An electrochromic device, a preparation method thereof, and an application thereof

Abstract

The present invention provides an electrochromic device, a preparation method thereof and an application. The electrochromic device includes a first substrate, a first conductive layer, an ion storage layer, an electrolyte layer, an electrochromic layer, a second conductive layer and a second substrate which are sequentially arranged; a bending portion is arranged on one side of the electrochromic device, and the first substrate, the bending portion and the second substrate are connected to each other to form an integral structure. The electrochromic device is formed by folding the electrochromic layer and the ion storage layer on the same substrate, which enhances the integrity and structural strength of the electrochromic device, reduces the risk of film layer separation, and at the same time reduces the contact area between the electrochromic layer and the environment, enhances the water and oxygen barrier performance of the device, improves the sealing performance, stability and color change uniformity of the device, and improves the quality of the electrochromic device and the electronic terminal.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromic display, and particularly relates to an electrochromic device, a preparation method thereof, and an application thereof. Background Art

[0002] The electrochromic phenomenon refers to the reversible color change of a material under the action of an external electric field; the essence of electrochromism is that the material undergoes an oxidation-reduction reaction under the action of an external electric field and current, resulting in a change in its structure, and further causing changes in the absorption spectrum and optical properties (such as absorption rate, transmittance, reflectance), which is manifested as a reversible change in color and transparency in appearance. In recent years, electrochromic devices have been widely used in fields such as energy-saving windows, automotive rearview mirrors, display devices, and mobile terminals, and have good market application prospects.

[0003] Existing electrochromic devices are usually of a layered structure, including two substrates. There are two conductive layers between the substrates, and an active material layer is provided between the two conductive layers. The active material includes an electrolyte, an electrochromic material, an ion storage material, etc. In the preparation process of the electrochromic device, it is necessary to use a conductive substrate to bond the color-changing material, and after the bonding is completed, ultraviolet curing is carried out. After curing, the electrochromic device is wound or slit and stored; however, the electrochromic device obtained by this method usually does not have the ability to isolate water and oxygen, and is easily affected by water and oxygen in the air, resulting in uneven color change. Therefore, improving the water and oxygen barrier and sealing performance of electrochromic devices is an important means to improve the device quality.

[0004] At present, many research works are dedicated to improving the sealing and barrier properties of electrochromic devices. For example, CN107422565A discloses an electrochromic device and a manufacturing method thereof. The electrochromic device includes a first substrate and a second substrate disposed opposite to each other, and a sealing frame structure for forming a sealed cavity between the first substrate and the second substrate. A liquid electrolyte is disposed in the sealed cavity. The sealing frame structure includes a packaging frame structure and a plugging structure. The packaging frame structure and the plugging structure are located between the first substrate and the second substrate. A liquid injection port for injecting the electrolyte is provided on the packaging frame structure; this electrochromic device can improve the sealing performance of the device, but the sealing performance is mainly reflected in preventing the leakage of the liquid electrolyte, and the process for achieving sealing is very complicated, with a high preparation cost, which is not conducive to large-scale application.

[0005] CN102830565A discloses an electrochromic film and an electrochromic device. The electrochromic device includes a first substrate and a second substrate which are oppositely arranged, a first transparent conductive layer disposed on the inner side of the first substrate, a second transparent conductive layer disposed on the inner side of the second substrate, and an organic-inorganic electrochromic film disposed between the first transparent conductive layer and the second transparent conductive layer. This electrochromic device has a good display effect, but it is prone to problems such as being affected by water and oxygen during winding or slitting processing, and problems such as film peeling and bending are likely to occur during wiring.

[0006] CN212009235U discloses an edge-sealed conductive substrate and an electrochromic device. The edge-sealed conductive substrate includes a base layer, a transparent conductive layer, at least one conductive part, at least one sealing part, and at least one side lead electrode connected to the conductive part; the electrochromic device includes a first conductive layer, a color-changing material layer, and a second conductive layer which are sequentially stacked, and the sealing part of the conductive layer is used for sealing the edge of the color-changing material layer. When using the edge-sealed conductive substrate to set up the electrochromic device, no additional electrode wiring operation is required, avoiding the influence of water and oxygen in the air. However, when a vertical force acts on the above electrochromic device, since the layers of materials are independent of each other, a phenomenon of film layer separation is likely to occur, seriously affecting the performance of the device; moreover, the electrochromic material is extremely sensitive to water vapor and oxygen, and the existing packaging technology has risks of film peeling and separation, resulting in the active materials in the device being exposed to the environment, and being prone to absorbing water and oxygen and failing.

[0007] Therefore, developing an electrochromic device with good integrity, good structural strength, high stability, and good water and oxygen barrier performance is an urgent problem to be solved in this field. Summary of the Invention

[0008] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an electrochromic device, its preparation method and application. The electrochromic device is provided with a bending part and is integrally connected with the first substrate and the second substrate, improving the integrity of the electrochromic device, reducing the risk of film layer separation, and effectively improving the water and oxygen barrier performance of the device, making the electrochromic device have better structural strength and stability, and significantly improving the quality of the device and the electronic terminal.

[0009] To achieve the purpose of this invention, the present invention adopts the following technical solutions:

[0010] In the first aspect, the present invention provides an electrochromic device, which includes a first substrate, a first conductive layer, an ion storage layer, an electrolyte layer, an electrochromic layer, a second conductive layer, and a second substrate which are stacked.

[0011] One side of the electrochromic device is provided with a bent portion, and the first substrate, the bent portion and the second substrate are connected to each other to form an integral structure; the "one side" means any side in the vertical direction of the first substrate.

