A potting and encapsulation method for electrochromic devices and its application

Abstract

This disclosure relates to the field of electrochromic technology, specifically providing a potting and encapsulation method for electrochromic devices and its application. The potting and encapsulation method includes the following steps: preparing an electrochromic solution or preparing a gel film containing an electrochromic material; forming a frame on the upward-facing surface of a first transparent substrate under vacuum; then introducing the electrochromic solution or the gel film containing the electrochromic material into the area enclosed by the frame and the first transparent substrate; next, bonding a second transparent substrate to the upward-facing surface of the frame and curing the frame; finally, releasing the vacuum to obtain the electrochromic device.

Description

Technical Field

[0001] This disclosure relates to the field of electrochromic technology, and in particular to a potting and encapsulation method for electrochromic devices and its application. Background Technology

[0002] Under the influence of an external voltage, the anti-glare rearview mirror can controllably and reversibly change its reflectivity to reduce the reflected light from strong glare behind the vehicle, thereby ensuring driving safety. The structure of the anti-glare rearview mirror includes two pieces of conductive glass, one transparent conductive glass and the other mirror-like conductive glass, with an electrochromic material sandwiched in between. The two pieces of conductive glass and the electrochromic material are bonded together by frame adhesive.

[0003] Chinese patent document CN115755482A discloses a liquid filling process for an electrochromic anti-glare rearview mirror. The liquid filling process first uses a plastic frame to set two conductive glass pieces with their conductive surfaces facing each other, then glues them together and leaves a liquid injection port to prepare a semi-finished anti-glare rearview mirror chamber; then the chamber is placed in a vacuum chamber, and the chamber is filled with electrochromic solution by vacuum suction; finally, the chamber is sealed to obtain the finished product.

[0004] However, the electrochromic material encapsulated within anti-glare rearview mirrors is typically sensitive to water and oxygen. Transferring it to a vacuum chamber for liquid aspiration exposes it directly to air, reducing material stability. In practical use, this manifests as a tendency for the mirror surface to yellow in its faded (high reflectivity) state, and the appearance of defects or residual fading. Furthermore, the sealing process requires wiping away the electrochromic material at the injection port. Even a small amount of residual material can affect the sealing effect, thus reducing device stability. Additionally, the injection port is too narrow, making fully automated sealing difficult and significantly limiting production efficiency. Summary of the Invention

[0005] This disclosure provides a potting and encapsulation method for electrochromic devices and its application, in order to address the shortcomings of related technologies.

[0006] According to a first aspect of the present disclosure, a potting and encapsulation method for an electrochromic device is provided, the potting and encapsulation method comprising the following steps:

[0007] Step 1: Prepare an electrochromic solution or prepare a gel membrane containing an electrochromic material;

[0008] Step 2: Provide a first transparent substrate, place the first transparent substrate in a vacuum environment, and form a frame on the upward-facing surface of the first transparent substrate; or, provide a first transparent substrate, form a frame on the upward-facing surface of the first transparent substrate, and then place the first transparent substrate in a vacuum environment; wherein, the upward-facing surface of the first transparent substrate is the surface on which a conductive layer is disposed;

[0009] Step 3: Add the electrochromic solution to the area enclosed by the frame and the first transparent substrate; or lay the gel film containing the electrochromic material in the area enclosed by the frame and the first transparent substrate.

[0010] Step 4: Adhere the conductive side of the second transparent substrate downwards to the upward-facing surface of the first transparent substrate, and cure the adhesive frame;

[0011] Step 5: Release the vacuum to obtain the electrochromic device.

[0012] In one aspect of this disclosure, the electrochromic device is an electrochromic anti-glare rearview mirror.

[0013] In one aspect of this disclosure, a potting and encapsulation method for an electrochromic device is provided, the potting and encapsulation method comprising the following steps:

[0014] Step 1: Prepare the electrochromic solution;

[0015] Step 2: Provide a first transparent substrate, place the first transparent substrate in a vacuum environment, and form a frame on the upward-facing surface of the first transparent substrate; wherein, the upward-facing surface of the first transparent substrate is the surface on which a conductive layer is disposed;

[0016] Step 3: Add the electrochromic solution to the area enclosed by the frame and the first transparent substrate;

[0017] Step 4: Attach the second transparent substrate to the surface of the adhesive frame facing upwards, and cure the adhesive frame;

[0018] Step 5: Release the vacuum to obtain the electrochromic device.

[0019] In one aspect of this disclosure, the electrochromic solution is prepared by the following steps:

[0020] The electrochromic material, the cathode electrochromic material, the electrolyte salt, and the organic solvent are mixed in an inert gas atmosphere to obtain the electrochromic solution.

[0021] In one aspect of this disclosure, the electrochromic solution further includes a polymer thickener and / or a gel precursor.

