Electrochromic device, preparation method thereof, panel and electronic equipment

Abstract

The application belongs to the technical field of electronic device component preparation, and specifically discloses an electrochromic device, a preparation method thereof, a panel and an electronic device. The electrochromic device comprises a first substrate and a second substrate arranged oppositely; an electrolyte layer and a spacer are located between the first substrate and the second substrate, and the spacer is arranged circumferentially along the outer side of the electrolyte layer; and the electrolyte layer comprises inorganic particles, and the particle size of at least part of the inorganic particles is the same as the thickness of the spacer. The electrochromic device provided in the application has good consistency between the two side electrodes, and the preparation method has high yield, and can be used for preparing a display panel or an electronic device.

Description

Technical Field

[0001] This application belongs to the field of electronic device component manufacturing technology, specifically relating to an electrochromic device and its manufacturing method, as well as a panel and electronic device. Background Technology

[0002] Electrochromic materials undergo reversible changes in their optical properties (transmittance or reflectance) under the influence of an applied electric field, resulting in a reversible change in color. Devices made of electrochromic materials are called electrochromic devices. Applying electrochromic devices to the housings of electronic devices can alter the appearance of the devices, and this alteration can be easily controlled by adjusting the electric field applied to the electrochromic device.

[0003] However, current electrochromic devices still suffer from uneven distribution of internal gap thickness. Summary of the Invention

[0004] The technical objective of this application is to solve the problem of uneven internal gap thickness distribution in existing electrochromic devices.

[0005] To address the aforementioned technical problems, this application provides an electrochromic device, comprising:

[0006] A first substrate and a second substrate disposed opposite to each other;

[0007] An electrolyte layer and a spacer are located between the first substrate and the second substrate, wherein the spacer is arranged circumferentially along the outer side of the electrolyte layer;

[0008] The electrolyte layer comprises inorganic particles, at least a portion of which have the same particle size as the thickness of the septum.

[0009] The inorganic particles in this application are uniformly dispersed between the first substrate and the second substrate, which can effectively ensure the uniformity of the gap thickness.

[0010] In some embodiments of this application, the inorganic particles satisfy one or two of the following:

[0011] (1.1) Based on the total volume of the inorganic particles, the particle size of more than 80% of the inorganic particles is the same as the thickness of the spacer.

[0012] (1.2) The particle size of the inorganic particles is 0.01 mm to 1 mm, preferably 0.1 mm to 1 mm;

[0013] (1.3) The inorganic particles comprise one or two of inorganic oxides or transparent silicates, wherein the inorganic oxide comprises one or two of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, and tungsten trioxide.

[0014] In some embodiments of this application, the electrolyte layer further comprises a gel polymer electrolyte.

[0015] In some embodiments of this application, the side of the septum is provided with a liquid outlet;

[0016] Preferably, the outlet includes one or more combinations of notches or through holes.

[0017] A second aspect of this application is to provide a method for fabricating a device, the method comprising:

[0018] A spacer is provided on one side surface of one of the substrates;

[0019] Electrolyte layer material A and electrolyte layer material B are prepared, wherein electrolyte layer material A contains inorganic particles and the viscosity of electrolyte layer material A is lower than that of electrolyte layer material B;

[0020] Electrolyte layer material A is filled into the inner part of the diaphragm;

[0021] The remaining portion of the spacer is filled with electrolyte layer material B;

[0022] Another substrate is disposed on the surface of the electrolyte layer material B.

[0023] The preparation method provided in this application has a high yield rate.

[0024] In some embodiments of this application, the method includes:

[0025] The inner portion of the diaphragm is filled with electrolyte layer material A and then cured to form an electrolyte layer.

[0026] and / or;

[0027] The remaining portion of the septum is filled with electrolyte layer material B so that the electrolyte layer material B extends beyond the edge of the septum.

[0028] In some embodiments of this application, the method further includes:

[0029] The substrate is pressurized to allow excess electrolyte layer material B to be discharged from the septum.