[0012] Through the structural design of the electrochromic device provided by the present invention, especially by connecting the first substrate, the bent portion and the second substrate into an integral structure, the integrity and structural strength of the electrochromic device are improved, and the risk of film layer separation is reduced; at the same time, the bent portion isolates the electrochromic layer from the external environment, reduces the area of the electrochromic layer in contact with the environment, enhances the barrier ability of the device to water vapor and oxygen, and improves the stability and color change uniformity of the electrochromic device.

[0013] Exemplarily, the structural schematic diagram of the electrochromic device is as Figure 1 shown, including a first substrate 11, a first conductive layer 21, an ion storage layer 3, an electrolyte layer 4, an electrochromic layer 5, a second conductive layer 22 and a second substrate 12 arranged in sequence; a bent portion 13 is provided on one side of the electrochromic device, and the bent portion 13, the first substrate 11 and the second substrate 12 are connected to each other to form an integral structure.

[0014] In a preferred technical solution, the materials of the first substrate, the bent portion and the second substrate are the same, and are all transparent substrate materials.

[0015] In a preferred technical solution, the thicknesses of the first substrate, the bent portion and the second substrate are equal, and are 20 - 500 μm. For example, they can be 30 μm, 50 μm, 70 μm, 90 μm, 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, 220 μm, 250 μm, 280 μm, 300 μm, 320 μm, 350 μm, 380 μm, 400 μm, 420 μm, 450 μm or 480 μm, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0016] In a preferred technical solution, the materials of the first conductive layer and the second conductive layer are transparent conductive materials.

[0017] Exemplarily, the transparent conductive material includes any one or a combination of at least two of ITO (indium-tin oxide), AZO (aluminum zinc oxide), FTO (fluorine doped tin oxide), silver nanowires, graphene, carbon nanotubes, metal grids or silver nanoparticles.

[0018] In a preferred technical solution, the thicknesses of the first conductive layer and the second conductive layer are each independently 0.1 to 500 nm. For example, they can be 0.3 nm, 0.5 nm, 0.8 nm, 1 nm, 3 nm, 5 nm, 8 nm, 10 nm, 20 nm, 50 nm, 80 nm, 100 nm, 120 nm, 150 nm, 180 nm, 200 nm, 220 nm, 250 nm, 280 nm, 300 nm, 320 nm, 350 nm, 380 nm, 400 nm, 420 nm, 450 nm or 480 nm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0019] In a preferred technical solution, the thickness of the ion storage layer is 1 to 1000 nm. For example, it can be 3 nm, 5 nm, 8 nm, 10 nm, 20 nm, 50 nm, 80 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm or 950 nm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0020] In a preferred technical solution, the thickness of the electrolyte layer is 10 to 200 μm. For example, it can be 20 μm, 30 μm, 50 μm, 70 μm, 90 μm, 100 μm, 110 μm, 130 μm, 150 μm, 170 μm or 190 μm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0021] In a preferred technical solution, the thickness of the electrochromic layer is 100 nm to 5 μm. For example, it can be 200 nm, 500 nm, 800 nm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 2.1 μm, 2.3 μm, 2.5 μm, 2.8 μm, 3 μm, 3.2 μm, 3.5 μm, 3.8 μm, 4 μm, 4.2 μm, 4.5 μm or 4.8 μm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0022] In a preferred technical solution, the cross-section of the bent portion is circular arc-shaped; the "cross-section" means the cross-section in the structural schematic diagram of the electrochromic device.

[0023] In a preferred technical solution, the perimeter of the cross-section of the bent portion is L, and the thickness of the electrolyte layer of the electrochromic device is d 1 , and L≥π·d 1 / 2.

[0024] In the present invention, the "perimeter of the cross-section of the bent portion" means the perimeter of the aforementioned arc shape.

[0025] In a preferred technical solution, the ratio of L to d 1 is (1.57 to 1.60):1. For example, it can be 1.571:1, 1.572:1, 1.573:1, 1.574:1, 1.575:1, 1.576:1, 1.577:1, 1.578:1, 1.579:1, 1.58:1, 1.583:1, 1.585:1, 1.587:1, 1.589:1, 1.59:1, 1.591:1, 1.593:1, 1.595:1, 1.597:1 or 1.599:1, etc.

[0026] In a preferred technical solution, a first lead-out structure is provided on the first conductive layer, and a second lead-out structure is provided on the second conductive layer; the first lead-out structure and the second lead-out structure are lead-out electrodes and / or bus bars.

[0027] In the present invention, the lead-out electrode is a single-point structure, and the bus bar is a strip-shaped structure; compared with the single-point lead-out electrode, the bus bar lead-out can achieve a more uniform color-changing effect.

[0028] In a preferred technical solution, the first lead-out structure is a first lead-out electrode, and the second lead-out structure is a second lead-out electrode; the first lead-out electrode is provided on the side of the first conductive layer away from the first substrate (not in contact with the ion storage layer), and the second lead-out electrode is provided on the side of the second conductive layer away from the second substrate (not in contact with the electrochromic layer).

[0029] In a preferred technical solution, the first lead-out structure is a first bus bar, and the second lead-out structure is a second bus bar; the first bus bar is provided on the side of the first conductive layer away from the first substrate or between the first conductive layer and the first substrate, and the second bus bar is provided on the side of the second conductive layer away from the second substrate or between the second conductive layer and the second substrate.

[0030] In the above technical solution, a first lead-out structure is provided on the first conductive layer, and a second lead-out structure is provided on the second conductive layer to achieve lead-out; however, in actual production of this structure, the device needs to be turned over for lead-out twice, and the process is complicated and not easy to automate; at the same time, in order to reduce the number of circuit interfaces, the lead-out structure FPC is a structure integrating positive and negative electrodes, and a part of the lead-out structure will be distorted, and the stress of this distortion will affect the connection stability between the lead-out structure and the device, and may even cause the film layer near the lead-out structure area to separate.