[0022] In one aspect of the embodiments of this disclosure, preferably, the electrochromic solution further includes a polymer thickener and a gel precursor.

[0023] In one aspect of this disclosure, the polymer tackifier is selected from at least one of polyvinyl alcohol and its derivatives, polyether compounds and their derivatives, polyurethane compounds and their derivatives, polyacrylate compounds and their derivatives, epoxy resin compounds and their derivatives, and phenolic resin compounds and their derivatives.

[0024] In one aspect of this disclosure, the gel precursor is selected from at least one of polyacrylonitrile, vinylidene fluoride hexafluoropropylene copolymer, polymethyl methacrylate, polyethylene oxide, polyurethane compounds, and epoxy resin compounds.

[0025] In one aspect of this disclosure, the anodic electrochromic material is selected from at least one of phenazine compounds and their derivatives, triphenylamine compounds and their derivatives, or phenothiazine compounds and their derivatives.

[0026] In one aspect of this disclosure, the cathode electrochromic material is selected from at least one of pyridine compounds and their derivatives, viologen compounds and their derivatives, polyaniline compounds and their derivatives, polypyrrole compounds and their derivatives, polythiophene compounds and their derivatives, polycarbazole compounds and their derivatives, polyfuran compounds and their derivatives, or polyfluorene compounds and their derivatives.

[0027] In one aspect of this disclosure, the electrolyte salt is selected from at least one of lithium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tributylmethylammonium bis(trifluoromethanesulfonyl)imide salt, tetrabutylammonium bis(trifluoromethanesulfonyl)imide salt, or bislithium(trifluoromethanesulfonyl)imide salt.

[0028] In one aspect of the embodiments of this disclosure, the organic solvent is selected from at least one of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl carbonate, propylene carbonate, γ-butyrolactone, or dimethyl sulfoxide.

[0029] In one aspect of this disclosure, the first transparent substrate includes a first conductive layer, and the second transparent substrate includes a second conductive layer; the first conductive layer and the second conductive layer are disposed opposite to each other.

[0030] In one aspect of this disclosure, the first conductive layer comprises at least one of the following metals: Ag, Fe, Sn, Ti, Pt, Al, Au, Mn, Cr, Pd, Rh, Ir, Os, or Ru.

[0031] In one aspect of the embodiments of this disclosure, the second conductive layer comprises at least one of indium tin oxide, fluorine-doped tin oxide, zinc aluminum oxide, silver nanowires, carbon nanotubes, graphene, or a metal mesh.

[0032] In one aspect of this disclosure, the adhesive frame contains rigid microparticles with a D90 particle size of a μm; the volume ratio of the rigid microparticles to the volume of the adhesive frame is b‰; the viscosity of the adhesive frame is η1 Pa·s, where a, b, and η1 satisfy the following relationship:

[0033] 10≤a≤500;2≤b≤200;0.1≤η1≤2000

[0034] Furthermore, η1×logb×log(0.1a)≥10.

[0035] In one aspect of this disclosure, the viscosity of the electrochromic solution is η² Pa·s, where a, b, η1, and η2 satisfy the following relationship:

[0036] 0.001≤η2≤20,

[0037] Furthermore, η2 2 / 2η1log(ab)≤0.1.

[0038] In one aspect of this disclosure, the material of the adhesive frame is selected from at least one of epoxy resin adhesive, polyurethane adhesive, and acrylic adhesive.

[0039] In one aspect of this disclosure, the volume fraction of the added electrochromic solution is selected from 95% to 110% based on the total volume of the area enclosed by the frame and the first transparent substrate.

[0040] In one aspect of this disclosure, the frame further includes brittle microparticles; the D90 particle size of the brittle microparticles is 1.01-1.2 times that of the D90 particle size of the rigid microparticles.

[0041] In one aspect of this disclosure, the volume of the brittle particles accounts for a percentage of the volume of the frame, which is c‰; the value of c ranges from 0.1b to b.

[0042] In one aspect of this disclosure, the brittle microparticles are selected from polystyrene particles.

[0043] In one aspect of this disclosure, the rigid microparticles are selected from silica particles; preferably, the rigid microparticles are selected from surface-hydroxylated silica nanoparticles.

[0044] In one aspect of the embodiments of this disclosure, the projections of the first transparent substrate and the second transparent substrate on the plane do not completely overlap.