[0030] In some embodiments of this application, the method further includes:

[0031] A circumferential seal is performed along the outer side of the spacer.

[0032] A third aspect of this application is to provide a panel comprising the electrochromic device described in the first aspect or the electrochromic device prepared by the preparation method described in the second aspect.

[0033] A fourth aspect of this application is to provide an electronic device, including the panel described in the third aspect, and further including a control circuit connected to the panel. Attached Figure Description

[0034] Figure 1 , Figure 2 This is a schematic diagram of the structure of an electrochromic device in the prior art;

[0035] Figure 3 This is a schematic diagram of the structure of the electrochromic device involved in some embodiments of this application;

[0036] Figure 4A , 4B for Figure 3 Schematic diagram of the structure of the partition pad;

[0037] Figure 5A , 5B 5C and 5D are schematic diagrams illustrating the process of preparing electrochromic devices according to some embodiments of this application;

[0038] Figure 6 This is a flowchart illustrating the preparation process involved in some embodiments of this application;

[0039] Figure 7 This is a flowchart illustrating the preparation process involved in some embodiments of this application;

[0040] The component numbers in the attached diagram are as follows:

[0041] 100, First substrate; 200, Second substrate; 300, Electrolyte layer; 400, Spacer; 500, Sealant;

[0042] 310 Inorganic particles; 320 Electrolyte layer material A; 330 Electrolyte layer material B; 410 Liquid outlet.

[0043] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the scope of this application. Furthermore, the same reference numerals denote the same parts throughout the drawings. Detailed Implementation

[0044] Electrochromic devices are classified into two main categories based on their structure, as follows: Figure 1 , Figure 2As shown, the first device includes a first transparent substrate, a first transparent conductive layer, an electrochromic gel, a second conductive layer, and a second substrate; the second device includes a first transparent substrate, a working electrode (including a transparent conductive layer and an electrochromic layer), an electrolyte layer, and a counter electrode (including a transparent conductive layer and an ion storage layer). For ease of description, the transparent substrate / transparent conductive layer, transparent substrate / working electrode, and transparent substrate / counter electrode are collectively referred to as transparent electrodes. In the second device structure, the electrolyte layer can be divided into three categories according to its composition and state: liquid electrolyte, polymer electrolyte, and inorganic solid electrolyte. Liquid electrolytes are prone to leakage during encapsulation and use, posing significant safety hazards, and have poor weather resistance and stability; currently, there are few electrochromic products that directly use liquid electrolytes. Inorganic solid electrolytes have low ionic conductivity, require coating equipment for preparation, and have low yield. Polymer electrolytes include solid polymer electrolytes, gel polymer electrolytes, and mixed polymer electrolytes. Gel polymer electrolytes are prepared by dissolving inorganic lithium salts in organic solvents and compounding them into a polar polymer matrix. They are mostly prepared by the sol-gel method. Their ion mobility is higher than that of solid-state types, and they have the advantages of low cost and easy operation. Electrochromic devices containing gels have the advantages of fast color change response (the response speed in this article refers to the time taken for the transmittance to reach 90% of the final change value when the device changes from a fading state to a colored state or from a colored state to a fading state) and high yield, which has attracted widespread attention.

[0045] However, due to the thinness of the gel layer, ranging from tens to hundreds of micrometers, and its low hardness, it is easily deformed. When the two electrode areas are large or thin, it can easily lead to uneven distribution of the gap thickness, resulting in uneven color and inconsistent color changes in electrochromic devices.

[0046] Patent (CN 114114776 A) discloses a method of applying a thin, uniformly thick insulating strip of adhesive to the inner edges and / or inner fixed surfaces of two rigid flat electrodes to achieve uniform and controllable gaps between the two electrodes and effective isolation between adjacent gaps. Patent (CN 114167657 A) discloses a method of achieving uniform and controllable gaps between two large-area electrodes by adding uniformly thick insulating wires or strips to the edges and / or interiors of two flat electrodes with a certain degree of rigidity.

