FIG. 21, the second conductive layer 200B comprises a reflective layer 200-1, the reflective layer 200-1 is provided with a transparent substrate 100-1 away from one side of the first conductive layer 100B, thereby the reflective layer 200-1 and the transparent substrate 100-1 form a conductive reflective film material 10-1, the reflective layer 200-1 comprises silver and palladium; in the reflective layer 200-1, the palladium content on the side close to the transparent substrate 100-1 is less than the palladium content on the side away from the transparent substrate 100-1.

[0413] The semi-reflective and semi-transmissive film on the market at present often adopts materials such as silicon, indium, niobium, titanium and chromium, and has poor conductive performance and is difficult to meet the needs of emerging electronic products such as touch display. The metal silver material is one of the materials with the best conductive performance in nature, but its chemical performance is relatively active and the diffusion activation energy is relatively low. The diffusion activation energy refers to the lowest energy barrier that needs to be overcome for atoms or molecules to escape from the crystal lattice. For metal materials, the higher the diffusion activation energy, the stronger the stability. Under an external electric field or high temperature, due to the low diffusion activation energy of silver, the vibration amplitude of internal metal ions increases, ion migration is easy to occur, and macroscopically, the film layer grows into a branch crystal or snowflake shape, leading to easy film layer peeling.

[0414] The present disclosure dopes palladium in the reflective layer containing silver. On the one hand, palladium and silver can be mutually soluble, avoiding affecting the overall performance of the material due to the mutual insolubility of the dopant and silver in some areas. On the other hand, doping palladium can increase the diffusion activation energy of silver, and palladium is easy to react with oxygen in the environment to form a passivation layer to improve the anti-electromigration corrosion performance of silver, thereby improving the stability of the reflective layer, reducing the film layer peeling phenomenon, having strong durability and stable performance, and long service life. Further, as the doping ratio of palladium increases, palladium can form a more dense oxide protective film, the corrosion resistance of the reflective layer increases, and increasing the doping ratio of palladium away from the transparent substrate can provide better protection against environmental factors causing corrosion of the film, thereby improving the overall stability of the reflective layer in the electric field cycle superposition. If the palladium doping ratio decreases away from the substrate, it is difficult to play a good anti-electric corrosion function, and film layer peeling is easy to occur.

[0415] In a multi-layer film structure, if each layer of material has uniform and consistent optical properties, the reflection of light waves between layers may interfere with each other due to phase differences, resulting in some wavelengths of light being enhanced and other wavelengths of light being weakened. Such interference can reduce the transmittance.

[0416] The present disclosure reduces the occurrence of interlayer interference of the reflective layer itself by setting the side close to the transparent substrate as a low palladium content (doping ratio) and the side away from the transparent substrate as a high palladium content (doping ratio), and is conducive to reducing light loss and resistance compared to the entire reflective layer being doped with a high palladium content, thereby improving the optical and electrical properties of the conductive thin film material.

[0417] In some embodiments, the transparent conductive layer includes ITO, silver alloy, aluminum alloy, chromium metal, copper metal, gold, and a mixture containing one or more of the above or a superimposed thin film structure, and the transparent substrate includes but is not limited to ITO.

[0418] According to an embodiment of the present disclosure, the palladium content in the reflective layer 200-1 gradually increases in the direction away from the transparent substrate 100-1. By using the above-mentioned gradient doping method, the gradient change of the refractive index can reduce or eliminate the interference effect between the layers. In this way, compared to the silver palladium alloy layer (silver and palladium are uniformly dispersed) superimposed on the surface of the silver layer, the light wave of the gradient optical structure of the present disclosure has reduced scattering and reflection loss when passing through the thin film, so that more light can better penetrate the material, thereby making the thin film have more uniform and excellent optical performance, improving the overall transmittance of the reflective layer, while also maintaining the required reflectivity, achieving the improvement of the optical performance of the thin film. Furthermore, because the metal thin film has high absorption characteristics, the higher the doping ratio, the greater the extinction coefficient K, the more light loss, and the lower the overall light efficiency of the device. The present disclosure gradually increases the palladium doping ratio to a high doping ratio, compared to directly using a high doping ratio, the overall extinction coefficient of the device is low, and the thin film has smaller absorption and higher optical transmission / reflection performance.

[0419] In the present disclosure, the term "palladium content" can be replaced by "palladium doping ratio", and "reflective layer" can be replaced by "thin film".

[0420] According to an embodiment of the present disclosure, the reflective layer 200-1 includes a plurality of sub-reflection layers arranged in layers, and the palladium content in the plurality of sub-reflection layers gradually increases in the direction away from the transparent substrate 100-1. The palladium content in the plurality of sub-reflection layers in the reflective layer is different and gradually increases in the direction away from the transparent substrate. As a result, the refractive index also has a gradient change, thereby reducing or eliminating the interference effect between the layers, reducing the light absorption rate of the reflective layer, improving the transmittance, while also maintaining the required reflectivity, achieving the optimization of the optical performance of the thin film.

[0421] According to an embodiment of the present disclosure, the sub-reflection layer closest to the transparent substrate 100-1 is a first sub-reflection layer, the sub-reflection layer farthest from the transparent substrate 100-1 is a second sub-reflection layer, the palladium content of the first sub-reflection layer is 0 mass% to 2 mass% based on the mass of the first sub-reflection layer, for example, can be 0 mass%, 0.1 mass%, 0.2 mass%, 0.3 mass%, 0.4 mass%, 0.5 mass%, 0.8 mass%, 1 mass%, 1.2 mass%, 1.5 mass%, 1.8 mass%, 2 mass%, preferably 0 mass% to 0.5 mass%; the palladium content of the second sub-reflection layer is 1 mass% to 10 mass% based on the mass of the second sub-reflection layer, for example, can be 1 mass%, 2 mass%, 3 mass%, 4 mass%, 5 mass%, 6 mass%, 7 mass%, 8 mass%, 9 mass%, 10 mass%, preferably 3 mass% to 6 mass%.

[0422] The palladium content in the sub-reflection layer meets the above conditions, palladium can form a more dense oxide protective film, improve the corrosion resistance and electromigration performance of silver, enhance the long-term stability of the film, reduce the film peeling phenomenon, increase the corrosion resistance of the reflection layer, and make the reflection layer have good stability and conductivity. In addition, the overall refractive index of the reflection layer is low, which reduces the interlayer interference effect, further improves the overall transmittance of the reflection layer, and also maintains the required reflectivity. Furthermore, the palladium content meets the above conditions, the resistivity of the reflection layer is low, and the conductivity of the film is good. Therefore, the overall optical performance of the film is improved.

[0423] According to an embodiment of the present disclosure, along the direction away from the transparent substrate 100-1, the palladium content in the sub-reflection layer is the same, and the difference between the palladium content of two adjacent sub-reflection layers is less than 1 mass% / nm. Therefore, the palladium content in each sub-reflection layer can be changed little, the interlayer interference caused by too large change in palladium content can be reduced, the light absorption rate of the reflection layer is reduced, the transmittance is improved, the required reflectivity is maintained, and the optical performance of the film is good.

[0424] According to an embodiment of the present disclosure, at the same depth from the transparent substrate, the difference in palladium content of the sub-reflection layer along the length and / or width extension direction is not greater than 0.1 mass% / nm. Therefore, palladium is uniformly doped in the sub-reflection layer to further improve the corrosion resistance and optical performance.

[0425] According to an embodiment of the present disclosure, along the direction away from the transparent substrate, the refractive index of the reflection layer gradually decreases. Therefore, compared with a multi-layer reflection layer with fixed refractive index, the interlayer interference can be reduced, and the light transmittance is improved.

[0426] According to an embodiment of the present disclosure, the content of palladium in the sub-reflection layer closest to the transparent substrate is X1, the content of palladium in the sub-reflection layer closest to the transparent substrate is X2, the refractive index of the reflection layer is N, X1, X2 and N satisfy: N = (0.055-2.333p)-i(3.320+9.867p), p is the average of X1 and X2, and i is an imaginary number. Thus, according to the preset X1 and X2, the average p of the two is calculated, and the refractive index N is calculated by substituting the above formula. Further, the thickness and material type of each layer of the conductive thin film material can be designed based on the refractive index N using optical materials, to meet different requirements of reflectivity and transmittance, that is, to adjust and control the reflectivity and transmittance of the reflection layer to meet different scene requirements, with high universality.

[0427] According to an embodiment of the present disclosure, the thickness of the reflection layer is 20-40 nm, for example, 20 nm, 30 nm or 40 nm. Thus, the reflection layer has good mechanical strength and durability, reducing the risk of cracks, peeling or other damage caused by excessive thickness or thinness. In addition, it helps to reduce the interference effect of light in the film, improve the transmittance, reduce the generation of adverse optical fluctuations, and improve the consistency and stability of optical performance. In some embodiments, the thickness of each sub-nanometer layer is 0.1-1 nm.

[0428] According to an embodiment of the present disclosure, a bonding transition layer 300-1 is arranged between the transparent substrate 100-1 and the reflection layer 200-1. Thus, it helps to enhance the adhesion between the reflection layer and the transparent substrate, prevent delamination or peeling caused by mismatched thermal expansion coefficients or mechanical stress, and improve the mechanical stability and durability of the structure. In addition, the bonding transition layer can also act as a protective layer to reduce the potential damage of environmental factors such as humidity, temperature change or chemical corrosion to the film, prolonging its service life. Furthermore, the bonding transition layer can provide a refractive index gradient interface matching the transparent substrate, reducing the interface reflection and scattering of light between the transparent substrate and the reflection layer, thereby improving the transmittance and overall optical performance of the light.

[0429] According to an embodiment of the present disclosure, the thickness of the bonding transition layer 300-1 is 50-100 nm, for example, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm. The adhesion between the reflection layer and the transparent substrate can be further enhanced, thereby improving the mechanical stability and durability of the structure and reducing the occurrence of film layer peeling. In addition, the reflection layer can be better protected, reducing the potential damage of environmental factors such as humidity, temperature change or chemical corrosion, prolonging its service life.

[0430] According to an embodiment of the present disclosure, the bonding transition layer 300-1 comprises at least one of silicon dioxide, aluminum trioxide, niobium oxide, indium tin oxide and zinc aluminum oxide. In this way, the stability of the bonding transition layer is further enhanced, the loss rate is low, and the reflectivity and transmittance are improved.

[0431] According to an embodiment of the present disclosure, the reflective layer 200-1 is provided with a protective layer 400-1 on the side away from the transparent substrate 100-1. Although the reflective layer has high reflectivity, it has low hardness and poor wear resistance. By providing a protective layer on the contact surface of the reflective layer with the external environment, potential damage to the film caused by external environmental factors is resisted, the service life of the film is effectively prolonged, the long-term stability of the optical and electrical properties of the film is maintained, and maintenance costs are reduced.

[0432] According to an embodiment of the present disclosure, the thickness of the protective layer 400-1 is 30-50 nm, for example, it can be 30 nm, 35 nm, 40 nm, 45 nm or 50 nm. In this way, the potential damage to the film caused by external environmental factors such as wear and tear can be better resisted, the service life of the film is improved, and the optical performance of the reflective layer is not hindered.

[0433] According to an embodiment of the present disclosure, the protective layer 400-1 comprises at least one of indium tin oxide, silicon nitride and zinc aluminum oxide. The above-mentioned materials have low light loss rate and high hardness, and can better protect the reflective layer from potential damage caused by external environmental factors such as wear and tear, improve the service life of the film, and not hinder the improvement of the optical performance of the reflective layer.

[0434] According to an embodiment of the present disclosure, the transparent substrate can be glass, sapphire, acrylic or plastic, etc.

[0435] According to an embodiment of the present disclosure, the reflectivity of the conductive film material is 80-86%, and / or the transmittance of the conductive film material is 12-16%. In this way, the conductive film material of the present disclosure has excellent optical performance.

[0436] According to an embodiment of the present disclosure, FIG. 24 is a schematic diagram of an electrochromic device structure, and FIG. 25 is a perspective view of an electrochromic device, the frame sealant 300 comprises a main bonding layer 310, a moisture curing layer 320 and a hydrophobic layer 330. Each structure will be described in detail below.

[0437] According to an embodiment of the present disclosure, the main bonding layer 310 is located between the first conductive layer 100B and the second conductive layer 200B and surrounds the first conductive layer 100B and the second conductive layer 200B to form a sealed cavity 400B. The main bonding layer mainly serves to bond the first conductive layer and the second conductive layer and form a sealed cavity containing electrochromic liquid.

[0438] According to an embodiment of the present disclosure, the moisture curing layer 320 covers at least part of the surface of the main adhesive layer 310 away from the sealed cavity 400B and is bonded with the first conductive layer 100B and the second conductive layer 200B respectively. The moisture curing layer can be cross-linked and cured in a moisture environment, thereby further enhancing the adhesive strength.

[0439] According to an embodiment of the present disclosure, the moisture curing layer 320 is connected to the main adhesive layer 310 at least through a siloxane bond. The two material layers can be connected through physical bonding (such as hydrogen bond, electrostatic force, van der Waals force) and chemical bond. Compared with the physical bonding, the chemical bond has stronger bonding force, thereby enhancing the stability and sealing performance of the frame sealant structure. Compared with other chemical bonds, the siloxane bond has higher thermal stability and chemical stability, which enables the material to maintain structural stability in a high-temperature environment and has good mechanical strength and flexibility, thereby enhancing the durability and crack resistance of the material.

[0440] According to an embodiment of the present disclosure, the main adhesive layer 310 comprises a first adhesive, and the raw material of the first adhesive comprises a first silane coupling agent. In this way, the silane coupling agent is conducive to forming a siloxane bond with the moisture curing layer, and the silane coupling agent has high adhesive strength, thermal stability and chemical stability, which enables the material to maintain structural stability in a high-temperature environment and has good mechanical strength and flexibility, thereby enhancing the durability and crack resistance of the material.

[0441] According to an embodiment of the present disclosure, the first silane coupling agent comprises at least one of γ-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, tetraepoxy cyclohexyl ethyl 2,4,6,8-tetramethylcyclotetrasiloxane and mono(2,3-epoxy)propyl ether terminated polydimethylsiloxane. The coupling agent has a siloxane group at one end, which can be bonded with the siloxane group in the moisture curing layer to form a siloxane bond, thereby enabling the main adhesive layer to be chemically bonded with the moisture curing layer. The coupling agent has an epoxy group at the other end, which is conducive to ring-opening bonding with the epoxy resin in the first adhesive, thereby improving the stability.