[0045] In one aspect of this disclosure, the potting and encapsulation method includes the following steps:

[0046] Step 1: Prepare the electrochromic solution;

[0047] Step 2: Provide a first transparent substrate, the first transparent substrate including a first conductive layer, and deposit an anodic electrochromic material layer on the surface of the first conductive layer away from the first transparent substrate; place the first transparent substrate in a vacuum environment, and form a frame on the surface of the anodic electrochromic material layer facing upward; wherein, the surface of the first transparent substrate facing upward is the surface on which the conductive layer is disposed;

[0048] Step 3: Add the electrochromic solution to the area enclosed by the frame and the first transparent substrate;

[0049] Step 4: Provide a second transparent substrate, the second transparent substrate including a second conductive layer, deposit a cathodic electrochromic material layer on the surface of the second conductive layer away from the second transparent substrate, the cathodic electrochromic material layer being in contact with the electrochromic solution; attach the second transparent substrate to the frame-up surface, and cure the frame;

[0050] Step 5: Release the vacuum to obtain the electrochromic device.

[0051] In one aspect of this disclosure, the anodic electrochromic material layer and the cathode electrochromic material layer are each independently selected from at least one of transition metal oxides, transition metal oxides doped with other metals, transition metal complexes, or polymers with redox activity. Specifically, the anodic electrochromic material layer is selected from nickel oxide, and the cathode electrochromic material layer is selected from tungsten trioxide, but is not limited thereto.

[0052] According to a second aspect of the present disclosure, an electrochromic device is provided, which is prepared by any of the aforementioned potting and encapsulation methods.

[0053] The technical solutions provided by the embodiments of this disclosure may include the following beneficial effects:

[0054] As can be seen from the above embodiments, a highly stable electrochromic device can be obtained through the potting and encapsulation method provided in this disclosure, which can be mainly applied in the field of anti-glare rearview mirrors.

[0055] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and are not intended to limit this disclosure. Attached Figure Description

[0056] The accompanying drawings, which are incorporated in and form a part of this specification, illustrate embodiments consistent with this disclosure and, together with the description, serve to explain the principles of this disclosure.

[0057] Figure 1This is a flowchart illustrating a potting and encapsulation method according to an exemplary embodiment;

[0058] Figure 2 This is a structural diagram of an electrochromic device according to an exemplary embodiment; wherein, 1 is a substrate, 2 is a mirror conductive layer (first conductive layer), 3 is a transparent conductive layer (second conductive layer), 4 is a frame, 5 is an electrochromic layer, and 6 is a second substrate;

[0059] Figure 3 This is a structural diagram of an electrochromic device according to another exemplary embodiment; wherein, 7 is a gel film layer;

[0060] Figure 4 This is a structural diagram of an electrochromic device according to yet another exemplary embodiment; wherein 21 is an anode electrochromic material layer and 31 is a cathode electrochromic material layer;

[0061] Figure 5 This is a schematic diagram of a plurality of closed adhesive frames prepared according to an exemplary embodiment; wherein, 9 is a cutting line on transparent conductive glass and 10 is a cutting line on mirror conductive glass;

[0062] Figure 6 This is an interface image of the frame and the electrochromic layer according to an exemplary embodiment;

[0063] Figure 7 This is an interface image of the frame and the electrochromic layer according to another exemplary embodiment; wherein 45 is a defect at the interface;

[0064] Figure 8 This is an interface image of the frame and the electrochromic layer according to an exemplary embodiment;

[0065] Figure 9 This is an interface image of the frame and the electrochromic layer according to another exemplary embodiment; wherein 45 is a defect at the interface; Detailed Implementation

[0066] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of this application. The embodiments of this application should not be construed as limiting this application.

[0067] For the sake of brevity, this article only discloses a few specific numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0068] In this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0069] In this description, unless otherwise stated, "above" and "below" include the stated number.

[0070] Unless otherwise stated, the terms used in this disclosure have their common meanings as commonly understood by those skilled in the art. Unless otherwise stated, the values ​​of the parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (e.g., they can be tested according to the methods given in the embodiments of this disclosure).

[0071] The term "about" is used to describe and indicate small variations. When used in conjunction with an event or situation, the term may refer to examples in which the event or situation occurred precisely or in examples in which the event or situation occurred very approximately. For example, when used in conjunction with numerical values, the term may refer to a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, quantities, ratios, and other numerical values ​​are sometimes presented in range format herein. It should be understood that such range format is for convenience and brevity and should be interpreted flexibly to include not only numerical values ​​explicitly specified as range limits but also all individual numerical values ​​or subranges covered within the range, as if each numerical value and subrange were explicitly specified.

[0072] The list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another instance, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

[0073] This disclosure provides a potting and encapsulation method for an electrochromic device, such as... Figure 1 and Figure 2 As shown, the preparation process provided in this disclosure includes: forming a frame 4 on a substrate 1, then placing it in a vacuum environment, adding a pre-prepared electrochromic solution and dripping it into the frame, then pressing and UV curing, and finally releasing the vacuum to obtain an electrochromic device.