[0031] To solve the above problems, in a preferred technical solution, a third conductive layer is provided at one end of the second substrate close to the bending part, and the third conductive layer is independent of the first conductive layer and the second conductive layer;

[0032] A first bus bar is provided between the first conductive layer and the first substrate, and the first bus bar extends to between the third conductive layer and the second substrate via the bending part; a second bus bar is provided between the second conductive layer and the second substrate;

[0033] Or, a third conductive layer is provided at one end of the first substrate close to the bending part, and the third conductive layer is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the first substrate; a second bus bar is provided between the second conductive layer and the second substrate, and the second bus bar extends to between the third conductive layer and the first substrate via the bending part.

[0034] In the present invention, the term "mutually independent" means that the third conductive layer, the first conductive layer, and the second conductive layer are disconnected from each other and do not make connections. The third conductive layer and the first conductive layer (or the second conductive layer) are provided on the substrate in the same area.

[0035] In the above two parallel technical solutions, by making any one of the bus bars extend to between the third conductive layer and the first substrate (or the second substrate) via the bending part, it is realized that lead-out can be carried out only on one side, greatly simplifying the lead-out process and increasing the stability of lead-out. However, the bus bar in this technical solution is provided between the conductive layer and the substrate, and the accuracy requirement for laser etching is very high in the actual preparation process.

[0036] In a preferred technical solution, the side of the third conductive layer away from the first substrate or the second substrate is in contact with the electrolyte layer.

[0037] In order to reduce the requirements for laser etching accuracy in the preparation process of the one-sided lead-out, in another preferred technical solution, a third conductive layer is provided at one end of the second substrate close to the bending portion, and the third conductive layer is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the ion storage layer, and the first bus bar extends to the third conductive layer through the bending portion; a second bus bar is provided between the second conductive layer and the electrochromic layer;

[0038] Alternatively, a third conductive layer is provided at one end of the first substrate close to the bending portion, and the third conductive layer is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the ion storage layer; a second bus bar is provided between the second conductive layer and the electrochromic layer, and the second bus bar extends to the third conductive layer through the bending portion.

[0039] In the present invention, the term "mutually independent" means that the third conductive layer, the first conductive layer, and the second conductive layer are disconnected from each other and do not connect. The third conductive layer and the first conductive layer (or the second conductive layer) are provided on the substrate in the same area.

[0040] In the above two parallel technical solutions, by making any one of the bus bars extend to the third conductive layer (i.e., the side of the third conductive layer away from the substrate) through the bending portion, it is realized that the lead-out can be carried out only on one side, greatly simplifying the lead-out process, increasing the stability of the lead-out, and reducing the requirements for laser etching accuracy.

[0041] In a preferred technical solution, the first conductive layer, the ion storage layer, the electrolyte layer, the electrochromic layer, and the second conductive layer form a conductive active part, and a cavity is formed between the conductive active part and the bending portion, and the cavity is filled with insulating glue.

[0042] Among them, the setting of the insulating glue can prevent the third conductive layer / bus bar at the bending portion from coming into contact with each other and causing a short circuit; preferably, the insulating glue has a sealing property and can play a role in isolating water and oxygen.

[0043] In a preferred technical solution, the electrochromic device further includes a sealing part, and the sealing part is arranged between the first substrate and the second substrate to seal the conductive active part formed by the first conductive layer, the ion storage layer, the electrolyte layer, the electrochromic layer, and the second conductive layer.

[0044] In a preferred technical solution, the material of the sealing part is sealing glue.

[0045] In a preferred technical solution, a first water and oxygen barrier layer is further provided on the side of the first substrate away from the first conductive layer, and / or a second water and oxygen barrier layer is further provided on the side of the second substrate away from the second conductive layer.

[0046] In a preferred technical solution, the outer side of the electrochromic device includes an adhesive layer and a base layer arranged in sequence, and the adhesive layer and the base layer are connected to the electrochromic device through a sealant.

[0047] Second, the present invention provides a method for preparing an electrochromic device as described in the first aspect. The preparation method includes the following steps:

[0048] (1) Divide the substrate into a first region and a second region. A first conductive layer and an ion storage layer are sequentially arranged on the first region, and a second conductive layer and an electrochromic layer are sequentially arranged on the second region. There is a spaced region between the first region and the second region to form a preform A;

[0049] (2) Fold the preform A obtained in step (1) in a direction such that the ion storage layer and the electrochromic layer face each other, inject an electrolyte material between the ion storage layer and the electrochromic layer, and cure to obtain the electrochromic device.

[0050] In a preferred technical solution, the method for preparing the spaced region in step (1) is laser etching.

[0051] Exemplarily, in step (1), first prepare (deposit) a conductive layer on one surface of the substrate, and then respectively arrange (coat) an ion storage layer and an electrochromic layer on the conductive layer. The electrochromic layer and the ion storage layer are arranged on the same substrate and are separated by a spaced region in the middle. At the same time, the spaced region divides the conductive layer into two corresponding regions, namely the first conductive layer and the second conductive layer; the spaced region can be formed by laser etching.

[0052] In a preferred technical solution, the folding method in step (2) is a roll pressing process.

[0053] Exemplarily, in step (2), place the preform A between two rubber rollers and fold it in a direction such that the ion storage layer and the electrochromic layer face each other through a roll pressing process, so that the spaced region forms a bent portion, and the width of the spaced region is the perimeter of the bent portion.

[0054] In the electrochromic device, the thickness (d 1 ) of the electrolyte layer is much larger than that of the first conductive layer, the ion storage layer, the electrochromic layer, and the second conductive layer. Therefore, the cross-sectional shape of the bent portion is a semi-circle, and its perimeter (i.e., the width of the spaced region) ≈ π·d 1 / 2.