[0442] According to an embodiment of the present disclosure, the first silane coupling agent accounts for 5wt% to 30wt% of the mass of the raw material of the first adhesive, for example, 5wt%, 10wt%, 15wt%, 20wt%, 25wt% or 30wt%. In this way, the adhesion of the main adhesive layer itself and the adhesion between the main adhesive layer and the moisture curing layer can be enhanced, the formation of chemical bonds and physical entanglements is promoted, and the stability and sealing performance of the frame sealant are improved.

[0443] According to an embodiment of the present disclosure, the raw material of the first adhesive further comprises an epoxy resin and an initiator. The epoxy resin not only has high adhesion and mechanical strength, but also does not contain polar functional groups, which is not easy to interact with the electrochromic liquid in the closed cavity, thereby reducing the occurrence of coloring residual phenomenon caused by the contact between the main adhesive layer and the electrochromic liquid, and has strong corrosion resistance. Furthermore, under the action of the initiator, the epoxy group in the epoxy resin and the epoxy group in the first silane coupling agent undergo ring-opening polymerization, thereby enhancing the stability, adhesion and aging resistance of the sealant.

[0444] According to an embodiment of the present disclosure, the epoxy resin comprises bisphenol A type epoxy resin, bisphenol F type epoxy resin and resorcinol diglycidyl ether. Thus, the epoxy resin has good environmental resistance, and the three have rigidity and flexibility, which can effectively bond.

[0445] According to an embodiment of the present disclosure, the epoxy resin accounts for 50wt% to 80wt% of the mass of the raw material of the first adhesive, for example, can be 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%. The proportion of epoxy resin meets the above conditions, which can further improve the adhesion and mechanical strength of the main adhesive layer.

[0446] According to an embodiment of the present disclosure, the initiator accounts for 0.1wt% to 10wt% of the mass of the first adhesive. Under the action of the initiator, the epoxy group can undergo ring-opening and crosslinking reaction. The proportion of the initiator meets the above conditions, which can make the epoxy resin and the first silane coupling agent quickly and completely crosslink to form an adhesive layer with stable structure and good adhesion.

[0447] According to an embodiment of the present disclosure, the bisphenol A type epoxy resin accounts for 10wt% to 40wt% of the mass of the raw material of the first adhesive, for example, can be 10wt%, 20wt%, 30wt%, 40wt%, preferably 10wt% to 30wt%.

[0448] According to an embodiment of the present disclosure, the bisphenol F type epoxy resin accounts for 10wt% to 40wt% of the mass of the raw material of the first adhesive, for example, can be 10wt%, 20wt%, 30wt%, 40wt%, preferably 10wt% to 30wt%.

[0449] According to an embodiment of the present disclosure, the resorcinol diglycidyl ether accounts for 30wt% to 45wt% of the mass of the raw material of the first adhesive, for example, can be 30wt%, 32wt%, 35wt%, 37wt%, 40wt%, 42wt%, 44wt%, 45wt%.

[0450] The proportions of bisphenol A type epoxy resin, bisphenol F type epoxy resin and resorcinol diglycidyl ether meet the above conditions, which can further improve the adhesion and mechanical strength of the main bonding layer, thereby improving the sealing and stability of the frame sealing glue.

[0451] According to an embodiment of the present disclosure, the initiator comprises a cationic initiator and / or a free radical photoinitiator; the cationic initiator comprises at least one of diazonium salt, diaryliodonium salt, triarylsulfonium salt, alkylsulfonium salt, iron arene salt, sulfonyloxy ketone and triarylsilyl ether; the free radical photoinitiator comprises benzotriazole and / or benzothiadiazo. In this way, the epoxy group can be rapidly subjected to ring-opening crosslinking reaction.

[0452] According to an embodiment of the present disclosure, the raw material of the first adhesive further comprises a filler, and the filler comprises silicon oxide and / or calcium carbonate. Silicon oxide and calcium carbonate have thermal stability and chemical stability, which can improve the aging resistance and chemical corrosion resistance of the main bonding layer, and also can improve the mechanical strength, wear resistance and impact resistance of the bonding layer.

[0453] According to an embodiment of the present disclosure, the filler accounts for 10wt%-50wt% of the total mass of the raw material of the first adhesive, for example, can be 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%. In this way, it is beneficial to further improve the aging resistance and chemical corrosion resistance of the main bonding layer, and also can further improve the mechanical strength, wear resistance and impact resistance of the main bonding layer.

[0454] According to an embodiment of the present disclosure, based on the total mass of the raw material of the first adhesive, the raw material of the first adhesive comprises:

[0455] 10-40 parts of bisphenol A type epoxy resin;

[0456] 10-40 parts of bisphenol F type epoxy resin;

[0457] 30-45 parts of resorcinol diglycidyl ether;

[0458] 5-30 parts of the first silane coupling agent;

[0459] 10-50 parts of the filler;

[0460] 0.1-5 parts of the initiator.

[0461] The raw material of the first adhesive meets the above conditions, which can further improve the adhesion, mechanical strength and stability of the main bonding layer, and has strong aging resistance and corrosion resistance, thereby further improving the sealing and stability of the electrochromic device.

[0462] According to embodiments of the present disclosure, the second silane coupling agent has an amino group, and the raw materials of the second adhesive further include an isocyanate prepolymer, a diisocyanate, and a siloxane-terminated polysiloxane.

[0463] In an environment with moisture (with water), the isocyanate prepolymer can polymerize with the diisocyanate to form a polymer, and at the same time, the amino group in the second silane coupling agent can also crosslink with the isocyanate group. Moreover, in the presence of the second silane coupling agent with an amino group and the environment with moisture (with water), the siloxane groups in the siloxane-terminated polysiloxane crosslink with each other, and the two ends of the substance are siloxane-Si(-O-R)3. In the presence of moisture, i.e. H2O, the reaction -Si(-O-R)3+ 3H2O = -Si(-OH)3+ 3ROH occurs. After the reaction of the siloxane-terminated polysiloxane molecules with water, the -Si(-OH)3 of the dehydrated and condensed siloxane-terminated polysiloxane molecules polymerizes: -Si(-OH)3+-Si(-OH)3= -Si(OH)2-O-Si(OH)2-+H2O, and the Si(OH)2 continues to react with the Si(OH)2 of other molecules to form a chain. The chain-extended polysiloxane is beneficial to improve the flexibility of the adhesive layer and make the adhesive layer have good deformation resistance. Moreover, the Si-O groups in the second silane coupling agent and the siloxane polymer also bond with the Si-O groups in the first silane coupling agent in the main adhesive layer to form a Si-O-Si structure, so as to enhance the stability of the frame sealant structure. Thus, the moisture curing layer gradually strengthens in the moisture environment, thereby further improving the adhesion and stability of the moisture curing layer and making the moisture curing layer have strong aging resistance.

[0464] According to embodiments of the present disclosure, the isocyanate prepolymer has a structure shown in Formula I:

[0465] R1 is a tolyl group,

[0466] R2 is an alkyl group with 2-8 carbons (for example, 2, 3, 4, 5, 6, 7, or 8 carbons); and n is an integer from 1 to 100.

[0467] According to embodiments of the present disclosure, the diisocyanate includes at least one of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HDMI), hexamethylene diisocyanate (HDI), and methylene diisocyanate (LDI).

[0468] According to embodiments of the present disclosure, the siloxane-terminated polysiloxane has a structure shown in Formula II:

[0469] R3 is a -Si-O-Si- repeating unit with an integer number of repetitions from 10 to 30;

[0470] R4 is methyl, ethyl, or propyl.

[0471] According to embodiments of this disclosure, the second silane coupling agent comprises

[0472] The moisture-curing layer formed from the second binder raw material containing the aforementioned isocyanate prepolymer, diisocyanate, and siloxane-terminated polysiloxane can gradually and effectively cure in a humid environment, thereby improving its bonding strength. Furthermore, the formed moisture-curing layer exhibits good flexibility and strong resistance to deformation.

[0473] According to embodiments of this disclosure, the isocyanate prepolymer accounts for 20 wt% to 60 wt% of the mass of the second binder raw material, for example, 20 wt%, 30 wt%, 40 wt%, 50 wt%, or 60 wt%, preferably 30 wt% to 50 wt%.

[0474] According to embodiments of this disclosure, the diisocyanate accounts for 10 wt% to 30 wt% of the mass of the second binder raw material, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%, preferably 15 wt% to 25 wt%.

[0475] According to embodiments of this disclosure, the siloxane polymer with siloxane-terminated ends accounts for 20 wt% to 60 wt% of the raw material mass of the second adhesive, for example, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, preferably 30 wt% to 50 wt%.

[0476] According to embodiments of this disclosure, the second silane coupling agent accounts for 10 wt% to 30 wt% of the raw material mass of the second binder, for example, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, preferably 15 wt% to 25 wt%.

[0477] Meeting the above conditions regarding the proportions of isocyanate prepolymer, diisocyanate, and siloxane polymers with siloxane end caps can improve the adhesion and stability of the moisture-cured layer. In particular, it can enhance curing in humid environments and exhibit excellent aging resistance.

[0478] According to embodiments of this disclosure, the raw materials of the second adhesive include:

[0479] 20-60 parts by weight of isocyanate prepolymer;

[0480] 10-30 parts by weight of diisocyanate;

[0481] 20-60 parts by weight of siloxane polymer having siloxane group terminated;

[0482] 10-30 parts by weight of second silane coupling agent.

[0483] The raw material of the second adhesive satisfies the above conditions, which can improve the adhesion and stability of the moisture curing layer, especially in the environment with moisture, which can strengthen the curing and has excellent aging resistance.

[0484] According to an embodiment of the present disclosure, a hydrophobic layer covers at least part of the surface of the moisture curing layer away from the sealed cavity and is bonded with the first conductive layer and the second conductive layer, respectively. In this way, water vapor condenses into water droplets and rolls off, reducing the penetration of water vapor. In this way, the sealing and stability of the sealant can be improved, and the aging resistance is strong.

[0485] According to an embodiment of the present disclosure, the hydrophobic layer includes a third adhesive, and the raw material of the third adhesive includes a third silane coupling agent. The Si-O group of the third silane coupling agent can bond with the Si-O group of the second silane coupling agent to form a Si-O bond, thereby enhancing the stability and sealing of the sealant structure.

[0486] According to an embodiment of the present disclosure, the third silane coupling agent has a fluorine group. In this way, it is helpful to make the third silane coupling agent have hydrophobicity.

[0487] According to an embodiment of the present disclosure, the third silane coupling agent includes at least one of heptadecafluorodecyltriethoxysilane, perfluorooctyltrimethoxysilane, and perfluorooctylethyltriethoxysilane. In this way, it can not only be efficiently bonded with the moisture curing layer to improve the adhesion and stability of the sealant, but also make the hydrophobic layer have better hydrophobicity to reduce the penetration of water vapor into the sealant and affect the performance of the electrochromic device.

[0488] According to an embodiment of the present disclosure, the third adhesive further includes a solvent, which can be perfluorocyclic ether.

[0489] According to an embodiment of the present disclosure, the thickness of the main adhesive layer is 50-150 μm, for example, 50 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 150 μm;

[0490] And / or, the thickness of the moisture curing layer is 50-150 μm, for example, 50 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 150 μm;

[0491] And / or, the thickness of the hydrophobic layer is 20 μm to 100 μm, for example, 20 μm, 40 μm, 50 μm, 60 μm, 80 μm, 100 μm.

[0492] Thus, the first adhesive layer, the second adhesive layer and the hydrophobic layer satisfying the above thickness have good adhesion, stability and mechanical strength, and improve the performance of the device.

[0493] According to an embodiment of the present disclosure, the sealant further comprises a through hole penetrating through the main adhesive layer 310, the moisture curing layer 320 and the hydrophobic layer 330, and the through hole is filled with a sealing glue. The through hole is designed to fill the electrochromic liquid into the sealed cavity, and then seal the through hole with the sealing glue.

[0494] According to an embodiment of the present disclosure, the electrochromic device further comprises a first substrate and a second substrate, the first substrate is arranged on the side of the first conductive layer away from the second conductive layer, and the second substrate is arranged on the side of the second conductive layer away from the first conductive layer.

[0495] In some embodiments, the first substrate and the second substrate can both be glass, which has high transparency and good hydrophobic vapor transmission performance.

[0496] According to an embodiment of the present disclosure, the electrochromic liquid comprises an anodic coloring material and a cathodic coloring material. Exemplarily, the anodic coloring material comprises at least one of tungsten trioxide, molybdenum trioxide, phenothiazine compound, phenoxazine compound (5,10-dimethylphenoxazine), thiophene compound, phthalocyanine, methylene blue, viologen, methyl viologen, ethyl viologen, phenyl viologen and propyl viologen; and the cathodic coloring material comprises at least one of phenylenediamine, nickel oxide, manganese dioxide, iridium oxide, polyaniline, Prussian blue, polypyrrole, 1,1'-disubstituted-4,4'-bipyridine and 1,1'-diheptyl-4,4'-bipyridine tetrafluoroborate. Exemplarily, the phenoxazine compound can be 5,10-dimethylphenoxazine.

[0497] According to an embodiment of the present disclosure, the sealed cavity 400B further comprises an electrolyte and a solvent. Exemplarily, the electrolyte comprises one or more of tetrabutylammonium bromide, tetrabutylammonium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis-trifluoromethylsulfonylimide, polyethylene oxide, polypropylene oxide and polymethyl methacrylate; and the solvent comprises at least one of propylene carbonate, butyrolactone, 2-acetylbutyrolactone, γ-valerolactone, ethylene carbonate, propylene carbonate, sulfolane, 3-methylsulfolane, dimethylacetamide, dimethylformamide, acetonitrile, glutaronitrile, 2-methylglutaronitrile, 3-hydroxypropionitrile, tetraethylene glycol dimethyl ether, dimethyl sulfoxide, ethoxyethanol and cyclopentanone.

[0498] The present disclosure also provides a method for preparing the electrochromic device. According to an embodiment of the present disclosure, the method comprises: arranging a sealant between the first conductive layer and the second conductive layer, and the sealant and the first conductive layer and the second conductive layer form the sealed cavity; filling the sealed cavity with the electrochromic liquid, and resealing the sealed cavity.

[0499] According to an embodiment of the present disclosure, referring to FIG. 26, the method comprises: S100C forming a main adhesive layer, S200C forming a moisture-cured layer, and S300C forming a hydrophobic layer, which will be described in detail below.

[0500] S100C forming a main adhesive layer

[0501] In this step, the main adhesive layer is formed between the first conductive layer and the second conductive layer, and the main adhesive layer is adhered to the first conductive layer and the second conductive layer to form a sealed cavity.