[0074] In another aspect of this disclosure, such as Figure 2 As shown, the preparation process provided in this disclosure may further include: first placing the substrate 1 in a vacuum environment, then forming a frame 4 on the substrate 1, adding a pre-prepared electrochromic solution and dripping it into the frame, then pressing and UV curing, and finally releasing the vacuum to obtain the electrochromic device.

[0075] In another aspect of this disclosure, such as Figure 3 As shown, the preparation process provided in this disclosure may further include: forming a gel frame 4 on a substrate 1, then placing it in a vacuum environment, laying a pre-prepared gel film containing electrochromic material into the gel frame, then pressing and UV curing, and finally releasing the vacuum to obtain an electrochromic device. The gel film containing electrochromic material can be bonded to the upward-facing surface of the substrate 1.

[0076] In another aspect of this disclosure, the preparation process provided may further include: first placing the substrate 1 in a vacuum environment, then forming a gel frame 4 on the substrate, laying a pre-prepared gel film containing electrochromic material into the gel frame, then pressing and UV curing, and finally releasing the vacuum to obtain the electrochromic device. The gel film containing electrochromic material can be bonded to the upward-facing surface of the substrate 1.

[0077] In this disclosure, such as Figure 2 and Figure 3As shown, the substrate 1 is a transparent substrate and includes a mirror conductive layer 2; the material of the mirror conductive layer 2 is selected from at least one of Ag, Fe, Sn, Ti, Pt, Al, Au, Mn, Cr, Pd, Rh, Ir, Os or Ru.

[0078] In this disclosure, such as Figure 2 and Figure 3 As shown, a second substrate 6 is used for lamination; the second substrate 6 is a transparent substrate and contains a transparent conductive layer 3; the material of the transparent conductive layer 3 is selected from at least one of indium tin oxide, fluorine-doped tin oxide, zinc aluminum oxide, silver nanowires, carbon nanotubes, graphene or metal mesh.

[0079] In this disclosure, the vacuum environment is achieved by evacuation, and the evacuation process includes, but is not limited to, achieving a vacuum level of 0.1-10000 mbar within 10-1000 s.

[0080] In this disclosure, such as Figure 2 As shown, the electrochromic solution forms an electrochromic material layer 5 after curing.

[0081] In this disclosure, such as Figure 3 As shown, a gel membrane containing electrochromic materials forms an electroactive gel membrane layer 7.

[0082] In this disclosure, the materials of substrate 1 and the second substrate 6 are selected from, but are not limited to, ITO conductive glass.

[0083] In this disclosure, such as Figure 4 As shown, the preparation process provided in this disclosure may further include: first forming a mirror conductive layer 2 and an anodic electrochromic material layer 21 on a substrate 1, and forming a transparent conductive layer 3 and a cathode electrochromic material layer 31 on a second substrate 6; placing the substrate 1 in a vacuum environment, then forming a frame 4 on the anodic electrochromic material layer 21, adding a pre-prepared electrochromic solution and dripping it into the frame, then pressing and UV curing, and finally releasing the vacuum to obtain an electrochromic device.

[0084] In this disclosure, the material of the frame needs to simultaneously meet the following requirements: good ability to isolate water and oxygen, as well as good thixotropic properties and shape retention; so that it will not collapse during the preparation process.

[0085] In this disclosure, rigid microparticles are added during the preparation of the frame. The role of these rigid microparticles is to improve the thixotropic properties and shape retention of the frame.

[0086] In one aspect of this disclosure, the D90 particle size of the rigid microparticles is 10-500 μm; preferably, the D90 particle size of the rigid microparticles is 50-250 μm; specifically, the D90 particle size of the rigid microparticles is 50 μm, 75 μm, 100 μm, 120 μm, 150 μm, 175 μm, 200 μm, 225 μm or 250 μm; but not limited thereto.

[0087] In one aspect of this disclosure, the volume ratio of rigid microparticles to the volume of the frame is 2-200‰; preferably, the volume ratio of rigid microparticles to the volume of the frame is 20-100‰; specifically, the volume ratio of rigid microparticles to the volume of the frame is 20‰, 25‰, 30‰, 35‰, 40‰, 45‰, 50‰, 55‰, 60‰, 65‰, 70‰, 75‰, 80‰, 85‰, 90‰, 95‰ or 100‰; but not limited thereto.

[0088] In one aspect of this disclosure, the viscosity of the adhesive frame is 0.1-2000 Pa·s; preferably, the viscosity of the adhesive frame is 25-150 Pa·s.

[0089] In one aspect of this disclosure, the rigid microparticles are surface-modified silica nanoparticles, wherein the surface modification is selected from surface hydroxylation modification, surface amination modification, or surface carboxylation modification.

[0090] In one aspect of this disclosure, preferably, the rigid microparticles are surface-hydroxylated modified silica nanoparticles with a D90 particle size of 50-250 μm.