[0055] When the width of the spacer region is equal to π / 2 times the thickness of the electrolyte layer, an electrochromic device with excellent performance can be formed by folding; when the width of the spacer region is less than π / 2 times the thickness of the electrolyte layer, to form a device with parallel upper and lower parts, part of the first conductive layer, part of the ion storage layer, part of the second conductive layer, and part of the electrochromic layer also need to be bent. When the multilayer structure is bent, the layer structure located inside is easily affected by compressive stress, and the layer structure located outside is easily affected by tensile stress, which will increase the possibility of film layer separation; when the width of the spacer region is greater than π / 2 times the thickness of the electrolyte layer, the color-changing region will shrink and decrease, affecting the device performance.

[0056] Therefore, in a preferred technical solution, the thickness of the electrolyte layer of the electrochromic device is d 1 , the width of the spacer region in step (1) is L, and L ≥ π·d 1 / 2, and more preferably L = π·d 1 / 2.

[0057] In a preferred technical solution, the ratio of L to d 1 is (1.57 - 1.60):1. For example, it can be 1.571:1, 1.572:1, 1.573:1, 1.574:1, 1.575:1, 1.576:1, 1.577:1, 1.578:1, 1.579:1, 1.58:1, 1.583:1, 1.585:1, 1.587:1, 1.589:1, 1.59:1, 1.591:1, 1.593:1, 1.595:1, 1.597:1 or 1.599:1, etc.

[0058] In a preferred technical solution, a first lead-out structure is provided on the first conductive layer, and a second lead-out structure is provided on the second conductive layer to achieve lead-out; in actual production, the device needs to be turned over for two lead-outs (lead out once on the lower sheet first, and then turn it over and lead out once on the upper sheet), and the process is complicated and not easy to automate; at the same time, in order to reduce the number of circuit interfaces, the lead-out structure FPC is a structure with integrated positive and negative electrodes, then part of the lead-out structure will be distorted, and the distortion stress will affect the connection stability between the lead-out structure and the device, and may even cause the film layer near the lead-out structure region to separate.

[0059] To solve the above problems, in a preferred technical solution, a third conductive layer is provided at one end of the second substrate close to the bending portion, and the third conductive layer is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the first substrate, and the first bus bar extends to between the third conductive layer and the second substrate via the bending portion; a second bus bar is provided between the second conductive layer and the second substrate; or, a third conductive layer is provided at one end of the first substrate close to the bending portion, and the third conductive layer is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the first substrate; a second bus bar is provided between the second conductive layer and the second substrate, and the second bus bar extends to between the third conductive layer and the first substrate via the bending portion. Taking the first technical solution as an example, the manufacturing process is as follows: (A1) The first bus bar and the second bus bar are respectively provided on one surface of the substrate, and then the conductive layer is deposited; (A2) The ion storage layer and the electrochromic layer are respectively coated on the conductive layer; (A3) Laser etching is performed, and the etching depth is the thickness of the conductive layer (the conductive layer is cut off, but the first bus bar cannot be cut off), so that the conductive layer is etched into the independent first conductive layer, third conductive layer and second conductive layer, and there is a spaced area between the first conductive layer and the third conductive layer; (A4) The materials (electrochromic materials) on the laser etching area and the third conductive layer are erased to form a preform A; then, folding is performed according to the process of the foregoing step (2) to obtain the electrochromic device.

[0060] In the above preparation process, there are high requirements for the depth accuracy of the laser etching in step (A3), that is, it is difficult to precisely cut off the conductive layer without damaging the bus bar. Therefore, in another preferred technical solution, a third conductive layer is provided at one end of the second substrate close to the bending portion, and the third conductive layer is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the ion storage layer, and the first bus bar extends to the third conductive layer through the bending portion; a second bus bar is provided between the second conductive layer and the electrochromic layer; or, a third conductive layer is provided at one end of the first substrate close to the bending portion, and the third conductive layer is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the ion storage layer; a second bus bar is provided between the second conductive layer and the electrochromic layer, and the second bus bar extends to the third conductive layer through the bending portion. Taking the first technical solution as an example, the preparation process is as follows: (B1) Deposit a conductive layer on one surface of the substrate; (B2) Perform laser etching with an etching depth equal to the thickness of the conductive layer (cut off the conductive layer), so as to etch the conductive layer into independent first, third, and second conductive layers, and there is a spaced area between the first conductive layer and the third conductive layer; (B3) Arrange the first bus bar on the first conductive layer and extend it to the third conductive layer through the spaced area, and arrange the second bus bar on the second conductive layer; (B4) Coat and prepare an ion storage layer on the first conductive layer (covering the part of the first bus bar on the first conductive layer), and coat and prepare an electrochromic layer on the second conductive layer (covering the second bus bar); (B5) Erase the materials (electrochromic materials) on the laser etching area and the third conductive layer to form a preform A; then fold it according to the process of the foregoing step (2) to obtain an electrochromic device.

[0061] Furthermore, in order to avoid short circuits caused by the mutual contact of the third conductive layer / bus bar at the bending portion and improve the water and oxygen barrier performance, it is preferred to fill an insulating glue in the cavity formed between the conductive active portion (composed of the first conductive layer, ion storage layer, electrolyte layer, electrochromic layer, and second conductive layer) and the bending portion; the specific preparation process is: before injecting the electrolyte material by rolling in step (2), first inject the insulating glue in the bending area, and then inject the electrolyte material and roll it after curing.