[0502] According to an embodiment of the present disclosure, the method for forming the main adhesive layer comprises:

[0503] In this step, the raw material of the first adhesive is applied to the surface of the first conductive layer, then the first conductive layer and the second conductive layer are brought close to each other, and the raw material of the first adhesive is adhered to the surface of the second conductive layer, and then a first curing treatment is performed to obtain the main adhesive layer.

[0504] In this step, the first curing treatment is performed under ultraviolet irradiation, and the irradiation power is not less than 1000 mJ / cm 2 (For example, it can be 1000 mJ / cm 2 , 2000 mJ / cm 2 , 3000 mJ / cm 2 , 4000 mJ / cm 2 , 5000 mJ / cm 2 , 6000 mJ / cm 2 , 7000 mJ / cm 2 , 8000 mJ / cm 2 ), and the irradiation time is 0.5 min to 5 min (for example, it can be 0.5 min, 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, 5 min). Thus, the first adhesive is quickly cured to form the main adhesive layer.

[0505] S200C forming a moisture-cured layer

[0506] In this step, raw materials of the second adhesive are applied to at least part of the surface of the side of the main adhesive layer away from the sealed cavity, and a second curing treatment is performed to obtain the moisture-cured layer.

[0507] According to an embodiment of the present disclosure, the method for forming the moisture-cured layer comprises:

[0508] In this step, raw materials of the second adhesive are applied to at least part of the surface of the side of the main adhesive layer away from the sealed cavity, and a second curing treatment is performed to obtain the moisture-cured layer.

[0509] The temperature of the third curing treatment is 100℃-150℃ (for example, 100℃, 110℃, 120℃, 130℃, 140℃, or 150℃), and the time is 20min-40min (for example, 20min, 25min, 30min, 35min, or 40min). Thus, the third adhesive is quickly cured to form the hydrophobic layer without affecting the properties of other materials.

[0510] S300C forming a hydrophobic layer

[0511] In this step, the electrochromic liquid is injected into the sealed cavity, and the sealed cavity is sealed again.

[0512] According to an embodiment of the present disclosure, the method for forming the hydrophobic layer comprises:

[0513] In this step, raw materials of the second adhesive are applied to at least part of the surface of the side of the main adhesive layer away from the sealed cavity, and a second curing treatment is performed to obtain the moisture-cured layer.

[0514] The temperature of the third curing treatment is 100℃-150℃ (for example, 100℃, 110℃, 120℃, 130℃, 140℃, or 150℃), and the time is 20min-40min (for example, 20min, 25min, 30min, 35min, or 40min). Thus, the third adhesive is quickly cured to form the hydrophobic layer without affecting the properties of other materials.

[0515] S400C injecting liquid

[0516] In this step, the electrochromic liquid is injected into the sealed cavity, and the sealed cavity is sealed again.

[0517] According to an embodiment of the present disclosure, the main adhesive layer is bonded with the first conductive layer and the second conductive layer to form a sealed cavity, the moisture-cured layer has a second liquid injection port, and the hydrophobic layer has a third liquid injection port.

[0518] The first liquid filling port, the second liquid filling port and the third liquid filling port are in communication. Thereby, the electrochromic liquid can be filled into the sealed cavity through the third liquid filling port, the second liquid filling port and the first liquid filling port.

[0519] According to embodiments of the present disclosure, before the electrochromic liquid is filled, the method further comprises:

[0520] The first electrode is electrically connected with the first conductive layer;

[0521] The second electrode is electrically connected with the second conductive layer;

[0522] The first silver paste covers at least part of the contact area between the first electrode and the first conductive layer;

[0523] The second silver paste covers at least part of the contact area between the second electrode and the first conductive layer or the second conductive layer, to obtain a semi-finished product;

[0524] The semi-finished product is subjected to a heating treatment;

[0525] The temperature of the heating treatment is 90-120℃ (for example, it can be 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃), and the time is 60-150min (for example, it can be 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min).

[0526] The semi-finished product is subjected to the heating treatment under the above conditions, which is beneficial to the solidification of the silver paste and further heat-curing of the main adhesive layer to strengthen the adhesion.

[0527] It should be noted that the features and advantages described above for the electrochromic liquid also apply to the method, device and electrochromic device for preparing the electrochromic liquid, and the method for preparing the electrochromic device, which will not be described here.

[0528] The present disclosure also provides an electronic device. According to embodiments of the present disclosure, the electronic device comprises the electrochromic device described above. Thereby, the electronic device of the present disclosure has excellent color-changing performance and service life.

[0529] According to embodiments of the present disclosure, the electronic device comprises a display, an anti-dazzle rearview mirror, a light-adjustable curtain, a light-adjustable glass window, light-adjustable color-changing glasses, electronic paper, etc.

[0530] The schemes of the present disclosure will be explained below in conjunction with examples. Those skilled in the art will understand that the examples below are only for illustration of the present disclosure and should not be considered as limiting the scope of the present disclosure. If no specific technology or condition is specified in the examples, the technology or condition described in the literature in the art or according to the product manual is used. If no manufacturer of the reagent or instrument is specified, it is a conventional product that can be obtained on the market.

[0531] Example 1

[0532] (1) In a glove box with water and oxygen content ≤0.1 ppm, propylene carbonate was treated to remove water and oxygen, and the treatment method was as follows: propylene carbonate was placed in a glass container for heating, the heating temperature was 100℃, vacuum was applied to make the internal pressure of the glass container 0.01 kpa, the temperature of the condenser was set to 15℃, and the collected condensate was recycled 2 times according to the above heating and condensing steps to obtain the target propylene carbonate solvent.

[0533] (2) In the above glove box, an electrochromic liquid was prepared, and the components included 5,10-dimethylphenazine anodic color-changing material with a concentration of 50 mmol / L, 1,1'-diheptyl-4,4'-bipyridine tetrafluoroborate cathodic color-changing material with a concentration of 50 mmol / L, lithium tetrafluoroborate electrolyte with a concentration of 50 mmol / L, and the target propylene carbonate solvent obtained in step (1). The components were mixed to obtain the electrochromic liquid.

[0534] (3) The cathode reflective conductive glass and the anode transparent conductive glass were cleaned, and a corresponding conductive structure was formed on the cathode glass coating surface by laser engraving. Then, the anode glass coating surface was subjected to dispensing operation, the dispensing width was 1.8 mm, and a 2 mm liquid filling port was reserved. After being attached to the cathode glass, ultraviolet curing was performed, and after complete curing, 1.0 g of conductive silver adhesive was applied on the intersection area between the anode and cathode glass, and heating curing was performed at 120℃ for 2 h. The assembled empty box device was moved into the step (2) glove box filled with nitrogen, the electrochromic liquid prepared in step (2) was filled into the liquid filling port, and the opening was sealed to obtain the electrochromic device.

[0535] Example 2

[0536] The difference from Example 1 is that in step (1), the number of cycles is 1.

[0537] Example 3

[0538] The difference from Example 1 is that in step (1), the number of cycles is 3.

[0539] Example 4

[0540] The difference from Example 1 is that in step (1), the internal pressure is 0.05 kpa.

[0541] Example 5

[0542] The difference from Example 1 is that the heating temperature in step (1) is 80°C.

[0543] Example 6

[0544] The difference from Example 1 is that the heating temperature in step (1) is 120°C.

[0545] Example 7

[0546] The difference from Example 1 is that in step (1), propylene carbonate is replaced by toluene.

[0547] Example 8

[0548] The difference from Example 1 is that in step (1), propylene carbonate is replaced by dimethylbenzene.

[0549] Comparative Example 1

[0550] The difference from Example 1 is that in step (2), 400 mmol / L of antioxidant 2-(2'-hydroxy-5'-methylphenyl) benzotriazole is added to the electrochromic liquid.

[0551] Comparative Example 2

[0552] The difference from Example 1 is that in step (2), 500 mmol / L of antioxidant 2-(2'-hydroxy-5'-methylphenyl) benzotriazole is added to the electrochromic liquid.

[0553] Comparative Example 3

[0554] The difference from Example 1 is that in step (2), 600 mmol / L of antioxidant 2-(2'-hydroxy-5'-methylphenyl) benzotriazole is added to the electrochromic liquid.

[0555] Comparative Example 4

[0556] The difference from Example 1 is that step (1) is not included, and the water content of the propylene carbonate solvent added in step (2) is 159 ppm, and the oxygen content is 188 ppm.

[0557] Comparative Example 5

[0558] The difference from Comparative Example 4 is that in step (2), 400 mmol / L of antioxidant 2-(2'-hydroxy-5'-methylphenyl) benzotriazole is added.

[0559] Test Example 1

[0560] 1. After the electrochromic liquid was prepared in step (2) in Examples 1-8 and Comparative Examples 1-5, the concentrations of water and dissolved oxygen were detected by an optical dissolved oxygen analyzer and a coulombic calorimeter, respectively. These values ​​were used as the initial water content and initial oxygen content of the experiment.

[0561] 2. The electrochromic devices prepared in Examples 1-8 and Comparative Examples 1-5 were placed in a room temperature environment (25°C, relative humidity 65%) for power-off and power-on cycle tests. The specific steps are as follows: First, the sample was energized with a voltage of 1.2V to change color and maintained for 30 seconds, then the power was turned off for 30 seconds. This is one cycle. Repeat this cycle for 40,000 and 60,000 cycles respectively.

[0562] The reflectance R of the device was measured using a UV-6100 ultraviolet spectrophotometer in the first, 40,000th, and 60,000th cycles after 30 seconds of power-on. a The reflectivity R of the device after 30 seconds of power failure b According to the formula, the contrast ΔR(%) = R b -R a Calculate the contrast of the first cycle, the 40,000th cycle, and the 60,000th cycle, and denote them as △R0, △R1, and △R2, respectively.

[0563] The L, a, and b values ​​of the device were measured using a UV-6100 ultraviolet spectrophotometer after a 30-second power outage in the first, 40,000th, and 60,000th cycles, respectively. The first cycle was recorded as "L0, a0, b0", the 40,000th cycle as "L1, a1, b1", and the 60,000th cycle as "L2, a2, b2".

[0564] All the above tests were performed three times, and the average value was calculated as the result of each experiment. The test results are represented as OK and NG. If the sample contrast R is ≥ 65%, it is OK; otherwise, it is NG. If the sample a and b values ​​are both in the range of [-3.5, 3.5] and the L value is in the range of [80, 90], it is OK; otherwise, it is NG.

[0565] The results are shown in Tables 1 and 2. It can be seen that after 40,000 and 60,000 cycles, compared with Comparative Examples 1 to 5, the electrochromic devices of Examples 1 to 8 still have higher contrast, and the L, a, and b values ​​all meet the requirements, indicating that they have better color-changing performance. Among them, the device of Example 1 has better overall performance, lower preparation cost, and lower energy consumption.

[0566] In Comparative Example 1-3, the antioxidant was added in the electrochromic device, although the water-oxygen content was in a low state in the initial state, the water-oxygen content was high after 60000 cycles, and a large amount of anode color material oxide and cathode color material hydrate were generated, which overall led to low color change performance of the device.

[0567] In Comparative Example 4, because the propylene carbonate solvent was not subjected to water-oxygen removal treatment, the electrochromic liquid still had a high water-oxygen content after multiple cycles, and a large amount of anode color material oxide and cathode color material hydrate were generated, which overall led to low color change performance of the device.

[0568] Comparative Example 4 and Comparative Example 5, for the propylene carbonate solvent which was not subjected to water-oxygen removal treatment, the addition of the antioxidant can to some extent reduce the water-oxygen content in the electrochromic liquid after multiple cycles, reduce the generation of anode color material oxide and cathode color material hydrate, so that the contrast of the device is improved, but compared with the device of Example 1 which is subjected to water-oxygen treatment and does not add an antioxidant, the overall performance is still poor.

[0569] Table 1 Water-oxygen content and contrast ratio of the power-off power-on cycle test (40000 cycles and 60000 cycles)

[0570] Table 2 L value, a value, b value of the power-off power-on cycle test (40000 cycles and 60000 cycles)

[0571] Test Example 2

[0572] The electrochromic devices prepared from Example 1 and Comparative Example 3 were tested respectively by the method of Test Example 1, wherein the cycle number "40000 cycles and 60000 cycles" was replaced by "80000 cycles and 100000 cycles".

[0573] The results are shown in Tables 3 and 4, compared with Comparative Example 3, the solvent of the electrochromic liquid of Example 1 was subjected to water-oxygen removal treatment and did not add an antioxidant, the contrast ratio of the device prepared after 80000 and 100000 cycles was still high, the L, a, b values still met the requirements, wherein it can maintain good color change performance after as high as 100000 cycles, and has a long service life.

[0574] Table 3 Water-oxygen content and contrast ratio of the power-off power-on cycle test (80000 cycles and 100000 cycles)

[0575] Table 4 L value, a value, b value of the power-off power-on cycle test (80000 cycles and 100000 cycles)

[0576] Test Example 3

[0577] 1. After preparing the electrochromic liquid in step (2) in Example 1 and Comparative Example 3, the concentrations of water and dissolved oxygen were detected by an optical dissolved oxygen analyzer and a coulometric calorimeter, respectively. These values ​​were used as the initial water content and initial oxygen content of the experiment.

[0578] 2. The electrochromic devices prepared in Example 1 and Comparative Example 3 were subjected to thermal cycling tests. The specific steps are as follows: The electrochromic device was continuously powered by a voltage of 1.2V. The ambient temperature was first raised to 80°C, maintained for 1 hour, then cooled to -20°C, and maintained for another hour. This is one cycle, and the cycles were repeated for a total of 360h and 480h.

[0579] The reflectance R of the device was measured using a UV-6100 ultraviolet spectrophotometer after a 1.2V voltage was applied for 30 seconds. a0 and reflectivity R after 30 seconds of power outage b0 Contrast ratio ΔR0(%) = R b0 -R a0 The reflectivity R of the device was measured after 360 hours of cycling and 30 seconds of power-on. a1 and reflectivity R after 30 seconds of power outage b1 Contrast ratio ΔR1(%) = R b1 -R a1 The reflectivity R of the device was measured after 30 seconds of power-on following a 480-hour cycle. a2 and reflectivity R after 30 seconds of power outage b2 Contrast ratio ΔR²(%) = R b2 -R a2 .