[0091] In one aspect of this disclosure, surface-hydroxylated modified silica nanoparticles are obtained through the following steps:

[0092] Silica nanoparticles with a D90 particle size of 50-250 μm are provided. After washing and drying, the silica nanoparticles are heated to 400℃-550℃ and held for 20-50 min to remove residual organic pollutants and adsorbed moisture on the surface of the silica nanoparticles. Subsequently, the silica sample is subjected to electro-induced hydroxylation treatment: the silica surface is electro-induced by direct current to break the Si-O-Si bonds and combine with H+ and OH- in the water, thereby effectively increasing the hydroxyl groups on the silica surface and obtaining surface-hydroxylated modified silica nanoparticles.

[0093] In one aspect of this disclosure, surface-alkylated modified silica nanoparticles are obtained through the following steps:

[0094] The surface-hydroxylated modified silica nanoparticles were placed in a silane coupling agent reaction solution containing coupling agent KH560, benzene and methanol, and subjected to shaking treatment and isothermal alkylation reaction in sequence. After the reaction was completed, surface-alkylated modified silica nanoparticles were obtained.

[0095] In one aspect of this disclosure, in the electrically excited hydroxylation treatment, the voltage is 1.5-1.7 V / cm, and the electrolyte is a magnesium chloride solution with a mass fraction of 0.025%-0.030% or a calcium chloride solution with a mass fraction of 0.025%-0.030%.

[0096] In one aspect of this disclosure, during the lamination process, a contact area is reserved in the region where the projections of the upper and lower substrates 1 and the second substrate 6 do not completely overlap. During lamination, the pressure should be distributed as evenly as possible along the entire adhesive line to ensure that the adhesive is pressed down completely.

[0097] In one aspect of this disclosure, the curing process includes curing the frame adhesive by irradiating it with a UV lamp.

[0098] In one aspect of this disclosure, curing should be carried out while the pressure is not removed during the curing process.

[0099] In one aspect of this disclosure, the change in the particle size of rigid particles requires a corresponding change in the volume fraction of rigid particles and the viscosity of the adhesive frame, and the rate of change is affected by the particle size range of the rigid particles. Specifically, η1×logb×log(0.1a) should be greater than or equal to 10. If the above conditions are not met, the accuracy and uniformity of the adhesive frame thickness will decrease, which will lead to a decrease in device performance or uneven internal potential distribution, thereby affecting the device's performance and service life.

[0100] In one aspect of this disclosure, the viscosity of the electrochromic solution precursor, the viscosity of the frame, the particle size of the rigid particles, and the volume fraction of the rigid particles should be mutually compatible; specifically, η2 2 / 2η1log(ab) should be less than or equal to 0.1. If the above conditions are not met, the interface defects of the frame / electrochromic precursor solution are more likely to occur, which will lead to local accelerated aging and affect the stability of the entire device.

[0101] In one aspect of this disclosure, the frame also contains brittle microparticles. During the pressing process, the frame thickness first reaches the diameter of the brittle microparticles. At this point, the electrochromic solution has not yet filled the cavity formed by the frame and the conductive glass. As the pressure continues to decrease slowly, the brittle microparticles gradually break and deform. When the electrochromic solution just fills the cavity formed by the frame and the conductive glass, the pressure is stopped, and the device is cured by UV lamp irradiation. At this point, the interface between the electrochromic solution and the frame is optimal, resulting in the best device stability. To achieve optimal interface conditions and device stability, the D90 particle size of the brittle microparticles needs to be 1.01-1.2 times the D90 particle size of the rigid microparticles; the volume of the brittle microparticles needs to account for a ratio of c‰ of the frame volume; where c ranges from 0.1b to b (b is the ratio of the volume of the rigid microparticles to the frame volume).

[0102] The present disclosure is further illustrated below with reference to embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the disclosure.

[0103] Examples and comparative examples:

[0104] Example 1:

[0105] Example 1 includes the following steps:

[0106] An electrochromic solution was prepared by dissolving 1,1′-diethyl-4,4′-bipyridine (bishexafluorophosphate), 5,10-dihydro-5,10-dimethylphenazine, lithium hexafluorophosphate, and polymethyl methacrylate (Mn = ~15000) in propylene carbonate and controlling the viscosity to 0.01 Pa·s.

[0107] Surface-hydroxylated silica nanoparticles with a diameter of 100 μm and D90 (prepared as described above, volume fraction 80‰) and polystyrene particles with a diameter of 110 μm and D90 (obtained commercially, volume fraction 10‰) were mixed in a UV adhesive at 20 Pa·s. A closed adhesive frame was then applied around the edge of the conductive surface of the mirror-like conductive glass, with an area of ​​20 cm². 2 After evacuating to 1 mbar, an electrochromic material solution was added dropwise in a volume of 0.2 mL. The conductive side of the transparent conductive glass was pressed down and solidified simultaneously. The vacuum was then released to obtain the sample of Example 1.