[0047] However, the above method is based on planar electrodes and is not suitable for fabricating electrochromic devices based on curved or flexible substrates. On the other hand, in order to ensure smooth operation during the filling process, a certain distance must be maintained between the spacers, which makes it impossible to guarantee the uniformity of the gap thickness within the area between the spacers.

[0048] In dye-based liquid crystal packaging technology, spacers are added between substrates to ensure uniform spacing between the two substrates. For example, patents (CN 111240103 A) and (CN 114791684 A) disclose cylindrical spacers PS (PhotoSpacer) and spherical spacers BS (Ball Spacer), respectively. Although the spacers can partially solve the problem of uneven gap thickness distribution, the yield of the products is not high due to the limitations of the entire manufacturing process.

[0049] To address the aforementioned technical problems, this application discloses an electrochromic device, such as... Figure 3 As shown, the electrochromic device includes: a first substrate 100 and a second substrate 200 disposed opposite to each other; an electrolyte layer 300 and a spacer 400 located between the first substrate 100 and the second substrate 200, the spacer 400 being arranged circumferentially along the outer side of the electrolyte layer 300; and the electrolyte layer 300 including inorganic particles 310, at least a portion of the inorganic particles 310 having the same particle size as the thickness of the spacer 400.

[0050] In this application, "at least part" includes both a portion and all of the particles. The term "particle size" in this application includes the maximum particle size of inorganic particles, which can be directly measured using conventional measuring instruments in the art.

[0051] The inorganic particles in this application are uniformly dispersed between the first substrate and the second substrate, which can effectively ensure the uniformity of the gap thickness.

[0052] In some embodiments of this application, the inorganic particles satisfy one or two of the following:

[0053] (1.1) Based on the total volume of inorganic particles, the particle size of more than 80% of inorganic particles is the same as the thickness of the spacer.

[0054] (1.2) The particle size of the inorganic particles is 0.01 mm to 1 mm, preferably 0.1 mm to 1 mm;

[0055] (1.3) The inorganic particles include one or two of inorganic oxides or transparent silicates, and the inorganic oxides include one or two of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, and tungsten trioxide.

[0056] This application selects inorganic particles with a particle size of more than 80% that is the same as the thickness of the spacer. These inorganic particles are uniformly and effectively distributed between the substrates, making it suitable for large-size electrochromic devices, flexible electrochromic devices, or electrochromic devices with curved surfaces.

[0057] The inorganic particles in this application have a particle size of any one of 0.01mm, 0.05mm, 0.08mm, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, and 1.0mm, or satisfy any of these ranges or specific values. This application chooses to set the particle size of the inorganic particles to 0.01mm to 1mm, which means the distance between the substrates is 0.01mm to 1mm. This ensures uniform color change of the device without affecting its conductivity. Furthermore, when the particle size of the inorganic particles is 0.1mm to 1mm, the overall performance in achieving uniform color change and conductivity is relatively superior.

[0058] The inorganic particle material selected in this application includes, but is not limited to, the types listed above. The inorganic particles containing this material have insulating and transparent properties, and have little impact on the electrochromic function of the device.

[0059] In some embodiments of this application, the electrolyte layer further comprises a gel polymer electrolyte.