[0580] The L, a, and b values ​​of the device were measured using a UV-6100 ultraviolet spectrophotometer after being powered on at 1.2V for 30 seconds and after being powered off for 30 seconds, and recorded as "L0, a0, b0". The L, a, and b values ​​of the device after being powered off for 30 seconds were measured after 360 hours of cycling and recorded as "L1, a1, b1". The L, a, and b values ​​of the device after being powered off for 30 seconds were measured after 480 hours of cycling and recorded as "L2, a2, b2".

[0581] All the above tests were performed three times, and the average value was calculated as the result of each experiment. The test results are represented as OK and NG. If the sample contrast R is ≥ 65%, it is OK; otherwise, it is NG. If the sample a and b values ​​are both in the range of [-3.5, 3.5] and the L value is in the range of [80, 90], it is OK; otherwise, it is NG.

[0582] The results are shown in Table 5 and Table 6. Compared with Comparative Example 3, the solvent in the electrochromic liquid of Example 1 was treated by water-oxygen and no antioxidant was added. After 360 h and 480 h of cold-heat cycle, the contrast of the prepared device was still high, and the L, a, and b values still met the requirements. After 480 h of cold-heat cycle, the device still maintained good color-changing performance and had a long service life.

[0583] Table 5 Water-oxygen content and contrast of cold-heat cycle test

[0584] Table 6 L value, a value, and b value of cold-heat cycle test

[0585] Test Example 4

[0586] 1. After the preparation of the electrochromic liquid in step (2), the moisture and dissolved oxygen concentrations of Example 1 and Comparative Example 3 were detected by using an optical dissolved oxygen analyzer and a coulomb method cartridge moisture analyzer, respectively. These values were used as the initial water content and initial oxygen content of the experiment.

[0587] 2. The electrochromic devices prepared from Example 1 and Comparative Example 3 were subjected to high-temperature and high-humidity cycle test, respectively. The specific steps were as follows: under the condition of 80% relative humidity and 80℃ environmental temperature, the electrochromic device was powered by 1.2 V voltage for 360 h and 480 h.

[0588] The reflectivity R of the device after 30 seconds of power-on and the reflectivity R after 30 seconds of power-off were measured by using a UV-6100 ultraviolet spectrophotometer, respectively. a0 b0 The contrast AR0(%) = R b0 -R a0 ; the reflectivity R of the device after 30 seconds of power-on and the reflectivity R after 30 seconds of power-off were measured by using a UV-6100 ultraviolet spectrophotometer, respectively. a1 b1 The contrast AR1(%) = R b1 -R a1 ; the reflectivity R of the device after 30 seconds of power-on and the reflectivity R after 30 seconds of power-off were measured by using a UV-6100 ultraviolet spectrophotometer, respectively. a2 b2 The contrast AR2(%) = R b2 -R a2 .

[0589] ​​​The L value, a value and b value of the device after being powered on for 30 seconds and powered off for 30 seconds at 1.2 V are measured by the UV-6100 ultraviolet spectrophotometer, and are recorded as "L0, a0, b0"; the L value, a value and b value of the device after being powered off for 30 seconds after 360 h of cycling are measured, and are recorded as "L1, a1, b1"; the L value, a value and b value of the device after being powered off for 30 seconds after 480 h of cycling are measured, and are recorded as "L2, a2, b2".

[0590] All the above tests are repeated three times, and the average value is calculated as the result of each test. The test result is represented as OK and NG. If the sample contrast R is greater than or equal to 65%, it is OK, otherwise it is NG. If the a and b values of the sample are in the interval [-3.5, 3.5], and the L value is in the interval [80, 90], it is OK, otherwise it is NG.

[0591] The results are shown in Tables 7 and 8. Compared with Comparative Example 3, the solvent in the electrochromic liquid of Example 1 is treated by water and oxygen and no antioxidant is added. After 360 h and 480 h of high temperature and high humidity cycling, the contrast of the prepared device is still high, and the L, a and b values still meet the requirements. After 480 h of high temperature and high humidity cycling, the device still maintains good color changing performance and has a long service life.

[0592] Table 7 Water and oxygen content and contrast in high humidity and high temperature test

[0593] Table 8 L value, a value and b value in high humidity and high temperature test

[0594] Example 1-1

[0595] In this example, the conductive thin film material is prepared according to the following method:

[0596] 1. A 0.6 mm glass substrate is provided, and the glass substrate is ultrasonically cleaned with acetone and ethanol, and then the surface is cleaned with deionized water and dried in a vacuum environment;

[0597] 2. The glass is placed on the working trolley of the sputtering coating machine, and vacuumizing is performed;

[0598] 3. When the vacuum degree of the coating chamber reaches 3 x 10 -3 Pa, the ICP ion source is turned on, argon gas is used, the argon gas flow is 250-300 sccm, the ICP power is 0.7 kw, and the time is 5 min;

[0599] 4. Turn on the working turntable to rotate it, continuously input argon, turn on the sputtering power of the silver target, set the sputtering power to 10 kw, at the same time, turn on the sputtering power of the palladium target, set the sputtering power to start from 0 kw, increase by 0.01 kw every 5 s in a linear gradient, until 0.6 kw, and the coating time is 300 s;

[0600] 5. Turn off the sputtering power of the silver target and the palladium target, and obtain a reflective layer with a gradient of 0%-6% Pd and a thickness of 30 nm.

[0601] Example 2-1

[0602] The difference from Example 1-1 is that step 4 is as follows:

[0603] Turn on the working turntable to rotate it, continuously input argon, turn on the sputtering power of the silver target, set the sputtering power to 10 kw, at the same time, turn on the sputtering power of the palladium target, set the sputtering power to start from 0 kw, increase by 0.02 kw every 6 s in a linear gradient, until 1 kw, and the coating time is 300 s.

[0604] Thus, a reflective layer with a gradient of 0%-10% Pd is obtained.

[0605] Example 3-1

[0606] The difference from Example 1-1 is that step 4 is as follows:

[0607] Turn on the working turntable to rotate it, continuously input argon, turn on the sputtering power of the silver target, set the sputtering power to 10 kw, at the same time, turn on the sputtering power of the palladium target, set the sputtering power to start from 0 kw, increase by 0.01 kw every 10 s in a linear gradient, until 0.3 kw, and the coating time is 300 s.

[0608] Thus, a reflective layer with a gradient of 0%-3% Pd is obtained.

[0609] Example 4-1

[0610] The difference from Example 1-1 is that step 4 is as follows:

[0611] Turn on the working turntable to rotate it, continuously input argon, turn on the sputtering power of the silver target, set the sputtering power to 10 kw, at the same time, turn on the sputtering power of the palladium target, set the sputtering power to start from 0 kw, increase by 0.01 kw every 4 s in a linear gradient, until 0.8 kw, and the coating time is 300 s.

[0612] Thus, a reflective layer with a gradient of 0%-8% Pd is obtained.

[0613] Example 5-1

[0614] The difference from Example 1-1 is that step 4 is as follows:

[0615] The working turntable is started to rotate, argon gas is continuously fed, the sputtering power of the silver target is set to 10 kw, the sputtering power of the palladium target is set to 0.3 kw, the sputtering power is increased by 0.01 kw every 10 s in a linear gradient until 0.6 kw, and the coating time is 300 s.

[0616] Thus, a reflective layer with a gradient of 3%-6% Pd is obtained.

[0617] Example 6-1

[0618] The difference from Example 1-1 is that step 4 is as follows:

[0619] The working turntable is started to rotate, argon gas is continuously fed, the sputtering power of the silver target is set to 10 kw, the sputtering power of the palladium target is set to 0.3 kw, the sputtering power is increased by 0.01 kw every 10 s in a linear gradient until 0.6 kw, and the coating time is 300 s.

[0620] Thus, a reflective layer with a gradient of 0%-6% Pd is obtained.

[0621] Comparative Example 1-1

[0622] In this comparative example, the conductive thin film material is prepared according to the following method:

[0623] 1. A 0.6 mm glass substrate is provided, and the glass substrate is ultrasonically cleaned with acetone and ethanol, and then the surface is cleaned with deionized water and dried in a vacuum environment;

[0624] 2. The glass is placed on the working turntable of the sputtering coating machine and vacuumized;

[0625] 3. When the vacuum degree of the coating chamber reaches 3 x 10 -3 Pa, the ICP ion source is turned on, argon gas is fed at a flow rate of 250-300 sccm, the ICP power is 0.7 kw, and the time is 5 min;

[0626] 4. Argon gas is continuously fed, the sputtering power of the silver target is set to 10 kw, and the coating time is 300 s.

[0627] 5. The sputtering power of the silver target is turned off, and the reflective layer of pure silver material is completed.

[0628] Comparative Example 2-1

[0629] The difference from Example 1-1 is that step 4 is as follows:

[0630] The self-rotation function of the substrate of the sputtering coating machine was closed, and the sample to be coated was parked between the two targets. The sputtering power of the silver target was 10 kw, and the sputtering power of the palladium target was 10 kw. The coating time was 300 s. In this way, the silver layer and the palladium layer arranged along the length direction of the transparent substrate were formed (Figure 18).

[0631] Comparative Example 3-1

[0632] The difference from Example 1-1 is that Step 4 is as follows:

[0633] The working turret was started to rotate, and the argon gas was continuously introduced. The sputtering power of the silver target was 10 kw, and the sputtering power of the palladium target was 1 kw. The coating time was 300 s.

[0634] In this way, a pure 10% Pd reflective layer was obtained.

[0635] Test Example 1-1

[0636] 1. The surface conductivity and diffusion activation energy of the conductive thin film materials prepared in Examples 1-1 to 6-1 and Comparative Examples 1-1 to 3-1 were tested respectively. The specific test method is as follows:

[0637] Surface conductivity: A four-probe tester was used. Four equally spaced probes were gently placed on the surface of the thin film, ensuring good contact between the probes and the thin film. A fixed current was applied using a current source, and the conductivity of the thin film was calculated.

[0638] Diffusion activation energy: The test was performed using an electrochemical workstation device.

[0639] The results are shown in Table 9. The overall performance of the conductive thin film materials prepared in Examples 1-1 to 6-1 is more excellent than that of Comparative Examples 1-1 to 3-1.

[0640] In the reflective layer of Comparative Example 1-1, there is no palladium element in the pure silver film layer. Although the surface resistivity of the reflective layer is reduced, the conductivity is enhanced. However, the diffusion activation energy of the reflective layer is low, the stability is poor, and the film layer is prone to fall off.

[0641] In the reflective layer of Comparative Example 2-1, the silver layer and the palladium layer are arranged separately. Although the overall diffusion activation energy of the reflective layer is improved, the diffusion activation energy of the part near the pure silver side is not significantly improved, and the film layer is prone to fall off. Moreover, the surface resistivity of the reflective layer is extremely high, and the conductivity performance is poor.

[0642] The reflective layer of Comparative Example 3-1 is a high proportion of pure silver palladium alloy layer. Although the diffusion activation energy is high, the resistivity is also high, and the conductivity performance is poor.

[0643] Since the diffusion activation energy of palladium is higher than that of silver, in Examples 1-1 to 6-1, the diffusion activation energy of the reflective layer is slightly increased as the proportion of palladium doping in the reflective layer is gradually increased, and palladium is prone to react with oxygen in the environment to form a passivation layer, thereby improving the anti-electromigration corrosion performance of silver, reducing the occurrence of film peeling, and improving the stability of the conductive thin film material. Since the resistivity of palladium is higher than that of silver, as the proportion of palladium doping increases, the surface resistivity of the reflective layer is slightly increased. Overall, the palladium content of the sub-reflection layer farthest from the transparent substrate is 3% to 6%, which is better.

[0644] Table 9

[0645] 2. The reflective layer structure prepared in Example 1-1 was analyzed using X-ray photoelectron spectroscopy-XPS deep sputtering technology. As shown in Figure 22, there is a certain amount of O element within 5 nm of the surface of the reflective layer, which is the natural oxidation of Pd element to form a dense protective film. As the depth of the film increases, the Ag and Pd contents of the product show linear changes, indicating a high-quality gradual doping ratio film.

[0646] Examples 10-11

[0647] The conductive thin film material was prepared according to the method of Example 1-1, except that:

[0648] a. After step 3 and before step 4, the following steps were further performed:

[0649] The argon gas was continuously supplied, the sputtering power of the Si target was turned on, and the oxygen gas was supplied. The sputtering power was 3.5 kw, the oxygen flow rate was 180-220 sccm, and the film plating time was 150 s. The sputtering power of the Si target was turned off, and the SiO2 bonding transition layer with a thickness of 20 nm and a visible light absorption rate of less than 0.01 was completed.

[0650] b. After step 5, the sputtering power of the indium tin oxide was turned on, the sputtering power was 5.5 kw, the oxygen flow rate was 20-40 sccm, the film plating time was 100 s, and the indium tin oxide protective layer with a thickness of 10 nm and a visible light absorption rate of less than 0.01 was completed.

[0651] Example 8-1

[0652] The conductive thin film material was prepared according to the method of Example 2-1, except that:

[0653] a. After step 3 and before step 4, the following steps were further performed:

[0654] The argon gas is continuously supplied, and the sputtering power of the Si target is turned on while the oxygen gas is supplied. The sputtering power is 3.5 kw, the oxygen flow rate is 180-220 seem, and the film forming time is 150 s. The sputtering power of the Si target is turned off, and the SiO2 bonding transition layer with a thickness of 20 nm and a visible light absorption rate of less than 0.01 is formed.

[0655] b. After step 5, the sputtering power of the indium tin oxide is turned on, the sputtering power is 5.5 kw, the oxygen flow rate is 20-40 seem, the film forming time is 100 s, and the indium tin oxide protective layer with a thickness of 10 nm and a visible light absorption rate of less than 0.01 is formed.

[0656] Example 9-1

[0657] The conductive thin film material is prepared according to the method of Example 3-1, except that:

[0658] a. After step 3 and before step 4, the following step is further performed:

[0659] The argon gas is continuously supplied, and the sputtering power of the Si target is turned on while the oxygen gas is supplied. The sputtering power is 3.5 kw, the oxygen flow rate is 180-220 seem, and the film forming time is 150 s. The sputtering power of the Si target is turned off, and the SiO2 bonding transition layer with a thickness of 20 nm and a visible light absorption rate of less than 0.01 is formed.

[0660] b. After step 5, the sputtering power of the indium tin oxide is turned on, the sputtering power is 5.5 kw, the oxygen flow rate is 20-40 seem, the film forming time is 100 s, and the indium tin oxide protective layer with a thickness of 10 nm and a visible light absorption rate of less than 0.01 is formed.