[0108] Example 2:

[0109] Example 2 includes the following steps:

[0110] An electrochromic solution was prepared by dissolving 1,1′-diethyl-4,4′-bipyridine (bishexafluorophosphate), 5,10-dihydro-5,10-dimethylphenazine, lithium hexafluorophosphate, and polymethyl methacrylate (Mn = ~120000) in propylene carbonate and controlling the viscosity to 2 Pa·s.

[0111] Surface-hydroxylated silica nanoparticles with a diameter of 250 μm and D90 (prepared as described above, volume fraction 40‰) and polystyrene particles with a diameter of 300 μm and D90 (obtained commercially available, volume fraction 5‰) were mixed in a UV adhesive at 50 Pa·s. A closed adhesive frame was then applied around the edge of the conductive surface of the mirror-like conductive glass, with an area of ​​20 cm². 2 After evacuating to 1 mbar, an electrochromic material solution was added dropwise in a volume of 0.52 mL. The conductive side of the transparent conductive glass was pressed down and solidified simultaneously. The vacuum was then released to obtain the sample of Example 2.

[0112] Example 3:

[0113] An electrochromic solution was prepared by dissolving 1,1′-diethyl-4,4′-bipyridine (bishexafluorophosphate), 5,10-dihydro-5,10-dimethylphenazine, lithium hexafluorophosphate, and polymethyl methacrylate (Mn = ~35000) in propylene carbonate and controlling the viscosity to 0.4 Pa·s.

[0114] Surface-hydroxylated silica nanoparticles with a diameter of 175 μm and D90 (prepared as described above, volume fraction 40‰) and polystyrene particles with a diameter of 200 μm and D90 (obtained commercially, volume fraction 10‰) were mixed in a UV adhesive at 230 Pa·s. A closed adhesive frame was then applied around the edge of the conductive surface of the mirror-like conductive glass, with an area of ​​20 cm². 2 After evacuating to 1 mbar, an electrochromic material solution was added dropwise in a volume of 0.36 mL. The conductive side of the transparent conductive glass was pressed down and solidified simultaneously. The vacuum was then released to obtain the sample of Example 3.

[0115] Example 4:

[0116] An electrochromic solution was prepared by dissolving 1,1′-diethyl-4,4′-bipyridine (bishexafluorophosphate), 5,10-dihydro-5,10-dimethylphenazine, lithium hexafluorophosphate, and polymethyl methacrylate (Mn = ~15000) in propylene carbonate and controlling the viscosity to 0.1 Pa·s.

[0117] Surface-hydroxylated silica nanoparticles with a diameter of 75 μm and D90 (prepared as described above, volume fraction 10‰) and polystyrene particles with a diameter of 80 μm and D90 (obtained commercially available, volume fraction 2‰) were mixed in a UV adhesive at 10 Pa·s. A closed adhesive frame was then applied around the edge of the conductive surface of the mirror-like conductive glass, with an area of ​​20 cm². 2 After evacuating to 1 mbar, an electrochromic material solution was added dropwise in a volume of 0.148 mL. The conductive side of the transparent conductive glass was pressed down and solidified simultaneously. The vacuum was then released to obtain the sample of Example 4.

[0118] Example 5:

[0119] An electrochromic solution was prepared by dissolving 1,1′-diethyl-4,4′-bipyridine (bishexafluorophosphate), 5,10-dihydro-5,10-dimethylphenazine, lithium hexafluorophosphate, and polymethyl methacrylate (Mn = ~15000) in propylene carbonate and controlling the viscosity to 0.1 Pa·s.

[0120] Surface-hydroxylated silica nanoparticles with a diameter of 75 μm and D90 (prepared as described above, volume fraction 30‰) and polystyrene particles with a diameter of 80 μm and D90 (obtained commercially available, volume fraction 6‰) were mixed in a UV adhesive at 10 Pa·s. A closed adhesive frame was then applied around the edge of the conductive surface of the mirror-like conductive glass, with an area of ​​20 cm². 2 After evacuating to 1 mbar, an electrochromic material solution was added dropwise in a volume of 0.148 mL. The conductive side of the transparent conductive glass was pressed down and solidified simultaneously. The vacuum was then released to obtain the sample of Example 5.

[0121] Example 6:

[0122] An electrochromic solution was prepared by dissolving 1,1′-diethyl-4,4′-bipyridine (bishexafluorophosphate), 5,10-dihydro-5,10-dimethylphenazine, lithium hexafluorophosphate, and polymethyl methacrylate (Mn = ~120000) in propylene carbonate and controlling the viscosity to 5 Pa·s.