[0060] The gel polymer electrolyte in this application comprises a solvent, polymer monomers, an initiator, an electrochromic material, a lithium salt, and an ionic liquid. The solvent includes, but is not limited to, one or a mixture of ethanol, dimethyl sulfoxide, isopropanol, propylene carbonate, ethylene carbonate, acetonitrile, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, or tetrahydrofuran. The monomers include, but are not limited to, one or a mixture of epoxy acrylate, urethane acrylate, polyester acrylate, vinyl polyester, acrylic resin, or methyl methacrylate. The lithium salt includes, but is not limited to, one or a mixture of LiPF6, LiClO4, LiAsF6, LiBF4, LiCF3SO3, LiBr, LiCl, LiI, or LiSCN. The initiator includes, but is not limited to, organic peroxides (acyl peroxides, hydroperoxides, dialkyl peroxides, ketone peroxides, dicarbonate peroxides), inorganic peroxides (sulfates), azo initiators, and redox initiators (generally any common redox pair materials are acceptable). Ionic liquids include, but are not limited to, those containing quaternary ammonium cations, imidazole cations, or pyrrole cations, as well as halide anions, tetrafluoroborate anions, or hexafluorophosphate anions. Electrochromic materials include viologen-based small molecule materials.

[0061] The choice of a gel polymer electrolyte as the main component of the electrolyte layer in this application is advantageous for the formation of electrochromic devices using the preparation method described in this application.

[0062] In some embodiments of this application, the side of the septum is provided with a liquid outlet.

[0063] In this application, the spacer acts as a spacer between the substrates. The material of the spacer is selected to be both insulating and not easily dissolved by the solvent in the gel polymer electrolyte, such as (1) polymer fiber materials: polypropylene fiber, polyethylene terephthalate fiber, polyacrylonitrile fiber, polyamide fiber, polypropylene fiber, polyethylene fiber, aromatic polyamide fiber, poly(p-phenylene benzobisoxazole) fiber, poly(benzimidazole) fiber, poly(p-phenylene pyridinium diimidazole) fiber or polyimide fiber polymer fiber materials, etc.; (2) ultraviolet (UV) or thermosetting adhesive: the main material is epoxy propylene ester, acrylate, polyurethane acrylate, polyester acrylate; and it also contains various additives such as plasticizers, stabilizers, and initiators.

[0064] This application has a liquid outlet on the side of the septum, which facilitates the uniform and effective dispersion of inorganic particles using gel polymer electrolytes.

[0065] In some embodiments of this application, at least one of the first substrate and the second substrate may be a flat plate, a curved plate, or a flexible plate, etc.

[0066] In some embodiments of this application, the outlet includes one or more combinations of notches or through holes.

[0067] like Figure 4A , 4B The outlet can be a notch or a through hole, the purpose of which is to drain excess gel polymer electrolyte and facilitate the uniform and effective dispersion of inorganic particles. Any shape of the notch and through hole is within the scope of protection of this application, and to reduce the loss of inorganic particles, this application selects the diameter or aperture of the notch and / or through hole to be smaller than the particle size of the inorganic particles.

[0068] The electrochromic device provided in this application can be used in panels, such as photochromic glass in aerospace equipment and automobiles. Furthermore, the electronic device formed by connecting this panel to a control circuit can be any of various types of computer system devices that are mobile or portable and perform wireless communication. The control circuit in this application can include storage circuitry and processing circuitry. The storage circuitry and processing circuitry can be memory, such as hard disk drive memory, non-volatile memory (e.g., flash memory or other electronically programmable read-only memory used to form solid-state drives), volatile memory (e.g., static or dynamic random access memory), etc. Thus, the functionalities of the electronic device can be realized.

[0069] Specifically, electronic devices can be mobile phones or smartphones (e.g., iPhone™, Android™ based phones), portable gaming devices (e.g., Nintendo DS™, PlayStation Portable™, Gameboy Advance™, iPhone™), laptops, PDAs, portable internet devices, music players and data storage devices, other handheld devices, and devices such as watches, in-ear headphones, pendants, and headphones. Electronic devices can also be other wearable devices (e.g., head-mounted devices such as electronic glasses, electronic clothing, electronic bracelets, electronic necklaces, electronic tattoos, electronic devices, or smartwatches).

[0070] The second aspect of this application is to provide a method for fabricating the above-mentioned device, as shown in Figure 5. Figure 6 , Figure 7 The method, as illustrated, includes:

[0071] S100, A spacer is provided on one side surface of one of the substrates;

[0072] S200. Prepare electrolyte layer material A and electrolyte layer material B. Electrolyte layer material A contains inorganic particles and the viscosity of electrolyte layer material A is lower than that of electrolyte layer material B.