[0661] Example 10-1

[0662] The conductive thin film material is prepared according to the method of Example 4-1, except that:

[0663] a. After step 3 and before step 4, the following step is further performed:

[0664] The argon gas is continuously supplied, and the sputtering power of the Si target is turned on while the oxygen gas is supplied. The sputtering power is 3.5 kw, the oxygen flow rate is 180-220 seem, and the film forming time is 150 s. The sputtering power of the Si target is turned off, and the SiO2 bonding transition layer with a thickness of 20 nm and a visible light absorption rate of less than 0.01 is formed.

[0665] b. After step 5, the sputtering power of the indium tin oxide is turned on, the sputtering power is 5.5 kw, the oxygen flow rate is 20-40 seem, the film forming time is 100 s, and the indium tin oxide protective layer with a thickness of 10 nm and a visible light absorption rate of less than 0.01 is formed.

[0666] Example 11-1

[0667] The conductive thin film material was prepared according to the method of Example 5-1, except that:

[0668] a. After step 3 and before step 4, the following step was further performed:

[0669] The argon gas was continuously supplied, and the sputtering power of the Si target was turned on while the oxygen gas was supplied. The sputtering power was 3.5 kw, the oxygen flow rate was 180-220 seem, and the film deposition time was 150 s. The sputtering power of the Si target was turned off, and the SiO2 bonding transition layer with a thickness of 20 nm and a visible light absorption rate of less than 0.01 was completed.

[0670] b. After step 5, the sputtering power of the indium tin oxide was turned on, the sputtering power was 5.5 kw, the oxygen flow rate was 20-40 seem, the film deposition time was 100 s, and the indium tin oxide protective layer with a thickness of 10 nm and a visible light absorption rate of less than 0.01 was completed.

[0671] Example 12-1

[0672] The conductive thin film material was prepared according to the method of Example 6-1, except that:

[0673] a. After step 3 and before step 4, the following step was further performed:

[0674] The argon gas was continuously supplied, and the sputtering power of the Si target was turned on while the oxygen gas was supplied. The sputtering power was 3.5 kw, the oxygen flow rate was 180-220 seem, and the film deposition time was 150 s. The sputtering power of the Si target was turned off, and the SiO2 bonding transition layer with a thickness of 20 nm and a visible light absorption rate of less than 0.01 was completed.

[0675] b. After step 5, the sputtering power of the indium tin oxide was turned on, the sputtering power was 5.5 kw, the oxygen flow rate was 20-40 seem, the film deposition time was 100 s, and the indium tin oxide protective layer with a thickness of 10 nm and a visible light absorption rate of less than 0.01 was completed.

[0676] Comparative Example 4-1

[0677] The conductive thin film material was prepared according to the method of Comparative Example 1-1, except that:

[0678] a. After step 3 and before step 4, the following step was further performed:

[0679] The argon gas is continuously supplied, and the sputtering power of the Si target is turned on while the oxygen gas is supplied. The sputtering power is 3.5 kw, the oxygen flow rate is 180-220 seem, and the film forming time is 150 s. The sputtering power of the Si target is turned off, and the SiO2 bonding transition layer with a thickness of 20 nm and a visible light absorption rate of less than 0.01 is formed.

[0680] b. After step 5, the sputtering power of the indium tin oxide is turned on, the sputtering power is 5.5 kw, the oxygen flow rate is 20-40 seem, the film forming time is 100 s, and the indium tin oxide protective layer with a thickness of 10 nm and a visible light absorption rate of less than 0.01 is formed.

[0681] Comparative Example 5-1

[0682] The conductive thin film material is prepared according to the method of Comparative Example 2-1, except that:

[0683] a. After step 3 and before step 4, the following step is further performed:

[0684] The argon gas is continuously supplied, and the sputtering power of the Si target is turned on while the oxygen gas is supplied. The sputtering power is 3.5 kw, the oxygen flow rate is 180-220 seem, and the film forming time is 150 s. The sputtering power of the Si target is turned off, and the SiO2 bonding transition layer with a thickness of 20 nm and a visible light absorption rate of less than 0.01 is formed.

[0685] b. After step 5, the sputtering power of the indium tin oxide is turned on, the sputtering power is 5.5 kw, the oxygen flow rate is 20-40 seem, the film forming time is 100 s, and the indium tin oxide protective layer with a thickness of 10 nm and a visible light absorption rate of less than 0.01 is formed.

[0686] Comparative Example 6-1

[0687] The conductive thin film material is prepared according to the method of Comparative Example 3-1, except that:

[0688] a. After step 3 and before step 4, the following step is further performed:

[0689] The argon gas is continuously supplied, and the sputtering power of the Si target is turned on while the oxygen gas is supplied. The sputtering power is 3.5 kw, the oxygen flow rate is 180-220 seem, and the film forming time is 150 s. The sputtering power of the Si target is turned off, and the SiO2 bonding transition layer with a thickness of 20 nm and a visible light absorption rate of less than 0.01 is formed.

[0690] b. After step 5, the sputtering power of the indium tin oxide is turned on, the sputtering power is 5.5 kw, the oxygen flow rate is 20-40 seem, the film forming time is 100 s, and the indium tin oxide protective layer with a thickness of 10 nm and a visible light absorption rate of less than 0.01 is formed.

[0691] Test Example 2-1

[0692] The reflectivity, transmittance, resistivity, charge-discharge cycle test and vibration wear test of the conductive thin film materials prepared in Example 1-1, 7-1 to 12-1 and Comparative Examples 4-1 to 6-1 were tested respectively, and the specific test methods are as follows:

[0693] Reflectivity and transmittance: tested by spectrometer, light loss rate / % = 100%-reflectivity-transmittance.

[0694] Resistivity: tested by four-probe tester.

[0695] Charge-discharge cycle test: power on for 5 seconds and discharge for 5 seconds under the voltage of 3V as a cycle, and after every 5000 cycles, whether the device appears blackening, color change, and peeling phenomenon was detected, and if there is no above phenomenon, the cycle continues.

[0696] Vibration wear test: the device and rubber particles were placed in the drum of the vibration wear tester, and rotated at the speed of 1s / cycle and the load of 1000g, and every 30min, whether the device surface appears peeling and scratching (width greater than 0.5mm*1mm) was observed, when the peeling or scratching with the width of not less than 0.5mm*1mm appears, it is considered as unqualified, recorded as NG, otherwise, it is considered as qualified, recorded as OK.

[0697] The results are shown in Table 10. Compared with Example 7-1, the increase of the combination of the transition layer and the protective layer, especially the protective layer, can improve the wear resistance and stability of the device and reduce the peeling phenomenon of the film layer. Compared with Comparative Examples 4-1 to 6-1, the optical, electrical and wear resistance and stability of the conductive thin film materials prepared in Examples 7-1 to 12-1 are more excellent as a whole.

[0698] The reflector of Comparative Example 4-1 only contains silver, although the light loss rate and resistivity are low, the charge-discharge cycle performance is poor. The silver layer and the palladium layer in the reflector of Comparative Example 5-1 are arranged separately, which is a non-uniform optical structure, and the reflectivity and transmittance cannot be accurately detected, and the resistivity is high.

[0699] The doping amount of palladium in the reflector of Comparative Example 6-1 is constant, and the interlayer interference phenomenon is serious, resulting in more light loss and higher resistivity.

[0700] In Examples 7-1 to 10-1, as the content of palladium in the reflector increases, the light loss rate increases slightly, and the conductivity also increases. Compared with the conductive thin film material with constant palladium doping amount in Comparative Example 6-1, the use of gradual doping can reduce the interlayer interference and thus reduce the light loss rate, and also reduce the conductivity to a certain extent.

[0701] Compared with Example 7-1, the palladium doping amount of Example 11-1 is high on the side closest to the bonding transition layer, so the palladium doping amount of the entire reflective layer is high, which slightly increases the light loss rate and the electrical conductivity.

[0702] In the reflective layer of Example 7-1, the palladium content in the sub-reflection layer increases by 0.2% / nm in the direction away from the glass substrate, and the corresponding value of Example 12-1 is 1% / nm. That is, compared with Example 7-1, the palladium content increase between adjacent sub-reflection layers of Examples 1-1 to 12-1 is more, which slightly enhances the interference phenomenon, resulting in a slight increase in light loss rate and a slight increase in resistivity.

[0703] Table 10

[0704] Example 1-2

[0705] 1, 20wt% of bisphenol A type epoxy resin, 20wt% of bisphenol F type epoxy resin, 30wt% of resorcinol diglycidyl ether, 10wt% of γ-glycidyl ether oxypropyl trimethoxysilane, 18wt% of silica inorganic filler, 1wt% of cationic initiator (diaryl iodonium salt) and 1wt% of photoinitiator (benzotriazole) are stirred and mixed uniformly to obtain a first adhesive. An automatic dispensing machine is used to coat the first adhesive along the edge of the reflective conductive glass (thickness of 1.6mm), leaving an opening of about 1.5mm at the short edge. The transparent conductive glass is positioned above the coated reflective conductive glass by means of a jig, and then placed in a UV curing box for curing for 3min under an illumination energy of 6000mJ / cm 2 The width of the main adhesive layer is 1.8-2.0mm, and the thickness is 100μm. A sealed cavity is formed between the main adhesive layer, the reflective conductive glass and the transparent conductive glass.

[0706] 2, 35wt% of isocyanate prepolymer R1 is tolyl, R2 is -CH2-CH2-CH2-CH2-, and n is 50; 15wt% of diisocyanate TDI, 35wt% of siloxane-terminated polysiloxane R3 is -Si-O-Si- repeating unit, the number of repetitions is 15, and R4 is ethyl; 15wt% of amino-containing silane coupling agent are stirred and mixed uniformly to obtain a second adhesive, which is stored in a vacuum sealed state for later use. The second adhesive is applied to the periphery of the main adhesive layer (i.e. the surface of the main adhesive layer away from the sealed cavity) by dispensing and brushing, and is completely enclosed inside, leaving the opening of step 1. After brushing, it is placed in an environment with a humidity of 70% and a temperature of 30°C for two hours to obtain a moisture cured layer with a thickness of 100μm.

[0707] 3. Brush perfluorocycloether containing 5 wt% of heptadecafluorodecyltriethoxysilane on the periphery of the moisture-cured layer (i.e. the side surface of the moisture-cured layer away from the sealed cavity) and completely surround the inside, leaving the opening of step 1, and then place it in an oven at 120°C for 30 min to obtain a hydrophobic layer with a thickness of 50 nm.

[0708] 4. Electrode attachment, silver paste coating, and 120°C, 60 min thermal curing of the silver paste are performed on the cured box. Functional electrochromic liquid (50 mmol / L 5,10-dimethylphenazine, 50 mmol / L 1,1'- diheptyl-4,4'-bipyridinium tetrafluoroborate, 50 mmol / L lithium tetrafluoroborate, and propylene carbonate) is injected into the box by negative pressure, and the opening is sealed by dispensing to obtain an electrochromic device.

[0709] Example 2-2

[0710] 1. 10 wt% of bisphenol A type epoxy resin, 15 wt% of bisphenol F type epoxy resin, 40 wt% of resorcinol diglycidyl ether, 10 wt% of 3-glycidyloxypropyl triethoxysilane, 15 wt% of silica inorganic filler, 5 wt% of cationic initiator (alkyl sulfonium salt), and 5 wt% of photoinitiator (benzotriazole) are stirred and mixed uniformly to obtain a first adhesive. An automatic dispensing machine is used to coat the first adhesive along the edge of the reflective conductive glass (thickness of 1.6 mm), leaving an opening of about 1.5 mm at the short edge. The transparent conductive glass is positioned above the reflective conductive glass with the aid of a jig, and then placed in a UV curing box for 6000 mJ / cm 2 of light irradiation energy for 3 min to obtain a main adhesive layer with a width of 1.8-2.0 mm and a thickness of 100 μm. A sealed cavity is formed between the main adhesive layer, the reflective conductive glass, and the transparent conductive glass.

[0711] 2. 50 wt% of isocyanate prepolymer R1 is R2 is -CH2-CH2-, and n is 50; 10 wt% of diisocyanate MDI, 20 wt% of siloxane-terminated polysiloxane R3 is a -Si-O-Si- repeating unit with a repetition number of 10, and R4 is ethyl; 20 wt% of amino-containing silane coupling agent are stirred and mixed uniformly to obtain a second adhesive, which is stored in a vacuum-sealed state for later use. The second adhesive is coated on the periphery of the main adhesive layer (i.e. the side surface of the main adhesive layer away from the sealed cavity) and completely surrounds the inside, leaving the opening of step 1. After coating, it is placed in an environment with a humidity of 70% and a temperature of 30°C for two hours to obtain a moisture-cured layer with a thickness of 100 μm.

[0712] 3. Apply a perfluorocyclic ether containing 5 wt% perfluorooctyltrimethoxysilane to the periphery of the moisture-cured layer (i.e., the side of the moisture-cured layer away from the sealed cavity) and completely enclose it inside, leaving the opening from step 1. After application, bake at 120°C for 30 minutes to obtain a hydrophobic layer with a thickness of 60 nm.

[0713] 4. The cured box is then fitted with electrodes and coated with silver paste. The silver paste is then heat-cured at 120°C for 60 minutes. The functional electrochromic liquid (same as in Examples 1-2) is injected into the box under negative pressure, and the opening is sealed with adhesive to obtain the electrochromic device.

[0714] Example 3-2

[0715] 1. Mix 20wt% bisphenol A epoxy resin, 20wt% bisphenol F epoxy resin, 30wt% resorcinol diglycidyl ether, 5wt% (2,3-epoxy) n-propyl ether-terminated polydimethylsiloxane, 23wt% silica inorganic filler, 1wt% cationic initiator (triarylsulfonium salt), and 1wt% photoinitiator (benzothiadiazole) until homogeneous to obtain the first adhesive. Apply the first adhesive along the edge of the reflective conductive glass (1.6mm thick) using an automatic dispensing machine, leaving an opening of approximately 1.5mm on the short side. Position the transparent conductive glass over the dispensed reflective conductive glass using a fixture, and then place it in a UV curing chamber at 6000mJ / cm². 2 The material is cured by light energy for 3 minutes to obtain the main adhesive layer, which has a width of 1.8-2.0 mm and a thickness of 100 μm. A sealed cavity is formed between the main adhesive layer, the reflective conductive glass, and the transparent conductive glass.