[0123] Surface-hydroxylated silica nanoparticles with a diameter of 150 μm and D90 (prepared as described above, volume fraction 60‰) and polystyrene particles with a diameter of 175 μm and D90 (obtained commercially available, volume fraction 12‰) were mixed in a UV adhesive at 35 Pa·s. A closed adhesive frame was then applied around the edge of the conductive surface of the mirror-like conductive glass, with an area of ​​20 cm². 2 After evacuating to 1 mbar, an electrochromic material solution was added dropwise in a volume of 0.3 mL. The conductive side of the transparent conductive glass was pressed down and solidified simultaneously. The vacuum was then released to obtain the sample of Example 6.

[0124] Comparative Example 1:

[0125] The steps of Comparative Example 1 and Example 1 are the same, except that polystyrene particles, which are brittle particles, are not added.

[0126] Performance testing:

[0127] The thickness uniformity of Examples 1-6 and Comparative Example 1, as well as the defects at the interface between the electrochromic layer and the adhesive path, are observed and recorded in Table 1 below:

[0128] Table 1:

[0129]

[0130] Figure 6 and Figure 7 These are images of the interface between the film frame and the electrochromic layer in Examples 2 and 6, respectively. It can be seen that... Figure 7 In the middle, there are defects at the interface between the electrochromic layer and the adhesive circuit (and Figure 6 There are no defects in the process, because the viscosity of the electrochromic solution precursor, the viscosity of the frame, the particle size of the rigid particles, and the volume fraction of the rigid particles should be compatible with each other (η2). 2 / 2η1log(ab) should be less than or equal to 0.1). If the above conditions cannot be met (as in Example 6), defects will appear at the interface of the frame / electrochromic precursor solution.

[0131] Figure 8 and Figure 9 The images shown are of the interface between the film frame and the electrochromic layer in Example 1 and Comparative Example 1, respectively. As can be seen, Figure 9 In the middle, there is a defect at the interface between the electrochromic layer and the adhesive path (the contact interface between the electrochromic layer and the adhesive frame is not perpendicular to the substrate, and...) Figure 8 This defect does not exist in the example because the frame contains brittle particles. During the pressing process, the thickness of the frame first reaches the diameter of the brittle particles. At this time, the electrochromic solution has not yet filled the cavity formed by the frame and the conductive glass. As the pressure continues to be applied slowly, the brittle particles gradually break and deform. When the electrochromic solution just fills the cavity formed by the frame and the conductive glass, the pressure is stopped, and then further curing is carried out. At this time, the state at the interface between the electrochromic solution and the frame is optimal. However, in Comparative Example 1, which does not contain brittle particles, the contact interface between the electrochromic layer and the frame is not perpendicular to the substrate.

[0132] Preparation Example 1:

[0133] Following the method in Example 1, multiple closed adhesive frames are dotted onto a large sheet of mirrored conductive glass, such as... Figure 5As shown, after vacuuming, electrochromic solution precursors are added to each area, and then another piece of transparent conductive glass is pressed onto the whole. After curing, the vacuum is released and the glass is removed. The transparent conductive glass is laser-cut along line 9, and the mirror conductive glass is laser-cut along line 10. Multiple electrochromic anti-glare rearview mirrors are prepared in one vacuum process in this way.

[0134] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein.

Claims

1. A method of potting an electrochromic device, characterized in that, The perfusion packaging method comprises the following steps: Step 1: preparing an electrochromic solution or preparing a gel film containing an electrochromic material; Step 2: providing a first transparent substrate, placing the first transparent substrate in a vacuum environment, and forming a rubber frame on the upward surface of the first transparent substrate; or providing a first transparent substrate, forming a rubber frame on the upward surface of the first transparent substrate, and then placing the first transparent substrate in a vacuum environment; wherein the upward surface of the first transparent substrate is the surface provided with a conductive layer; Step 3: adding the electrochromic solution to the area formed by the rubber frame and the first transparent substrate; or laying the gel film containing the electrochromic material in the area formed by the rubber frame and the first transparent substrate; Step 4: bonding the downward conductive surface of the second transparent substrate to the upward surface of the first transparent substrate, and curing the rubber frame; Step 5: releasing the vacuum to obtain the electrochromic device; The rubber frame contains rigid particles, the D90 particle size of the rigid particles is a μm; the volume ratio of the rigid particles to the volume of the rubber frame is b‰; the viscosity of the rubber frame is η1 Pa·s, wherein a, b, η1 satisfy the following relationships: 10≤a≤500; 2≤b≤200; 0.1≤η1≤2000, And η1×logb×log(0.1a)≥10; The viscosity of the electrochromic solution is η2 Pa·s, Wherein a, b, η1, η2 satisfy the following relationships: 0.001≤η2≤20, And, η2 2 / 2η1log(ab)≤0.