[0062] In order to further block water and oxygen and improve the sealing performance, the electrochromic device further includes a sealing part, which is arranged between the first substrate and the second substrate to seal the conductive active part composed of the first conductive layer, the ion storage layer, the electrolyte layer, the electrochromic layer and the second conductive layer. The specific preparation process is as follows: after completing the curing process in step (2), laser etch a groove on the other three sides of the first substrate (or the second substrate) (the three sides facing the electrochromic device and not connected to the bending part), fill the groove with a sealant, and then attach a water and oxygen barrier layer on the side of the first substrate and the second substrate away from the electrolyte layer to achieve sealing.

[0063] In a third aspect, the present invention provides an electronic terminal, and the electronic terminal includes the electrochromic device described in the first aspect.

[0064] Compared with the prior art, the present invention has the following beneficial effects:

[0065] One side of the electrochromic device provided by the present invention is provided with a bending part, which is integrally connected with the first substrate and the second substrate; the electrochromic device is formed by folding the electrochromic layer and the ion storage layer on the same substrate, which enhances the integrity and structural strength of the electrochromic device, reduces the risk of film layer separation, and at the same time reduces the contact area between the electrochromic layer and the environment, enhances the water and oxygen barrier performance of the device, improves the stability and color change uniformity of the electrochromic device, and thus improves the quality of the electrochromic device and the electronic terminal. Description of the Drawings

[0066] Figure 1 Schematic structural diagram of the electrochromic device provided for Examples 1 and 2;

[0067] Figure 2 Schematic structural diagram of the preform A for preparing the electrochromic device provided for Example 1;

[0068] Figure 3 Schematic diagram of the folding preparation process of the electrochromic device provided for Example 1;

[0069] Figure 4 Schematic structural diagram of the preform A for preparing the electrochromic device provided for Example 2;

[0070] Figure 5 Top view structural diagram of the preform A for preparing the electrochromic device provided for Example 2;

[0071] Figure 6 Schematic structural diagram of the electrochromic device provided for Example 3;

[0072] Figure 7Schematic structural diagram of preform A for preparing an electrochromic device provided in Example 3;

[0073] Figure 8 Schematic structural diagram of the electrochromic device provided in Example 4;

[0074] Figure 9 Schematic structural diagram of the electrochromic device provided in Example 5;

[0075] Figure 10 Schematic structural diagram of preform A for preparing an electrochromic device provided in Example 5;

[0076] Figure 11 Schematic diagram of the lead-out of the electrochromic device provided in Example 1;

[0077] Figure 12 Schematic diagram of the lead-out structure in the electrochromic device provided in Example 1;

[0078] Figure 13 Schematic structural diagram of preform A for preparing an electrochromic device provided in Example 6;

[0079] Figure 14 Schematic structural diagram of the electrochromic device provided in Example 7;

[0080] Figure 15 Schematic structural diagram of the electrochromic device provided in Example 8;

[0081] Figure 16 Schematic structural diagram of the electrochromic device provided in Example 9;

[0082] Among them, 1 - electrochromic device, 10 - substrate, 11 - first substrate, 12 - second substrate, 13 - bending part, 21 - first conductive layer, 22 - second conductive layer, 23 - third conductive layer, 3 - ion storage layer, 4 - electrolyte layer, 5 - electrochromic layer, 61 - first lead-out electrode, 62 - second lead-out electrode, 60 - lead-out structure, 601 - FPC negative electrode, 602 - FPC positive electrode, 603 - circuit interface, 71 - first bus bar, 72 - second bus bar, 8 - cavity, 9 - sealing part, 101 - first water and oxygen barrier layer, 102 - second water and oxygen barrier layer, 111 - bonding layer, 112 - base layer, 113 - sealant, A1 - first region, A2 - second region, A3 - spacer region, B1 - rubber roller, B2 - electrolyte storage device. Detailed implementation manners

[0083] The technical solutions of the present invention will be further described below through specific implementation manners. Those skilled in the art should understand that the described embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0084] Example 1

[0085] This example provides an electrochromic device and a preparation method thereof. The structural schematic diagram of the electrochromic device is as follows Figure 1 shown, including a first substrate 11, a first conductive layer 21, an ion storage layer 3, an electrolyte layer 4, an electrochromic layer 5, a second conductive layer 22, and a second substrate 12 arranged in sequence; a bending portion 13 is provided on one side of the electrochromic device, and the bending portion 13, the first substrate 11, and the second substrate 12 are connected to form an integral structure.

[0086] The preparation method includes the following steps:

[0087] (1) Preparation of preform A: The structural schematic diagram of preform A is as follows Figure 2 shown. The substrate 10 (PET) is divided into a first region A1 and a second region A2. A conductive layer (ITO, with a thickness of 5 nm) is deposited on the substrate, and then an ion storage layer 3 (with a thickness of 100 nm) and an electrochromic layer 5 (with a thickness of 1 μm) are respectively coated on the conductive layer. An intermediate spacer region A3 (with a width of 157 μm) is formed by laser etching, and the conductive layer is divided into a first conductive layer 21 and a second conductive layer 22; a first lead electrode 61 is provided at the exposed edge of the first conductive layer 21, and a second lead electrode 62 is provided at the exposed edge of the second conductive layer.

[0088] (2) Folding preparation of the electrochromic device: The process schematic diagram is as follows Figure 3 shown. The preform A obtained in step (1) is placed between two rubber rollers B1, and is folded by a roller pressing process in the direction in which the ion storage layer 3 and the electrochromic layer 5 face each other. An electrolyte material is injected between the ion storage layer 3 and the electrochromic layer 5 from an electrolyte storage device B2, and is cured to form an electrolyte layer with a thickness of 100 μm, obtaining the electrochromic device.