[0716] 2. Add 35 wt% isocyanate prepolymer R1 is R2 is -CH2-CH2-CH2-CH2-CH2-CH2-, n is 50; 15 wt% diisocyanate HDI, 32 wt% siloxane-terminated polysiloxane. R3 is a -Si-O-Si- repeating unit, repeated 20 times; R4 is an ethyl group; 18 wt% amino-containing silane coupling agent. Stir and mix thoroughly to obtain the second adhesive, which is then vacuum-sealed and stored for later use. Apply the second adhesive to the outer periphery of the main adhesive layer (i.e., the side of the main adhesive layer away from the sealed cavity) using a dotting and brushing method, completely enclosing it inside, leaving the opening from step 1. After application, place it in an environment with 70% humidity and 30°C for two hours to obtain a moisture-cured layer with a thickness of 100μm.

[0717] 3. Brush perfluorocycloether containing 5 wt% of perfluorooctyltrimethoxysilane on the periphery of the moisture-cured layer (i.e. the side surface of the moisture-cured layer away from the sealed cavity) and completely surround the inside, leaving the opening of step 1, and then place in an oven at 120 °C for 30 min to obtain a hydrophobic layer with a thickness of 50 nm.

[0718] 4. Electrode attachment, silver paste coating, and 120 °C, 60 min thermal curing of the silver paste are performed on the cured box. The functional electrochromic liquid (same as in Example 1-2) is injected into the box by negative pressure, and the opening is sealed by dispensing to obtain an electrochromic device.

[0719] Example 4-2

[0720] 1. Stir and mix 10 wt% of bisphenol A type epoxy resin, 10 wt% of bisphenol F type epoxy resin, 30 wt% of resorcinol diglycidyl ether, 30 wt% of tetraepoxy cyclohexylethyl 2,4,6,8-tetramethylcyclotetrasiloxane, 18 wt% of silica inorganic filler, 1 wt% of cationic initiator (diaryl iodonium salt), and 1 wt% of photoinitiator (benzotriazole) to obtain a first adhesive. The first adhesive is coated along the edge of the reflective conductive glass (thickness of 1.6 mm) using an automatic dispensing machine, leaving an opening of about 1.5 mm at the short edge. The transparent conductive glass is positioned above the reflective conductive glass with the aid of a jig, and then placed in a UV curing box for 6000 mJ / cm2light energy curing for 3 min to obtain a main adhesive layer with a width of 1.8-2.0 mm and a thickness of 100 μm. A sealed cavity is formed between the main adhesive layer, the reflective conductive glass, and the transparent conductive glass. 2

[0721] 2. Stir and mix 20 wt% of isocyanate prepolymer R1 is R2 is -CH2-CH2-CH2-CH2-, n is 50; 30 wt% of diisocyanate IPDI, 20 wt% of siloxane-terminated polysiloxane R3 is -Si-O-Si- repeating unit, with a repetition number of 30, and R4 is ethyl; 30 wt% of amino-containing silane coupling agent Stir and mix to obtain a second adhesive, which is stored in a vacuum-sealed container for later use. The second adhesive is coated on the periphery of the main adhesive layer (i.e. the side surface of the main adhesive layer away from the sealed cavity) and completely surrounds the inside using a dispensing coating method, leaving the opening of step 1. After coating, it is placed in an environment of 70% humidity and 40 °C for two hours to obtain a moisture-cured layer with a thickness of 100 μm.

[0722] ​3. Apply a perfluorocyclic ether containing 5 wt% heptadecafluorodecyltriethoxysilane to the periphery of the moisture-cured layer (i.e., the surface of the moisture-cured layer away from the sealed cavity) and completely enclose it inside, leaving the opening from step 1. After application, bake at 120°C for 30 minutes to obtain a hydrophobic layer with a thickness of 60 nm.

[0723] 4. The cured box is then fitted with electrodes and coated with silver paste. The silver paste is then heat-cured at 120°C for 60 minutes. The functional electrochromic liquid (same as in Examples 1-2) is injected into the box under negative pressure, and the opening is sealed with adhesive to obtain the electrochromic device.

[0724] Example 5-2

[0725] The difference from Examples 1-2 is that in step 1, the bisphenol A epoxy resin is replaced with bisphenol S type epoxy resin.

[0726] Example 6-2

[0727] The difference from Examples 1-2 is that in step 2, the... Replace with

[0728] Example 7-2

[0729] The difference from Examples 1-2 is that in step 2, the amino-containing silane coupling agent is replaced with vinyltriethoxysilane.

[0730] Example 8-2

[0731] The difference from Examples 1-2 is that in step 3, heptadecafluorodecyltriethoxysilane is replaced with decyltriethoxysilane.

[0732] Example 9-2

[0733] The difference from Examples 1-2 is that in step 1, the content of bisphenol A epoxy resin is 50 wt%, the content of bisphenol F epoxy resin is 10 wt%, and the content of resorcinol diglycidyl ether is 10 wt%.

[0734] Example 10-2

[0735] The difference from Examples 1-2 is that in step 2, the isocyanate prepolymer content is 10 wt% and the diisocyanate content is 40 wt%.

[0736] Example 11-2

[0737] The difference from Examples 1-2 is that in step 1, γ-glycidyl etheroxypropyltrimethoxysilane is not added, and the amount of silica inorganic filler added is 28 wt%.

[0738] Example 12-2

[0739] The difference from Example 1-2 is that in Step 2, no amino-containing silane coupling agent is added, the isocyanate prepolymer content is 40wt%, and the siloxyl-terminated polysiloxane is 45wt%.

[0740] Example 13-2

[0741] The difference from Example 1-2 is that in Step 3, heptadecafluorodecyltriethoxysilane is replaced by decyltriethoxysilane.

[0742] Example 14-2

[0743] The difference from Example 1-2 is that in Step 1, the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, and the resorcinol diglycidyl ether are all replaced by a bisphenol S type epoxy resin.

[0744] Comparative Example 1-2

[0745] The difference from Example 1-2 is that Steps 2 and 3 are not included.

[0746] Comparative Example 2-2

[0747] The difference from Example 1-2 is that Step 2 is not included.

[0748] Comparative Example 3-2

[0749] The difference from Example 1-2 is that Step 3 is not included.

[0750] Test Example

[0751] The electrochromic devices prepared in Examples 1-2 to 14-2 and Comparative Examples 1-2 to 3-2 were respectively tested, and the specific test method is as follows:

[0752] (1) High temperature boiling: the device is placed in a 90℃ water bath, timing is started, and the condition of the device in the water bath is observed. When bubbles appear on the lens, the device is considered to have failed, and the time is recorded.

[0753] (2) High temperature and high humidity: the device is placed in a constant temperature oven, the temperature is adjusted to 85℃, the humidity is adjusted to 90%, and the on-off cycle is carried out at 1.2V, wherein the on time is 30s and the off time is 30s. Timing is started when the first cycle starts to turn on, and the device is considered to have failed when bubbles appear on the lens, and the time is recorded.

[0754] The results are shown in Table 11. The stability and high-temperature and high-humidity resistance of the electrochromic device prepared in Examples 1-2 to 14-2 are better than those of Comparative Examples 1-2 to 3-2. In comparison with Comparative Examples 1-2 to 3-2, Example 1-2 contains a moisture curing layer and a hydrophobic layer. The moisture curing layer can strengthen cross-linking and curing in a moisture environment, thereby further enhancing the bonding strength. Water vapor condenses into water droplets on the hydrophobic layer and rolls off, reducing the penetration of water vapor. Thus, the sealing frame glue containing the three-layer structure can effectively improve the sealing, stability and high-temperature and high-humidity resistance of the electrochromic device.

[0755] Table 11

[0756] Example 1-3

[0757] 1. The ITO-coated anode glass and the Ag-coated second conductive layer of the cathode glass were washed with water, and then the water-washed glass was subjected to plasma cleaning using a plasma cleaning machine. The cleaning agent contained potassium hydroxide, and the pH value was 10. The conductive layer of the cleaned cathode glass had a Dk value of 34, and the conductive layer of the anode glass had a Dk value of 38.

[0758] 2. The adhesive liquid (9 parts of bisphenol A type epoxy resin, 10 parts of bisphenol F type epoxy resin, 30 parts of fumed silica, 1 part of 4,4'-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether, 38 parts of resorcinol diglycidyl ether, 5 parts of trioctyl trimellitate, 27.5 parts of talc, 0.1 parts of plastic balls with a diameter of 100 μm, 5 parts of γ-glycidyl ether propyltrimethoxysilane, 1.5 parts of diphenyl iodonium hexafluoroantimonate, and 3 parts of 4-chlorobenzophenone, with a viscosity of 60,000 mpa·s, a thixotropic index of 3, and a curing shrinkage of 1%) was uniformly dispensed on the plasma-treated cathode glass to form an adhesive layer with a width of 2 mm and a thickness of 100 μm, and a liquid filling port was reserved. The cathode glass was turned over with the adhesive layer facing down, and the ITO-coated film of the anode glass was smoothly attached to the Ag-coated film of the cathode glass. LED lamp curing was performed with a total curing energy of 7,000 mJ / cm 2 , and then heated at 120°C for 2 h to form the sealing frame glue.

[0759] 3. After filling the electrochromic electrolyte solution (the electrochromic solution contains 50 mmol / L of anodic color material 5,10-dimethylphenazine, 50 mmol / L of cathodic color material 1,1'-dihexyl-4,4'-bipyridinium tetrafluoroborate, 50 mmol / L of electrolyte lithium tetrafluoroborate, and 5% wt of polymethyl methacrylate in propylene carbonate) into the filling port, the UV sealant is used for sealing. An electrode sheet is connected to each of the long sides of the anode glass and the cathode glass, respectively, and the conductive silver paste is used for electrically connecting the electrode sheet to the ITO and Ag, respectively, and the conductive silver paste covers 90% of the long side, to obtain an electrochromic device (25 cm long and 6.5 mm wide).

[0760] The differences between Examples 2-3 to 21-3 and Comparative Examples 1-3 to 2-3 and Example 1-3 are shown in Table 12, wherein the viscosity and thixotropic index of the adhesive liquid are adjusted by adjusting the addition amount of fumed silica in the adhesive liquid; the curing energy of the adhesive liquid is adjusted by adjusting the addition amount of initiator diphenyl iodonium hexafluoroantimonate and 4-chlorobenzophenone; and the dawes value of the conductive layer is adjusted by adjusting the addition amount of potassium hydroxide in the cleaning agent, so as to adjust the pH value of the cleaning agent. The thixotropic index, curing energy and dawes value are tested in the following manner:

[0761] Thixotropic index: tested by a thixotropic index tester.

[0762] Dawes value: tested by a dawes pen.

[0763] Curing energy: tested by a UV energy meter and obtained based on power and time calculation.

[0764] Test Example 1-3

[0765] 1. The devices of Examples 1-3 to 21-3 and Comparative Examples 1-3 to 2-3, which are not filled with the electrochromic electrolyte solution prepared in step 2, are disassembled, and the frame sealant structure on the surface of the cathode glass and the anode glass is observed, and the X value and the Y value are respectively determined by a metallographic microscope, wherein X is the extension length of the casting part connected to the anode glass, and Y is the extension length of the casting part connected to the cathode glass.

[0766] 2. The color difference phenomenon, color change uniformity and time for returning to the initial state after power-off of the electrochromic devices of Examples 1-3 to 21-3 and Comparative Examples 1-3 to 2-3 are respectively tested in the following manner:

[0767] (1) The electrochromic device is connected to a 1.2V direct current, and the power is turned off after 30 seconds, 1 hour, 3 hours and 8 hours of continuous power supply. The width A of the color residue strip appearing on the edge of the frame glue after power-off is measured by a micrometer. A < 0.1 cm indicates no abnormal color; 0.1 cm ≤ A < 0.5 cm indicates slight abnormal color; 0.5 cm ≤ A < 1 cm indicates obvious abnormal color; and A ≥ 1 cm indicates serious abnormal color.

[0768] (2) The time for the color change to recover to the initial state after 1 hour of power-on and power-off is recorded.

[0769] All test results are shown in Table 12. It can be seen that, in Comparative Examples 1-3 and Comparative Example 2-3, due to the absolute value of the difference between X and Y being too high, the electrochromic device showed serious abnormal color after 1 hour of power-off. The electrochromic devices of Examples 1-3 to 21-3 did not show serious abnormal color after 1 hour of power-off, and could recover to the initial state in a short time.

[0770] Table 12

[0771] Example 22-3

[0772] This example provides a sulfonate modified polyacrylate, and the specific preparation method is as follows:

[0773] Take 0.5 mol of sodium allyl sulfonate (CAS No. 2495-39-8) and 0.5 mol of cetyltrimethylammonium bromide (CTAB) into a reaction container, add 200 mL of acetonitrile, and stir at 60°C for 2 h. Filter the reaction product, remove the acetonitrile from the obtained filtrate under reduced pressure at 40°C, seal and cool to crystallize to obtain cetyltrimethylammonium allyl sulfonate monomer.

[0774] Add methyl methacrylate, cetyltrimethylammonium allyl sulfonate, and methyl allyl sulfonate into a reaction container to form a mixture with a molar ratio of methyl methacrylate (CAS No. 80-62-6), cetyltrimethylammonium allyl sulfonate, and methyl allyl sulfonate of 1:0.01:0.001; then add 1000 mL of propylene carbonate (CAS No. 108-32-7) to remove water and oxygen, and after fully dissolving, add 0.001 mol of azobisisobutyronitrile (CAS No. 78-67-1) as a free radical polymerization initiator, and heat to 80°C for stirring reaction for 12 h.

[0775] After cooling to room temperature, add anhydrous ethanol to the reaction product to precipitate solid product, and then wash the unreacted monomer, residual initiator and reaction solvent with acetonitrile. The precipitated polyelectrolyte solid is dried under reduced pressure in a vacuum drying oven at 70°C for 24 h.

[0776] Polyelectrolyte infrared spectrum analysis results: 1060 cm -1 (S=O double bond), 1245 cm -1 (S=O double bond), 1720 cm -1 (C=O double bond).

[0777] The structure of ammonium hexadecyl trimethyl methacrylate sulfonate is as follows:

[0778] The structure of methyl acrylate sulfonate is as follows:

[0779] Example 23-3

[0780] This example provides a sulfonate modified polyacrylate, and the specific preparation method is as shown in Example 22-3, with the difference being that:

[0781] The molar ratio of methyl methacrylate, ammonium hexadecyl trimethyl methacrylate sulfonate, and methyl acrylate sulfonate is 1:0.001:0.001.

[0782] Polyelectrolyte infrared spectrum analysis results: 1058 cm -1 (S=O double bond), 1246 cm -1 (S=O double bond), 1723 cm -1 (C=O double bond).