1.

2. The method of potting encapsulation according to claim 1, wherein, The electrochromic solution is prepared by the following steps: Mixing an anode electrochromic material, a cathode electrochromic material, an electrolyte salt and an organic solvent in an inert gas atmosphere to obtain the electrochromic solution.

3. The method of potting encapsulation according to claim 2, wherein, The electrochromic solution further comprises a polymer tackifier and / or a gel precursor; The polymer tackifier is selected from at least one of polyvinyl alcohol and its derivatives, polyether compounds and their derivatives, polyurethane compounds and their derivatives, polyacrylate compounds and their derivatives, epoxy resin compounds and their derivatives, and phenolic resin compounds and their derivatives; The gel precursor is selected from at least one of precursors of polyacrylonitrile, vinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyvinyl oxide, polyurethane compounds, and epoxy resin compounds.

4. The method of potting encapsulation according to claim 2, wherein, The anode electrochromic material is selected from at least one of phenazine compounds and their derivatives, triphenylamine compounds and their derivatives, or phenothiazine compounds and their derivatives; and / or The cathode electrochromic material is selected from at least one of pyridine compounds and their derivatives, viologen compounds and their derivatives, polyaniline compounds and their derivatives, polypyrrole compounds and their derivatives, polythiophene compounds and their derivatives, polycarbazole compounds and their derivatives, polyfuran compounds and their derivatives, or polyfluorene compounds and their derivatives; and / or the electrolyte salt is selected from at least one of lithium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tributylmethylammonium bis-trifluoromethanesulfonimide salt, tetrabutylammonium bis-trifluoromethanesulfonimide salt or bis-lithium trifluoromethanesulfonimide salt; and / or the organic solvent is selected from at least one of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl carbonate, propylene carbonate, gamma-butyrolactone or dimethyl sulfoxide.

5. The method of potting encapsulation according to claim 1, wherein, the first transparent substrate comprises a first conductive layer, and the second transparent substrate comprises a second conductive layer; the first conductive layer and the second conductive layer are oppositely arranged; further, the first conductive layer comprises at least one of metal Ag, Fe, Sn, Ti, Pt, Al, Au, Mn, Cr, Pd, Rh, Ir, Os or Ru; the second conductive layer comprises at least one of indium tin oxide, fluorine-doped tin oxide, aluminum zinc oxide, silver nanowire, carbon nanotube, graphene or metal mesh.

6. The method of potting encapsulation according to claim 1, wherein, the material of the glue frame is selected from at least one of epoxy resin glue, polyurethane glue and acrylate glue.

7. The method of potting encapsulation according to claim 1, wherein, based on the total volume of the area formed by the glue frame and the first transparent substrate, the volume fraction of the added electrochromic solution is selected from 95%-110%.

8. The method of potting encapsulation according to claim 1, wherein, the projections of the first transparent substrate and the second transparent substrate on the plane do not completely overlap.

9. A method of potting an electrochromic device, characterized in that, the perfusion packaging method comprises the following steps: Step 1: preparing an electrochromic solution; Step 2: providing a first transparent substrate comprising a first conductive layer, depositing an anode electrochromic material layer on the surface of the first conductive layer away from the first transparent substrate; placing the first transparent substrate in a vacuum environment to form a glue frame on the surface of the anode electrochromic material layer facing upward; wherein the upward surface of the first transparent substrate is the surface provided with the conductive layer; Step 3: adding the electrochromic solution to the area formed by the glue frame and the first transparent substrate; Step 4: providing a second transparent substrate comprising a second conductive layer, depositing a cathode electrochromic material layer on the surface of the second conductive layer away from the second transparent substrate, the cathode electrochromic material layer being in contact with the electrochromic solution; bonding the second transparent substrate with the upward surface of the glue frame, and curing the glue frame; Step 5: releasing the vacuum to obtain the electrochromic device; the glue frame comprises rigid particles, the D90 particle size of the rigid particles is a μm; the volume ratio of the rigid particles to the volume of the glue frame is b‰; the viscosity of the glue frame is η1 Pa·s, wherein a, b, η1 satisfy the following relationships: 10≤a≤500; 2≤b≤200; 0.1≤η1≤2000, and η1×logb×log(0.1a)≥10; the viscosity of the electrochromic solution is η2 Pa·s, wherein a, b, η1, η2 satisfy the following relationships: 0.001≤η2≤20, And, η2 2 / 2η1log(ab)≤0.

1.

10. An electrochromic device, characterized in that, the electrochromic device is prepared by the perfusion packaging method of any one of claims 1-8 or the perfusion packaging method of claim 9.

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