[0073] S300, fill the inner part of the septum with electrolyte layer material A;

[0074] S400, Fill the remaining portion of the septum with electrolyte layer material B;

[0075] S500, Place another substrate on the surface of electrolyte layer material B.

[0076] In this application, the difference in the composition of electrolyte layer material A and electrolyte layer material B is that electrolyte layer material A contains inorganic particles, and a more suitable solvent is used in electrolyte layer material A to make its viscosity lower than that of electrolyte layer material B. The purpose is to facilitate the uniform and effective distribution of inorganic particles in electrolyte layer material A.

[0077] The preparation method provided in this application has a high yield rate.

[0078] In some embodiments of this application, the method includes: partially filling the interior of the septum with electrolyte layer material A and curing it to form an electrolyte layer.

[0079] In some embodiments of this application, the method includes filling the remaining portion of the septum with electrolyte layer material B such that the electrolyte layer material B extends beyond the edge of the septum.

[0080] In some embodiments of this application, the method further includes: pressurizing the substrate to cause excess electrolyte layer material B to drain from the spacer.

[0081] In some embodiments of this application, the method further includes: circumferential sealing along the outside of the spacer.

[0082] Example 1

[0083] A method for fabricating an electrochromic device is provided:

[0084] (1) Composition of electrochromic device: ITO and WO3 thin films are deposited sequentially on a flat glass (1000mm*800mm), which is called the bottom transparent electrode; ITO and NiO thin films are deposited sequentially on another flat glass (1000mm*800mm), which is called the upper transparent electrode. The middle layer is a gel polymer electrolyte, which contains the solvent propylene carbonate, the polymer monomer contains methyl methacrylate, the initiator is dicarbonate peroxide, the electrochromic material is viologen-type small molecule material, lithium salt and ionic liquid.

[0085] (2) Apply adhesive to the four edges of the bottom transparent electrode to form a perimeter septum, leaving an outlet. The septum is 0.2 mm high and 2 mm wide. The adhesive contains an acrylic adhesive.

[0086] (3) Spray a layer of low viscosity prepolymer A in the area of ​​the surrounding spacer frame, dissolve lithium salt, methyl methacrylate and silica glass beads in propylene carbonate to form prepolymer A, wherein the diameter of the silica glass beads is 0.2 mm; heat at 80°C for 2 hours, the prepolymer A solidifies, and fixes the silica glass particles on the surface of the bottom transparent electrode.

[0087] (4) A layer of gel polymer B is scraped onto the surface of the solidified prepolymer A, and lithium salt and polymethyl methacrylate are dissolved in propylene carbonate to form gel polymer B.

[0088] (5) The upper transparent electrode is laminated on top of the lower transparent electrode. Pressure is applied evenly to the surface of the upper transparent electrode. During the pressure application, excess gel polymer B is squeezed out from the outlet. Wipe away the excess gel polymer around the electrode edges and apply sealant along the septum to seal it.

[0089] (6) Transmittance at 550nm wavelength: The deviation of the transmittance of the entire device under colored and faded conditions is ≤2%. Specifically: Under colored conditions, the transmittance deviation of the entire surface of the device is ≤2%; under faded conditions, the transmittance deviation of the entire surface is ≤2%.

[0090] Example 2

[0091] A method for fabricating an electrochromic device is provided:

[0092] The preparation process is the same as in Example 1, except that the flat glass is replaced with a multi-curvature curved glass, which has different curvatures in different areas. The material of this curved glass is a conventional material in the art, such as tempered glass.

[0093] For example, this embodiment uses an electrochromic device with an arch height of about 150mm, and its coloring and fading transmittance at a wavelength of 550nm: the deviation of the coloring and fading transmittance of the entire device is ≤2.5%.