[0089] In the electrochromic device provided in this example, by arranging the electrochromic layer and the ion storage layer on the same substrate, the integrity of the device is enhanced, and the possibility of film layer separation is reduced; at the same time, the setting of the bending portion isolates the electrochromic layer from the environment, enhancing the moisture barrier ability of the device.

[0090] Example 2

[0091] This example provides an electrochromic device and a preparation method thereof. The structural schematic diagram of the electrochromic device is as follows Figure 1As shown, it includes a first substrate 11, a first conductive layer 21, an ion storage layer 3, an electrolyte layer 4, an electrochromic layer 5, a second conductive layer 22, and a second substrate 12 arranged in sequence; a bending portion 13 is provided on one side of the electrochromic device, and the bending portion 13, the first substrate 11, and the second substrate 12 are connected to each other to form an integral structure.

[0092] The difference between the preparation method and that of Example 1 is only that in step (1), a first bus bar 71 is provided at the exposed edge of the first conductive layer 21, and a second bus bar 72 is provided at the exposed edge of the second conductive layer. The structural schematic diagram of the obtained preform A is as Figure 4 shown, and the top view structural schematic diagram of the preform A is as Figure 5 shown; compared with the single-point structure first lead electrode and second lead electrode in Example 1, in this embodiment, bus bars are provided, which can improve the uneven color change phenomenon that may be caused by the single-point lead electrode.

[0093] Example 3

[0094] This embodiment provides an electrochromic device and a preparation method thereof. The structural schematic diagram of the electrochromic device is as Figure 6 shown, and it includes a first substrate 11, a first conductive layer 21, an ion storage layer 3, an electrolyte layer 4, an electrochromic layer 5, a second conductive layer 22, and a second substrate 12 arranged in sequence; a bending portion 13 is provided on one side of the electrochromic device, and the bending portion 13, the first substrate 11, and the second substrate 12 are connected to each other to form an integral structure; a first bus bar 71 is provided between the first substrate 11 and the first conductive layer 21, and a first bus bar 72 is provided between the second conductive layer 22 and the second substrate 12.

[0095] The difference between the preparation method and that of Example 1 is only that in step (1), the first bus bar 71 and the first bus bar 72 are first provided on the substrate 10 (PET), and then the conductive layer is deposited; the structural schematic diagram of the obtained preform A is as Figure 7 shown.

[0096] Example 4

[0097] This embodiment provides an electrochromic device and a preparation method thereof. The structural schematic diagram of the electrochromic device is as Figure 8 shown, and it includes a first substrate 11, a first conductive layer 21, an ion storage layer 3, an electrolyte layer 4, an electrochromic layer 5, a second conductive layer 22, and a second substrate 12 arranged in sequence; a bending portion 13 is provided on one side of the electrochromic device, and the bending portion 13, the first substrate 11, and the second substrate 12 are connected to each other to form an integral structure.

[0098] The difference between the preparation method and that of Example 1 is only that in step (1), the width of the interval region A3 is 50 μm.

[0099] Since the width of the spacer region in this embodiment is small (less than π / 2 times the thickness of the electrolyte layer), to form a device with parallel upper and lower parts, part of the first conductive layer, part of the ion storage layer, part of the second conductive layer, and part of the electrochromic layer also need to be bent. Therefore, the electrochromic layer and the ion storage layer located in the inner layer are easily affected by compressive stress, and the bent part located in the outer layer is easily affected by tensile stress, which increases the possibility of film layer separation.

[0100] Embodiment 5

[0101] This embodiment provides an electrochromic device and a preparation method thereof. The structural schematic diagram of the electrochromic device is as Figure 9 shown, including a first substrate 11, a first conductive layer 21, an ion storage layer 3, an electrolyte layer 4, an electrochromic layer 5, a second conductive layer 22, and a second substrate 12 arranged in sequence; a bent part 13 is arranged on one side of the electrochromic device, and the bent part 13, the first substrate 11, and the second substrate 12 are connected to form an integral structure; a third conductive layer 23 is arranged at one end of the first substrate 11 close to the bent part 13, and the third conductive layer 23 is independent of the first conductive layer 21 and the second conductive layer 22; a first bus bar 71 is arranged between the first conductive layer 21 and the first substrate 11; a second bus bar 72 is arranged between the second conductive layer 22 and the second substrate 12, and the second bus bar 72 extends to between the third conductive layer 23 and the first substrate 11 via the bent part 13.

[0102] The difference between the preparation method and that of Embodiment 1 is only that the specific process of step (1) is as follows: (A1) The first bus bar 71 and the second bus bar 72 are respectively arranged on one surface of the substrate 10, and then the conductive layer is deposited; (A2) The ion storage layer 3 and the electrochromic layer 5 are respectively coated on the conductive layer; (A3) Laser etching is carried out, and the etching depth is the thickness of the conductive layer (the conductive layer is cut off, but the first bus bar cannot be cut off), so as to etch the conductive layer into independent first conductive layer 21, third conductive layer 23, and second conductive layer 22, and there is a spacer region A3 between the third conductive layer 23 and the second conductive layer 22; (A4) The materials on the laser etching region and the third conductive layer 23 are erased to form a preform A, and its structural schematic diagram is as Figure 10 shown.

[0103] Taking Embodiment 1 as an example, the lead-out schematic diagram of a conventional electrochromic device is as Figure 11As shown, lead-out structures 60 are respectively arranged on the first conductive layer (the first lead-out structure region C1) and the second conductive layer (the second lead-out structure region C2) to achieve lead-out. In actual production, the device needs to be turned over to perform lead-out twice (lead out once on the lower wafer first, and then turn it over to lead out once on the upper wafer), and the process is complicated and not easy to automate. At the same time, in order to reduce the number of circuit interfaces, the lead-out structure 60 (FPC) is a structure integrating the positive and negative electrodes. As Figure 12 shown, it includes an FPC negative electrode 601, an FPC positive electrode 602, and a circuit interface 603. A part of this lead-out structure will be distorted, and the distortion stress will affect the connection stability between the lead-out structure and the device, and may even cause the film layer near the lead-out structure region to separate.

