Electrochromic device structure

Abstract

The present disclosure relates to the field of electrochromism, and provides an electrochromic device structure. The electrochromic device structure comprises: a first transparent substrate layer, a first transparent conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, a second transparent conductive layer and a second transparent substrate layer, wherein the first transparent substrate layer is a flexible substrate; the first transparent conductive layer is located on the top surface of the first transparent substrate layer; the electrochromic layer is located on the top surface of the first transparent conductive layer; the electrolyte layer is located on the top surface of the electrochromic layer; the ion storage layer is located on the top surface of the electrolyte layer; the second transparent conductive layer is located on the top surface of the ion storage layer; and the second transparent substrate layer is located on the top surface of the second transparent conductive layer, and is a flexible substrate. By using the solution, a flexible device structure with bendable properties can be prepared.

Description

An electrochromic device structure

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to the Chinese patent application No. 202322304503.5 filed with the China Patent Office on August 25, 2023, the entire contents of which are incorporated by reference into this application. Technical Field

[0003] The present disclosure relates to the field of electrochromism, and in particular to an electrochromic device structure. Background Art

[0004] Electrochromism (EC) refers to the phenomenon in which, under the influence of an external electric field, a material undergoes oxidation or reduction, resulting in a reversible change in its transmission or reflection of light, manifesting as a reversible change in color and transparency. Electrochromic devices have shown promising real-world applications and are widely used in products such as electrochromic energy-saving smart windows, automotive rearview mirrors, electrochromic displays, electrochromic memory devices, and color-changing sunglasses. Electrochromic materials have a broad range of applications, and with the advancement of science and technology in the new century and continued in-depth research and exploration, electrochromic materials and their devices will undoubtedly become more widely used.

[0005] Existing electrochromic devices generally use rigid substrates, including rigid transparent or colored glass, which are not bendable. Therefore, a flexible electrochromic device structure with bendability is needed.

[0006] Summary of the Invention

[0007] The present disclosure provides an electrochromic device structure to at least solve the above technical problems existing in the prior art.

[0008] According to a first aspect of the present disclosure, there is provided an electrochromic device structure, comprising:

[0009] a first transparent substrate layer, wherein the first transparent substrate layer is configured as a flexible substrate;

[0010] a first transparent conductive layer, wherein the first transparent conductive layer is located on a top surface of the first transparent base layer;

[0011] an electrochromic layer, the electrochromic layer being located on a top surface of the first transparent conductive layer;

[0012] an electrolyte layer, the electrolyte layer being located on a top surface of the electrochromic layer;

[0013] an ion storage layer, the ion storage layer being located on a top surface of the electrolyte layer;

[0014] a second transparent conductive layer, wherein the second transparent conductive layer is located on a top surface of the ion storage layer;

[0015] a second transparent substrate layer, the second transparent substrate layer being located on a top surface of the second transparent conductive layer, and the second transparent substrate layer being configured as a flexible substrate;

[0016] The electrochromic layer and the ion storage layer are configured to have at least two superimposed colors when subjected to voltage.

[0017] In one embodiment, the electrochromic layer includes: a first electrochromic layer and a second electrochromic layer covering a top surface of the first electrochromic layer.

[0018] In one embodiment, the total thickness of the first electrochromic layer and the second electrochromic layer is 200 nm-1600 nm.

[0019] In one embodiment, the ion storage layer is constructed as a NiO composite film layer having a three-dimensional network pore structure.

[0020] In one embodiment, the electrolyte layer is constructed as a nickel tungstate electrolyte layer, and the nickel tungstate electrolyte layer is made by the lithium ions of the lithium ion solid electrolyte film deposited on the top surface of the NiO composite film layer reacting at the interface of the WO3 composite film color-changing layer.

[0021] In one embodiment, the radius of the lithium ions is smaller than the radius of the pores of the NiO composite film layer.

[0022] In one embodiment, the first transparent substrate layer and the second transparent substrate layer are both made of ultra-thin transparent glass, polyimide or PET.

[0023] In one embodiment, the first transparent conductive layer and the second transparent conductive layer are both constructed of one of transparent ITO, a transparent nanosilver conductive layer, or a transparent conductive metal grid.

[0024] In one possible implementation, the electrochromic device structure further includes: a water and oxygen barrier film layer;

[0025] The water and oxygen barrier film layer is located on the side of the first transparent substrate layer away from contact with air; and / or

[0026] The water and oxygen barrier film layer is located on a side of the second transparent substrate layer away from contact with air.

[0027] The electrochromic device structure disclosed herein includes a first transparent substrate layer and a second transparent substrate layer, each of which is a flexible substrate. This allows the entire electrochromic device structure to be flexible and bendable. Furthermore, the electrochromic layer and the ion storage layer are configured to exhibit at least two superimposed color changes, allowing the glass to undergo at least two superimposed color changes under the action of a voltage. This allows for a superimposed color change effect, further enhancing the shielding effect.

[0028] It should be understood that the contents described in this section are not intended to identify the key or important features of the embodiments of the present disclosure, nor are they intended to limit the scope of the present disclosure. Other features of the present disclosure will become readily understood through the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The above and other objects, features and advantages of the exemplary embodiments of the present disclosure will become readily understood by reading the detailed description below with reference to the accompanying drawings, in which several embodiments of the present disclosure are shown by way of example and not limitation, wherein:

[0030] In the drawings, the same or corresponding reference numerals denote the same or corresponding parts.