[0094] Example 3

[0095] A method for fabricating an electrochromic device is provided:

[0096] The preparation process is the same as in Example 1, except that the flat glass is replaced with a flexible PET film with a thickness of about 150 μm.

[0097] Coloring and fading transmittance at 550nm wavelength: The deviation of coloring and fading transmittance across the entire device is ≤2%.

[0098] In summary, this application provides an electrochromic device and its fabrication method. The electrochromic device exhibits good uniformity in the spacing between its two electrodes, and the fabrication method boasts a high yield rate, making it suitable for fabricating display panels or electronic devices.

[0099] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. An electrochromic device, characterized in that, include: A first substrate and a second substrate disposed opposite to each other; An electrolyte layer and a spacer are located between the first substrate and the second substrate, wherein the spacer is arranged circumferentially along the outer side of the electrolyte layer; The electrolyte layer comprises inorganic particles, at least a portion of which have the same particle size as the thickness of the spacer. The method for preparing the electrochromic device includes: A spacer is provided on one side surface of one of the substrates; Electrolyte layer material A and electrolyte layer material B are configured. The difference between electrolyte layer material A and electrolyte layer material B is that electrolyte layer material A contains inorganic particles, and the viscosity of electrolyte layer material A is lower than that of electrolyte layer material B by adjusting the solvent in electrolyte layer material A and electrolyte layer material B. The inner portion of the septum is filled with electrolyte layer material A, and the electrolyte layer material A is cured. The remaining portion of the spacer is filled with electrolyte layer material B; Another substrate is disposed on the surface of the electrolyte layer material B.

2. The device according to claim 1, characterized in that, The inorganic particles satisfy one or more of the following combinations: (1.1) Based on the total volume of the inorganic particles, the particle size of more than 80% of the inorganic particles is the same as the thickness of the spacer; (1.2) The particle size of the inorganic particles is 0.01 mm to 1 mm; (1.3) The inorganic particles comprise one or two of inorganic oxides or transparent silicates, wherein the inorganic oxide comprises one or two of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, and tungsten trioxide.

3. The device according to claim 1, characterized in that, The inorganic particles have a particle size of 0.1 mm to 1 mm.

4. The device according to claim 1, characterized in that, The electrolyte layer also contains a gel polymer electrolyte.

5. The device according to any one of claims 1 to 4, characterized in that, The septum has a liquid outlet on its side.

6. The device according to claim 5, characterized in that, The liquid outlet includes one or both of the following: a notch or a through hole.

7. A method for fabricating the device according to any one of claims 1 to 6, characterized in that: The method includes: A spacer is provided on one side surface of one of the substrates; Electrolyte layer material A and electrolyte layer material B are configured. The difference between electrolyte layer material A and electrolyte layer material B is that electrolyte layer material A contains inorganic particles, and the viscosity of electrolyte layer material A is lower than that of electrolyte layer material B by adjusting the solvent in electrolyte layer material A and electrolyte layer material B. The inner portion of the septum is filled with electrolyte layer material A, and the electrolyte layer material A is cured. The remaining portion of the spacer is filled with electrolyte layer material B; Another substrate is disposed on the surface of the electrolyte layer material B.

8. The method according to claim 7, characterized in that: The method includes: The remaining portion of the septum is filled with electrolyte layer material B so that the electrolyte layer material B extends beyond the edge of the septum.

9. The method according to claim 8, characterized in that: The method further includes: The substrate is pressurized to allow excess electrolyte layer material B to be discharged from the septum.

10. The method according to claim 7, 8, or 9, characterized in that: The method further includes: A circumferential seal is performed along the outer side of the spacer.

11. A panel, characterized in that, It includes the electrochromic device according to any one of claims 1 to 6 or the electrochromic device prepared by the preparation method according to any one of claims 7 to 10.

12. An electronic device, characterized in that, The device includes the panel of claim 11, and further includes a control circuit connected to the panel.

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