[0104] In this embodiment, by extending a bus bar to the region where the bending part is located, it is realized that lead-out can be performed on only one side, greatly simplifying the lead-out process and increasing the stability of lead-out.

[0105] Embodiment 6

[0106] This embodiment provides an electrochromic device and a preparation method thereof. The difference between the electrochromic device and that in Embodiment 5 is only that a first bus bar 71 is arranged between the first conductive layer 21 and the ion storage layer 3; a second bus bar 72 is arranged between the second conductive layer 22 and the electrochromic layer 5, and the second bus bar 72 extends to the third conductive layer 23 via the bending part 13.

[0107] The difference between the preparation method and that in Embodiment 5 is only that the specific process of step (1) is as follows: (B1) Deposit a conductive layer on the surface of the substrate 10; (B2) Perform laser etching, and the etching depth is the thickness of the conductive layer (etching through the conductive layer), so as to etch the conductive layer into independent first conductive layer 21, third conductive layer 23, and second conductive layer 22. There is a spacing region A3 between the third conductive layer 23 and the second conductive layer 22; (B3) Arrange the first bus bar 71 on the first conductive layer 21, arrange the second bus bar 72 on the second conductive layer 22 and extend it to the third conductive layer 23 via the spacing region A3; (B4) Coat the ion storage layer 3 on the first conductive layer 21 (covering the first bus bar 71), and coat the electrochromic layer 5 prepared on the second conductive layer 22 (covering the part of the second bus bar 72 located on the second conductive layer 22); (B5) Erase the materials in the laser etching region and on the third conductive layer to form a preform A, and its structural schematic diagram is as Figure 13 shown.

[0108] In this embodiment, by extending a bus bar to the area where the bending part is located, it is possible to perform lead-out on only one side, simplifying the lead-out process and increasing the lead-out stability. At the same time, compared with Embodiment 5, the preparation method of this embodiment has lower requirements for the depth accuracy of laser etching, which is more conducive to large-scale production and application.

[0109] Embodiment 7

[0110] This embodiment provides an electrochromic device and a preparation method thereof. The schematic structural diagram of the electrochromic device is as Figure 14 shown. The difference from Embodiment 5 is only that an insulating glue is filled in the cavity 8 formed between the conductive active part (the first conductive layer 21, the ion storage layer 3, the electrolyte layer 4, the electrochromic layer 5, and the second conductive layer 22) and the bending part 13.

[0111] The difference in its preparation method from Embodiment 5 is only that before roll-pressing and injecting the electrolyte material in step (2), an insulating glue is first injected into the bending area, and after curing, the electrolyte material is injected and roll-pressed.

[0112] In this embodiment, filling the insulating glue in the cavity formed between the conductive active part (composed of the first conductive layer, the ion storage layer, the electrolyte layer, the electrochromic layer, and the second conductive layer) and the bending part not only avoids short circuits caused by the mutual contact of the third conductive layer / bus bar at the bending part, but also can effectively isolate water and oxygen, improving the sealing performance of the device.

[0113] Embodiment 8

[0114] This embodiment provides an electrochromic device and a preparation method thereof. The schematic structural diagram of the electrochromic device is as Figure 15 shown. The difference from Embodiment 1 is only that it further includes a sealing part 9, which is arranged between the first substrate 11 and the second substrate 12 to seal the conductive active part composed of the first conductive layer 21, the ion storage layer 3, the electrolyte layer 4, the electrochromic layer 5, and the second conductive layer 22. A first water and oxygen barrier layer 101 is further arranged on the outer side of the first substrate 11, and a second water and oxygen barrier layer 102 is further arranged on the outer side of the second substrate 12.

[0115] The difference in the preparation method from Embodiment 1 is only that after completing the curing process in step (2), a groove is laser-etched on the other three sides (the three sides not connected to the bending part) of the side of the first substrate 11 close to the first conductive layer, and a sealing glue is filled in the groove to form the sealing part 9. Then, a water and oxygen barrier layer is attached to the side of the first substrate and the second substrate away from the electrolyte layer, and the sealing part 9 is in contact with the first water and oxygen barrier layer 101.

[0116] In this embodiment, by introducing a sealing part and a water and oxygen barrier layer, the water and oxygen barrier property and sealing property of the electrochromic device are further improved.

[0117] Example 9

[0118] This embodiment provides a packaging structure of an electrochromic device, and its structural schematic diagram is as Figure 16 shown, including an electrochromic device 1, and an adhesive layer 111 and a base layer 112 arranged outside the electrochromic device 1; the adhesive layer 111 and the base layer 112 are connected to the electrochromic device 1 through a sealant 113.

[0119] In this embodiment, by sequentially arranging an adhesive layer and a base layer outside the electrochromic device, the sealing performance of the electrochromic device can be further improved.

[0120] The applicant declares that the present invention uses the above embodiments to illustrate an electrochromic device and its preparation method and application of the present invention, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of the raw materials selected for the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. An electrochromic device, characterized in that, the electrochromic device includes a first substrate, a first conductive layer, an ion storage layer, an electrolyte layer, an electrochromic layer, a second conductive layer and a second substrate which are stacked; a bending portion is provided on one side of the electrochromic device, and the first substrate, the bending portion and the second substrate are connected to each other to form an integral structure; The cross-section of the bent portion is circular arc-shaped, the perimeter of the cross-section of the bent portion is L, and the thickness of the electrolyte layer of the electrochromic device is d 1 , the ratio of the L to d 1 is (1.57 - 1.60):

1.