[0783] Example 24-3

[0784] This example provides a sulfonate modified polyacrylate, and the specific preparation method is as shown in Example 22-3, with the difference being that:

[0785] The molar ratio of methyl methacrylate, ammonium hexadecyl trimethyl methacrylate sulfonate, and methyl acrylate sulfonate is 1:0.05:0.001.

[0786] Polyelectrolyte infrared spectrum analysis results: 1051 cm -1 (S=O double bond), 1249 cm -1 (S=O double bond), 1731 cm -1 (C=O double bond).

[0787] Example 25-3

[0788] This example provides a sulfonate modified polyacrylate, and the specific preparation method is as shown in Example 22-3, with the difference being that:

[0789] The molar ratio of methyl methacrylate, ammonium hexadecyl trimethyl methacrylate sulfonate, and methyl acrylate sulfonate is 1:0.1:0.001.

[0790] Polyelectrolyte IR spectrum analysis results: 1056 cm -1 (S=O double bond), 1243 cm -1 (S=O double bond), 1726 cm -1 (C=O double bond).

[0791] Example 26-3

[0792] This example provides a sulfonate-modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0793] The molar ratio of methyl methacrylate, ammonium hexadecyl trimethyl methacrylate sulfonate and methyl acrylate sulfonate is 1:0.5:0.001.

[0794] Polyelectrolyte IR spectrum analysis results: 1058 cm -1 (S=O double bond), 1245 cm -1 (S=O double bond), 1720 cm -1 (C=O double bond).

[0795] Example 27-3

[0796] This example provides a sulfonate-modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0797] The molar ratio of methyl methacrylate, ammonium hexadecyl trimethyl methacrylate sulfonate and methyl acrylate sulfonate is 1:0.01:0.01.

[0798] Polyelectrolyte IR spectrum analysis results: 1056 cm -1 (S=O double bond), 1242 cm -1 (S=O double bond), 1730 cm -1 (C=O double bond).

[0799] Example 28-3

[0800] This example provides a sulfonate-modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0801] The addition amount of azobisisobutyronitrile is replaced by 0.005 mol.

[0802] Polyelectrolyte IR spectrum analysis results: 1058 cm -1 (S=O double bond), 1246 cm -1 (S=O double bond), 1723 cm -1 (C=O double bond).

[0803] Example 29-3

[0804] This example provides a sulfonate modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0805] The addition amount of azobisisobutyronitrile is replaced by 0.01 mol.

[0806] Polyelectrolyte infrared spectrum analysis results: 1058 cm -1 (S=O double bond), 1243 cm -1 (S=O double bond), 1725 cm -1 (C=O double bond).

[0807] Example 30-3

[0808] This example provides a sulfonate modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0809] The addition amount of azobisisobutyronitrile is replaced by 0.01 mol, and the temperature of the polymerization reaction is 100°C.

[0810] Polyelectrolyte infrared spectrum analysis results: 1056 cm -1 (S=O double bond), 1242 cm -1 (S=O double bond), 1726 cm -1 (C=O double bond).

[0811] Example 31-3

[0812] This example provides a sulfonate modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0813] The temperature of the polymerization reaction is 120°C.

[0814] Polyelectrolyte infrared spectrum analysis results: 1058 cm -1 (S=O double bond), 1243 cm -1 (S=O double bond), 1724 cm -1 (C=O double bond).

[0815] Example 32-3

[0816] This example provides a sulfonate modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0817] The temperature of the polymerization reaction is 120°C, and the reaction time is 18h.

[0818] Polyelectrolyte infrared spectrum analysis results: 1062 cm -1 (S=O double bond), 1248 cm -1 (S=O double bond), 1720 cm-1 (C=O double bond).

[0819] Example 33-3

[0820] This example provides a sulfonate modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0821] The hexadecyl trimethyl methacrylate sulfonic acid ammonium is replaced by hexadecyl trimethyl methacrylate sulfonic acid ammonium. The synthesis formula of hexadecyl trimethyl methacrylate sulfonic acid ammonium is shown in formula V:

[0822] Polyelectrolyte infrared spectrum analysis results: 1051 cm -1 (S=O double bond), 1240 cm -1 (S=O double bond), 1723 cm -1 (C=O double bond).

[0823] Example 34-3

[0824] This example provides a sulfonate modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0825] The hexadecyl trimethyl methacrylate sulfonic acid ammonium is replaced by hexadecyl trimethyl 4-styrene sulfonic acid ammonium. The synthesis formula of hexadecyl trimethyl 4-styrene sulfonic acid ammonium is shown in formula VI:

[0826] Polyelectrolyte infrared spectrum analysis results: 1070 cm -1 (S=O double bond), 1271 cm -1 (S=O double bond), 1745 cm -1 (C=O double bond).

[0827] Example 35-3This example provides a sulfonate modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0828] The propylene sulfonic acid methyl ester is replaced by methyl methacrylate sulfonic acid methyl ester, and the structure formula of methyl methacrylate sulfonic acid methyl ester is shown as follows:

[0829] Polyelectrolyte infrared spectrum analysis results: 1046 cm -1 (S=O double bond), 1232 cm -1 (S=O double bond), 1718 cm -1 (C=O double bond).

[0830] Example 36-3

[0831] This example provides a sulfonate-modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0832] Propyl sulfonate is replaced by 4-vinyl benzene sulfonate (CAS number is 16736-97-3).

[0833] Polyelectrolyte infrared spectrum analysis results: 1058cm -1 (S=O double bond), 1236cm -1 (S=O double bond), 1719cm -1 (C=O double bond).

[0834] Example 37-3

[0835] This example provides a sulfonate-modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0836] Methyl methacrylate is replaced by isobutyl methacrylate (CAS number is 97-86-9).

[0837] Polyelectrolyte infrared spectrum analysis results: 1062cm -1 (S=O double bond), 1240cm -1 (S=O double bond), 1723cm -1 (C=O double bond).

[0838] Example 38-3

[0839] This example provides a sulfonate-modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0840] Methyl methacrylate is replaced by hydroxyethyl methacrylate (CAS number is 868-77-9).

[0841] Polyelectrolyte infrared spectrum analysis results: 1060cm -1 (S=O double bond), 1241cm -1 (S=O double bond), 1719cm -1 (C=O double bond), 3442cm -1 (OH).

[0842] Example 39-3

[0843] This example provides a sulfonate-modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0844] Hexadecyl trimethyl methacrylate ammonium is replaced by tetraethyl methacrylate ammonium (CAS number is 733-44-8).

[0845] Polyelectrolyte infrared spectrum analysis results: 1060 cm -1 (S=O double bond), 1241 cm -1 (S=O double bond), 1726 cm -1 (C=O double bond).

[0846] Example 40-3

[0847] This example provides a sulfonate modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0848] Hexadecyl trimethyl ammonium methacrylate sulfonate is replaced by triethyl methacrylate sulfonate (CAS No. 3637-26-1), which is obtained by heating methacrylate sulfonate and triethylamine at 80°C.

[0849] Polyelectrolyte infrared spectrum analysis results: 1063 cm -1 (S=O double bond), 1242 cm -1 (S=O double bond), 1728 cm -1 (C=O double bond).

[0850] Example 41-3

[0851] This example provides a sulfonate modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0852] Hexadecyl trimethyl ammonium methacrylate sulfonate is replaced by dodecyl trimethyl ammonium methacrylate sulfonate, and the structural formula of dodecyl trimethyl ammonium methacrylate sulfonate is:

[0853] Polyelectrolyte infrared spectrum analysis results: 1060 cm -1 (S=O double bond), 1245 cm -1 (S=O double bond), 1720 cm -1 (C=O double bond).

[0854] Example 42-3

[0855] This example provides a sulfonate modified polyacrylate, the specific preparation method is shown in Example 22-3, the difference is that:

[0856] Hexadecyl trimethyl ammonium methacrylate sulfonate is replaced by triethyl methacrylate sulfonate, which is obtained by heating methacrylate sulfonate and triethylamine at 60°C, which needs to be carried out in a glove box or under nitrogen protection.

[0857] Among them, the synthesis formula of triethyl methacrylate sulfonate is shown in formula VII:

[0858] Polyelectrolyte infrared spectrum analysis results: 1066 cm -1 (S=O double bond), 1260 cm -1 (S=O double bond), 1724 cm -1 (C=O double bond).

[0859] Molecular weight test:

[0860] The molecular weight of the polymers prepared in Example 22-3 to Example 42-3, Comparative Example 3-3 and Comparative Example 4-3 was detected by gel permeation chromatography, and the detection results are shown in Table 13.

[0861] Comparative Example 3-3

[0862] The polymer provided in this comparative example is PMMA (Polymethyl Methacrylate, abbreviated as PMMA).

[0863] Comparative Example 4-3

[0864] The structural formula of the polymer provided in this comparative example is shown in Table 13.

[0865] Example 43-3

[0866] This example provides an electrochromic electrolyte, and the specific preparation method is as shown below:

[0867] In the glove box, the polymers prepared in Example 22-3 to Example 31-3, Example 33-3 to Example 42-3, Comparative Example 3-3 and Comparative Example 4-3 were respectively dissolved in propylene carbonate solvent without water and oxygen, diluted to 5wt%, 1,1'-dihexyl-4,4'-bipyridine tetrafluoroborate (35mmol / L) and 5,10-dihydrodimethylphenazine (35mmol / L, CAS number 15546-75-5) were added to prepare an electrochromic electrolyte. The structural formula of 1,1'-dihexyl-4,4'-bipyridine tetrafluoroborate is as shown below:

[0868] Example 45-3

[0869] This example provides an electrochromic electrolyte, and the specific preparation method is as shown in Example 43-3, the difference is that the polymer prepared in Example 11-3 is dissolved in propylene carbonate solvent without water and oxygen, and diluted to 2.5wt%.

[0870] Example 46-3 This example provides an electrochromic device, and the specific preparation method is as shown below:

[0871] The electrolytes prepared in Examples 43-3 and 44-3 were poured into electrochromic devices and sealed with UV adhesive. The electrochromic devices were 25 cm x 10 cm in size, and the sheet resistance of the transparent ITO coating was 16 Ω / cm. 2 The sheet resistance of the reflective conductive layer is 2Ω / cm 2 The edges of the electrochromic device were connected by conductive silver paste to obtain a large-size electrochromic device. The electrochromic devices obtained from the polymers prepared in Examples 22-3-43-3, Comparative Examples 3-3 and 4-3 were named 1#, 2#, 3#, 4#, 5#, 6#, 7#, 8#, 9#, 10#, 11#, 12#, 13#, 14#, 15#, 16#, 17#, 18#, 19#, 20#, 21#, D1#, and D2#, respectively.

[0872] Performance testing

[0873] 1. Testing methods.

[0874] (1) Connect the electrochromic device to the electrochemical workstation and use 1.2V DC for testing, recording the current changes. The detection results for sample 1# are shown in Figure 6. Among them, 0~8000s is the current stabilization stage (i.e., stage one), indicating that the electrophoretic phenomenon of the device is effectively suppressed and the current remains stable; 8000s~30000s

[0875] During the stage of continuous current increase (i.e., stage two), the electrophoretic phenomenon begins to appear. The internal anode and cathode color-changing materials move towards the two electrodes, the current increases, and it tends to stabilize after 30,000s.

[0876] (2) The aggregation degree evaluation method in patent CN103045228A is adopted. The aggregation degree near the electrode lead is equal to the aggregation length / electrode length × 100%. The larger the aggregation degree value, the greater the migration rate of the electrochromic material in the non-uniform electric field.

[0877] 2. Test results.

[0878] Table 13 Performance test results of electrochromic devices

[0879] Note: In the molecular structure formula corresponding to sample 16#, "i" represents isobutyl.

[0880] The above test results show that after adding sulfonate modified polyacrylate polymer electrolyte, the anti-delamination effect of the electrochromic device can last for more than 8000s, and the color change aggregation degree is ≤5.6% in 12h. Example 26-3 shows that the higher the proportion of sulfonate in the polymer, the better the anti-delamination effect. Example 31-3 shows that the larger the molecular weight of the polymer electrolyte, the better the anti-delamination effect. Comparative Example 3-3 and Comparative Example 4-3 show that the anti-delamination effect of adding non-ionic polyelectrolyte and carboxylate polyelectrolyte in large-size electrochromic devices is significantly lower than that of adding sulfonate modified polyacrylate polymer electrolyte in electrochromic devices.

[0881] The current-time curve adopted by the embodiments of the present disclosure can better analyze the delamination phenomenon of the device, has higher accuracy, and has better repeatability.

[0882] Example 47-3

[0883] 1 Provide ITO light-transmitting conductive coated glass (one side containing an insulating coating) and Ag reflective conductive coated glass, clean the reflective conductive coated glass, and use laser engraving to form the patterned structure, center part, spacing area and edge part of the present disclosure on the reflective conductive coated surface (as shown in FIGS. 7 and 11). The width of the edge part and the spacing area is 0.12mm and 2.88mm respectively, the total width is 3mm, and the resistance of the edge part is 9Ω. The first through-hole on the patterned structure has a hole diameter of 1.8mm, and the shortest distance from the edge of the first through-hole to the side of the patterned structure away from the center part is 0.12mm. The width of the edge part and the spacing area accounts for 90% of the total width of the edge part, the spacing area, the first and second resistance regulating paths, and the resistance of the patterned structure is 9Ω. The resistance of the first resistance regulating path and the second resistance regulating path is 100Ω at both ends, the parallel resistance is 50Ω, the resistance difference is 0Ω, and the resistance of the electrochromic device is 37.5Ω.

[0884] 2 Apply (frame sealant composition: bisphenol A type epoxy resin (9 parts), bisphenol F type epoxy resin (10 parts), 4,4'-bis(hydroxyhexafluoroisopropyl) phenyl diglycidyl ether (1 part), resorcinol diglycidyl ether (38 parts), trioctyl trimellitate (5 parts), talc (27.5 parts), γ-glycidyl ether oxypropyl trimethoxysilane (5 parts), diphenyl iodonium hexafluoroantimonate (1.5 parts), 4-chlorobenzophenone (3 parts) and polystyrene microspheres with a diameter of 100μm (0.1 part)) on the coated surface of the light-transmitting conductive coated glass, the application width is 1.8mm, and a 2mm liquid filling port is reserved. After the reflective conductive coated glass treated in the previous step is attached to the coated surface, it is subjected to ultraviolet curing, and after complete curing, 1.0g of conductive silver paste is applied on the area covered with the edge part and the patterned structure, and it is subjected to heating and curing at 120℃ for 2h. The assembled empty box device is moved into a glove box filled with nitrogen.

[0885] 3. Prepare the electrochromic solution in a glove box, which contains 50 mmol / L of anodic electrochromic material 5,10-dimethylphenazine, 50 mmol / L of cathodic electrochromic material 1,1'-dihexyl-4,4'-bipyridinium tetrafluoroborate, 50 mmol / L of electrolyte lithium tetrafluoroborate, and 5% wt of a mixture of polymethyl methacrylate and propylene carbonate, and the purity of the above raw materials needs to be >98%.

[0886] 4. Inject the prepared electrochromic solution into the reserved liquid injection port of step 2 in a glove box, seal the liquid injection port with ultraviolet sealant, and ultraviolet cure.

[0887] 5. Prepare the electrode sheet

[0888] 5.1. Place the copper-silver plated metal sheet flat on the laser engraving machine stage, and use laser processing to process a mesh opening structure, with a hole diameter of 0.5 mm.

[0889] 5.2. Send the laser-engraved semi-finished product into the punch press for one-time punch forming to obtain a Z-shaped electrode sheet with a first bending angle and a second bending angle.

[0890] 5.3. Place the formed electrode sheet into a box-type plasma machine and clean it in an N2 atmosphere for 300 s using 80 W power to remove surface organic matter and enhance surface energy. The reason for this step is to enhance the surface activity of the electrode sheet through plasma, greatly improving the bonding strength of the electrode sheet and the frame sealant conductive coating in the subsequent process, and in addition, it helps the soldering tin to better wet the substrate when welding the circuit on the electrode sheet, improving the conductivity.

[0891] 5.4. Place the plasma-cleaned electrode sheet in the mold, and paste high-temperature-resistant double-sided tape on the bonding surface 810A and the bonding surface 830A.

[0892] The thickness of the Z-shaped electrode sheet is 50 μm, and its structure is shown in FIG. 15, wherein a1 is 20 mm, a2 is 10 mm, a3 is 10 mm, b1 is 15 mm, b2 is 1.6 mm (90% of the thickness of the reflective conductive coated glass), b3 is 1 mm, the first bending angle (first included angle) is 85°, and the second bending angle (second included angle) is 90°.

[0893] 6. Place the already pasted lens outer glass face down, find the position to be pasted with the electrode sheet, and paste the bonding surface 810A and the bonding surface 830A tightly against the back surface and the side surface of the glass substrate, respectively.

[0894] Examples 48-3 to 73-3 differ from Example 1-3 as shown in Table 14, wherein,

[0895] Example 62-3 differs from Example 47-3 in that the patterned structure, the first resistance regulating path and the second resistance regulating path are not engraved.

[0896] Example 63-3 differs from Example 47-3 in that the ac, bd micro-short circuit path is an open circuit.

[0897] Example 64-3 differs from Example 47-3 in that the bd micro-short circuit path is an open circuit.

[0898] Example 70-3 differs from Example 47-3 in that the second portion extends towards the electrochromic layer, i.e. the first included angle is 270°.

[0899] Example 71-3 differs from Example 47-3 in that the electrode sheet does not contain a meshed opening.

[0900] Example 72-3 differs from Example 47-3 in that the electrode sheet does not contain a third portion 830.

[0901] Example 73-3 differs from Example 47-3 in that the electrode sheet does not contain an adhesive.

[0902] Comparative Example 5-3

[0903] Example 47-3 differs in that in Step 1, the reflective conductive coated glass is cut to remove 3mm of conductive material from both ends, i.e. does not contain an edge portion, a first resistance regulating path, a second resistance regulating path and a patterned structure.

[0904] Table 14

[0905] Test Example

[0906] The performance of the electrochromic devices prepared in Examples 47-3 to 73-3 and Comparative Example 5-3 were tested, respectively, according to the following specific methods:

[0907] As shown in Figure 11, the resistance of ab (on the edge portion A), cd (on the patterned structure B) and ac, bd (micro-short circuit paths) were measured using a multimeter, respectively, and the parallel resistance of the first resistance regulating path ac and the second resistance regulating path bd was the theoretical calculation value; the resistance of the electrochromic device was the resistance measured by the multimeter after the resistance of the cathode and anode electrode sheets was stabilized.

[0908] The bleaching time, contrast ratio and color change uniformity of the left, middle and right regions of the device were detected, and the ultraviolet curing time of the sealing glue was detected, according to the following specific detection methods:

[0909] Fading time: The time required for the reflectance of the electrochromic device to increase from 10% to 65% at a wavelength of 550 nm after the device is powered on is recorded using a timer.

[0910] Contrast ratio: The display area of the electrochromic device is equally divided into left, middle and right regions along the length direction. After the device is powered on for 1 minute, any one of the three regions is randomly selected and the reflectance at this position is detected using a reflectance tester. The foregoing step is repeated 2 times, and each time a different region is selected as a parallel test. The contrast ratio is calculated by subtracting the low reflectance value after the device is powered on stably from the high reflectance value in the off state of the device, and the variance B of the contrast ratio is obtained. B≤1 indicates that the color change uniformity is excellent; B is greater than 1 and less than 20, indicating that the color change uniformity is medium; and B>20, indicating that the color change uniformity is poor.

[0911] Curing time of the frame sealant: The curing time P of the frame sealant is recorded using a timer, and the unit is min. P≤1 indicates “easy”; 1

[0912] The results are shown in Table 15. It can be seen that, compared with Comparative Example 5-3, the electrochromic devices of Examples 47-3 to 73-3 have faster fading speed, better color change uniformity, and more excellent overall performance.

[0913] Table 15

[0914] Test Example

[0915] 1. The convenience of use of different electrode sheets of Examples 47-3, 70-3 to 73-3 was tested, and the specific steps were as follows:

[0916] A random operator was selected on the production line to complete the installation of the electrode sheets of Examples 47-3, 70-3 to 73-3 according to the job standard, and the completion time of each group was timed using a stopwatch. The data was counted and summarized.

[0917] 2. The thickness (referred to as “cell thickness”) of the electrochromic layer at the installation position of different electrode sheets of Examples 47-3, 70-3 to 73-3 was tested, and the specific steps were as follows:

[0918] The cell thickness of the devices produced by the above process near the electrode sheet was checked using a height gauge, and the yield of 20 electrode sheets (100±10 μm of cell thickness was qualified) was calculated.

[0919] 3. Three electrode sheet samples were randomly selected from each of Examples 47-3, 70-3 to 73-3 for cold-heat cycle durability testing, and the specific steps were as follows:

[0920] The electrode sheet is placed in an environment with a temperature range of 85°C to -30°C, and is cycled in a manner that first maintains 85°C for 30 minutes, then reduces the temperature to -30°C for 30 minutes, and is cycled in this manner for 300 groups. The cycled electrode sheet is installed to prepare an electrochromic device. A digital multimeter is used to measure the resistance value of the silver paste surface at a distance of 30 mm from the cathode electrode sheet, and the average resistance value of each example is statistically summarized.

[0921] The electrode sheet is subjected to a tensile destructive test, and the specific steps are as follows: the lens is fixed using a jig, one end of the anode wiring is linked to a tensile tester, a tensile force is applied in a direction perpendicular to the lens surface until the electrode sheet falls off, the maximum tensile force at which the electrode sheet falls off is recorded, and the average value of the maximum tensile force of each group is statistically summarized.

[0922] In this test, if the resistance value is ≥1.2Ω and the tensile force is <10N, it is determined to be unqualified, in which case the device has high power consumption, there is a risk of poor contact, and cannot meet the use requirements.

[0923] The results are shown in Table 16, and it can be seen that, compared with Examples 70-3 to 73-3, the electrode sheet of Example 47-3 has faster installation speed, uniform box thickness, high yield, better conductive stability, and a more stable structure.

[0924] Table 16

[0925] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present disclosure. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, different embodiments or examples described in the present specification and the features of different embodiments or examples can be combined and combined by those skilled in the art without contradiction.

[0926] Although the embodiments of the present disclosure have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limiting the present disclosure, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present disclosure.

Claims

1. An electrochromic device, wherein, Comprise: A first conductive layer and a second conductive layer arranged in a stack; A sealant between and surrounding the first conductive layer and the second conductive layer to form a sealed cavity, the sealed cavity comprising an electrochromic material; The sealant comprises: A sealant body; A first flow portion on a side surface of the sealant body facing the sealed cavity and connected to the first conductive layer; A second flow portion on a side surface of the sealant body facing the sealed cavity and connected to the second conductive layer; In the direction of the sealed cavity, the extension length of the first flow portion is X, and the extension length of the second flow portion is Y, and the difference between X and Y is not more than 60μm.

2. The electrochromic device of claim 1, wherein, The difference between X and Y is not more than 20μm.

3. The electrochromic device of claim 1 or 2, wherein, At least one of the following conditions is met: The extension length of the first flow portion is 0.1μm-100μm; The extension length of the second flow portion is 0.1μm-100μm.

4. The electrochromic device according to any one of claims 1 to 3, wherein, The distance between the first conductive layer and the second conductive layer is 50μm-120μm.

5. The electrochromic device according to any one of claims 1 to 4, wherein, The material forming the sealant comprises a viscous liquid, which satisfies at least one of the following conditions: The viscosity of the viscous liquid is 10000mpa·s-150000mpa·s; The thixotropic index of the viscous liquid is 1-8; The adhesive liquid has a curing energy of 1000 mj / cm 2 ~ 10000 mj / cm 2 ; The viscous liquid contains gap balls, and the thickness of the gap balls is 50μm-120μm.

6. The electrochromic device according to any one of claims 1 to 5, wherein, The material forming the sealant comprises a viscous liquid, which satisfies at least one of the following conditions: The viscosity of the viscous liquid is 30000mpa·s-80000mpa·s; The thixotropic index of the viscous liquid is 3-6; The adhesive liquid has a curing energy of 5000 mj / cm 2 ~ 100000 mj / cm 2 .

7. The electrochromic device of claim 5, wherein, The material of the gap balls comprises at least one of glass, ceramic, calcium barium, polystyrene, polymethyl methacrylate, and talc.

8. The electrochromic device according to any one of claims 1 to 7, wherein, The first conductive layer is electrically connected to a positive electrode tab, and the second conductive layer is electrically connected to a negative electrode tab; The dyne value of the first conductive layer is A, and the dyne value of the second conductive layer is B, and A and B satisfy at least one of the following conditions: A-B is -30-30; A is 30-60; B is 30-60.

9. The electrochromic device of claim 8, wherein, A-B is -2-18; Or, A-B is 4-10.

10. The electrochromic device according to any one of claims 1 to 9, wherein, The sealed cavity comprises at least two electrochromic materials.

11. The electrochromic device of claim 1, wherein, The sealed cavity comprises an electrochromic liquid, and the water content and oxygen content of the electrochromic liquid are not more than 15ppm.

12. The electrochromic device of claim 11, wherein, The electrochromic liquid does not contain an antioxidant and a water removal agent.

13. The electrochromic device of claim 11 or 12, wherein, The electrochromic liquid comprises an anodic color-changing material, a cathodic color-changing material, an electrolyte, and a solvent.

14. The electrochromic device of claim 13, wherein, Further comprising: an oxide of the anodic color-changing material and a hydrate of the cathodic color-changing material, and at least one of the following conditions is met: The content of the oxide of the anodic color-changing material is not more than 50ppm; The content of the hydrate of the cathodic color-changing material is not more than 50ppm.

15. The electrochromic device of claim 14, wherein, At least one of the following conditions is met: The content of the oxide of the anodic color-changing material is not more than 10ppm; The content of the hydrate of the cathodic color-changing material is not more than 10ppm.

16. The electrochromic device according to any one of claims 13 to 15, wherein, At least one of the following conditions is met: The anodic color-changing material comprises at least one of nickel oxide, iridium oxide, phenazine compound, polyaniline, polypyrrole, Prussian blue, thiophene compound, phthalocyanine compound, tungsten trioxide, molybdenum trioxide, phenothiazine compound, methylene blue, viologen, methyl viologen, ethyl viologen, phenyl viologen, and propyl viologen; The cathodic color-changing material comprises at least one of tungsten trioxide, molybdenum trioxide, phenylenediamine, nickel oxide, manganese dioxide, iridium oxide, polyaniline, Prussian blue, polypyrrole, manganese dioxide, methyl viologen, ethyl viologen, phenyl viologen, propyl viologen, 1,1'-disubstituted-4,4'-bipyridine, and 1,1'-diheptyl-4,4'-bipyridine tetrafluoroborate; The electrolyte comprises one or more of tetrabutylammonium bromide, tetrabutylammonium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis-trifluoromethylsulfonylimide, polyethylene oxide, polypropylene oxide, and polymethyl methacrylate; The solvent comprises at least one of propylene carbonate, toluene, xylene, butyrolactone, 2-acetylbutyrolactone, gamma-valerolactone, ethylene carbonate, propylene carbonate, sulfolane, 3-methylsulfolane, dimethylacetamide, dimethylformamide, acetonitrile, glutaronitrile, 2-methylglutaronitrile, 3-hydroxypropionitrile, tetraethylene glycol dimethyl ether, dimethyl sulfoxide, ethoxyethanol, and cyclopentanone.

17. The electrochromic device according to any one of claims 1 to 16, wherein, The first conductive layer is provided with a first substrate on a side away from the second conductive layer; The second conductive layer is provided with a second substrate on a side away from the first conductive layer.

18. A method for preparing the electrochromic device of any one of claims 1-17, comprising: applying the sealant between the first conductive layer and the second conductive layer to form a closed cavity with the sealant surrounding the first conductive layer and the second conductive layer; filling the closed cavity with an electrolyte containing the electrochromic material, and resealing the closed cavity to obtain the electrochromic device.

19. The method of claim 18, wherein, The applying of the sealant between the first conductive layer and the second conductive layer comprises: applying an adhesive liquid on a first surface of the first conductive layer to form an adhesive layer, and reserving a filling opening on the adhesive layer; turning over the first conductive layer with the first surface facing downward, adhering the second conductive layer to the side of the first conductive layer provided with the adhesive layer, and performing a curing treatment to form the sealant surrounding the first conductive layer and the second conductive layer.

20. The method of claim 19, wherein, The curing treatment comprises normal temperature curing treatment, ultraviolet light curing treatment, or ultraviolet and heat double curing treatment.

21. The method of any one of claims 18-20, wherein, The first conductive layer and the second conductive layer are subjected to a cleaning treatment before the sealant is applied between the first conductive layer and the second conductive layer.

22. An electronic device, comprising: The electrochromic device of any one of claims 1-17.

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