2. The electrochromic device according to claim 1, characterized in that, the first substrate, the bending portion and the second substrate are made of the same material, which is a transparent substrate material.

3. The electrochromic device according to claim 1, characterized in that, the first substrate, the bending portion and the second substrate have the same thickness, which is 20 - 500 μm.

4. The electrochromic device according to claim 1, characterized in that, the materials of the first conductive layer and the second conductive layer are transparent conductive materials.

5. The electrochromic device according to claim 1, characterized in that, the thicknesses of the first conductive layer and the second conductive layer are independently 0.1 - 500 nm.

6. The electrochromic device according to claim 1, characterized in that, the thickness of the ion storage layer is 1 - 1000 nm.

7. The electrochromic device according to claim 1, characterized in that, the thickness of the electrolyte layer is 10 - 200 μm.

8. The electrochromic device according to claim 1, characterized in that, the thickness of the electrochromic layer is 100 nm - 5 μm.

9. The electrochromic device according to claim 1, characterized in that, a first lead-out structure is provided on the first conductive layer, and a second lead-out structure is provided on the second conductive layer; the first lead-out structure and the second lead-out structure are lead-out electrodes and / or bus bars.

10. The electrochromic device according to claim 9, characterized in that, the first lead-out structure is a first lead-out electrode, and the second lead-out structure is a second lead-out electrode; the first lead-out electrode is provided on the side of the first conductive layer away from the first substrate, and the second lead-out electrode is provided on the side of the second conductive layer away from the second substrate.

11. The electrochromic device according to claim 9, characterized in that, the first lead-out structure is a first bus bar, and the second lead-out structure is a second bus bar; the first bus bar is provided on the side of the first conductive layer away from the first substrate or between the first conductive layer and the first substrate, and the second bus bar is provided on the side of the second conductive layer away from the second substrate or between the second conductive layer and the second substrate.

12. The electrochromic device according to claim 1, characterized in that, a third conductive layer is provided at one end of the second substrate close to the bending portion, and the third conductive layer is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the first substrate, and the first bus bar extends through the bending portion to between the third conductive layer and the second substrate; a second bus bar is provided between the second conductive layer and the second substrate.

13. The electrochromic device according to claim 1, characterized in that, One end of the first substrate near the bending portion is provided with a third conductive layer, which is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the first substrate; a second bus bar is provided between the second conductive layer and the second substrate, and the second bus bar extends to between the third conductive layer and the first substrate via the bending portion.

14. The electrochromic device according to claim 13, characterized in that one side of the third conductive layer away from the first substrate or the second substrate is in contact with the electrolyte layer.

15. The electrochromic device according to claim 1, characterized in that one end of the second substrate near the bending portion is provided with a third conductive layer, which is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the ion storage layer, and the first bus bar extends to the third conductive layer via the bending portion; a second bus bar is provided between the second conductive layer and the electrochromic layer.

16. The electrochromic device according to claim 1, characterized in that one end of the first substrate near the bending portion is provided with a third conductive layer, which is independent of the first conductive layer and the second conductive layer; a first bus bar is provided between the first conductive layer and the ion storage layer; a second bus bar is provided between the second conductive layer and the electrochromic layer, and the second bus bar extends to the third conductive layer via the bending portion.

17. The electrochromic device according to claim 1, characterized in that the first conductive layer, the ion storage layer, the electrolyte layer, the electrochromic layer and the second conductive layer form a conductive active part, a cavity is formed between the conductive active part and the bending portion, and the cavity is filled with insulating glue.

18. The electrochromic device according to claim 1, characterized in that the electrochromic device further includes a sealing part, which is arranged between the first substrate and the second substrate to seal the conductive active part formed by the first conductive layer, the ion storage layer, the electrolyte layer, the electrochromic layer and the second conductive layer.

19. The electrochromic device according to claim 18, characterized in that the material of the sealing part is sealing glue.

20. The electrochromic device according to claim 1, characterized in that a first water and oxygen barrier layer is further provided on one side of the first substrate away from the first conductive layer, and / or a second water and oxygen barrier layer is further provided on one side of the second substrate away from the second conductive layer.

21. The electrochromic device according to claim 1, characterized in that the outside of the electrochromic device includes an adhesive layer and a base layer arranged in sequence, and the adhesive layer and the base layer are connected to the electrochromic device through sealing glue.

22. A method for manufacturing an electrochromic device according to any one of claims 1 to 21, characterized in that the manufacturing method includes the following steps: (1) Divide the substrate into a first area and a second area. The first conductive layer and the ion storage layer are sequentially arranged on the first area, the second conductive layer and the electrochromic layer are sequentially arranged on the second area, and an interval area is between the first area and the second area to form a preform A; (2) Fold the preform A obtained in step (1) in a direction such that the ion storage layer and the electrochromic layer face each other, inject an electrolyte material between the ion storage layer and the electrochromic layer, and cure to obtain the electrochromic device.

23. The preparation method according to claim 22, characterized in that, The thickness of the electrolyte layer of the electrochromic device is d 1 , the width of the spacer region in step (1) is L, and L≥π·d 1 / 2.

24. The preparation method according to claim 23, characterized in that, The ratio of L to d 1 is (1.57 to 1.60):

1.

25. The preparation method according to claim 22, characterized in that, the preparation method of the spacer region in step (1) is laser etching.

26. The preparation method according to claim 22, characterized in that, the folding method in step (2) is a rolling process.

27. An electronic terminal, characterized in that, the electronic terminal includes the electrochromic device according to any one of claims 1 to 21.

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