[0031] FIG1 shows a first schematic diagram of a layered structure of an electrochromic device structure according to an embodiment of the present disclosure.

[0032] FIG2 shows a second schematic diagram of the layered structure of the electrochromic device structure according to an embodiment of the present disclosure.

[0033] FIG3 shows a third schematic diagram of the layered structure of the electrochromic device structure according to an embodiment of the present disclosure.

[0034] Explanation of the numbers in the figure: 10 - electrochromic device structure; 11 - first transparent substrate layer; 12 - first transparent conductive layer; 13 - electrochromic layer; 14 - electrolyte layer; 15 - ion storage layer; 16 - second transparent conductive layer; 17 - adhesive layer; 18 - second transparent substrate layer; 181 - water and oxygen barrier film layer; 19 - sealant. DETAILED DESCRIPTION

[0035] To make the purposes, features, and advantages of the present disclosure more apparent and understandable, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present disclosure, not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present disclosure without creative work shall fall within the scope of protection of the present disclosure.

[0036] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used here to describe the spatial positional relationship between one or more components or features shown in the figures and other components or features. It should be understood that spatially relative terms include not only the orientation of the components as described in the figures, but also different orientations during use or operation. For example, if the components in the drawings are inverted as a whole, the situation where the components are "above other components or features" or "above other components or features" will include the situation where the components are "below other components or structures" or "below other components or structures". Thus, the exemplary term "above" may include both the orientations "above" and "below". In addition, these components or features may also be positioned at other different angles (e.g., rotated 90 degrees or other angles), and this document is intended to include all of these situations.

[0037] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present disclosure. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, parts, components and / or combinations thereof.

[0038] It should be noted that the terms "first," "second," and the like in the specification, claims, and drawings of the present disclosure are used to distinguish similar objects, and are not necessarily used to describe a specific order or precedence. It should be understood that the terms used in this manner are interchangeable where appropriate, such that the embodiments of the present disclosure described herein are intended to be implemented in an order other than that illustrated or described herein.

[0039] In the description of the present disclosure, it should be understood that the orientation or positional relationship indicated by the directional words is usually based on the orientation or positional relationship shown in the accompanying drawings, and is only for the convenience of describing the present disclosure and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the device or element referred to must have a specific orientation or be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the scope of protection of the present disclosure; the directional words "inside" and "outside" refer to the inside and outside relative to the outline of each component itself.

[0040] The electrochromic device glass currently used does not have bendable properties, which results in limited application scenarios for it.

[0041] In order to improve the bendability of an electrochromic device structure, an embodiment of the present disclosure provides an electrochromic device structure. The electrochromic device structure includes, but is not limited to, applications in automobile windows.

[0042] The electrochromic device structure 10 provided in the embodiment of the present disclosure, with reference to Figures 1 to 3, may include, from bottom to top, a first transparent substrate layer 11, a first transparent conductive layer 12, an electrochromic layer 13, an electrolyte layer 14, an ion storage layer 15, a second transparent conductive layer 16, and a second transparent substrate layer 18. The first transparent substrate layer 11 may be configured as a flexible substrate; the first transparent conductive layer 12 is located on the top surface of the first transparent substrate layer 11; the electrochromic layer 13 is located on the top surface of the first transparent conductive layer 12; the electrolyte layer 14 is located on the top surface of the electrochromic layer 13, and the ion storage layer 15 is located on the top surface of the electrolyte layer 14; the second transparent conductive layer 16 is located on the top surface of the ion storage layer 15; and the second transparent substrate layer 18 is located on the top surface of the second transparent conductive layer 16. The second transparent substrate layer 18 is configured as a flexible substrate. The electrochromic layer 13 of the embodiment of the present disclosure may be formed using a corresponding deposition process according to actual needs.

[0043] The electrochromic device structure 10 of the disclosed embodiment, employing a flexible substrate with a first transparent substrate layer 11 and a second transparent substrate layer 18, enables the entire electrochromic device structure 10 to possess flexible and bendable properties. Furthermore, the electrochromic layer 13 and the ion storage layer 15 are configured to exhibit at least two superimposed color changes under the action of a voltage. This allows the glass to undergo at least two superimposed color changes under the action of a voltage, thereby superimposing the at least two color change effects and further enhancing the shielding effect.

[0044] In some embodiments, the electrochromic layer 13 includes a first electrochromic layer 13 and a second electrochromic layer 13 covering the top surface of the first electrochromic layer 13 .

[0045] Depending on the requirements of structural performance, the first electrochromic layer 13 can be the same as or different from the second electrochromic layer 13. In this way, the electrochromic layer 13 of the embodiment of the present disclosure can enhance the effect of color change of blue light or other color light, thereby further achieving the blocking effect of color superposition.

[0046] In some embodiments, the first electrochromic layer and the second electrochromic layer are both configured as cathode electrochromic WO3 composite thin film color-changing layers containing niobium.

[0047] In some embodiments, the overall thickness of the first electrochromic layer and the second electrochromic layer is 200 nm to 1600 nm.

[0048] In some embodiments, the ion storage layer 15 is constructed as a NiO composite film layer with a three-dimensional mesh pore structure. In this way, the three-dimensional mesh pore structure of the ion storage layer 15 can provide a migration channel for lithium ions, preparing for the migration and color change of lithium ions under the action of voltage.

[0049] In some embodiments, the electrolyte layer 14 is constructed as a nickel tungstate electrolyte layer. The nickel tungstate electrolyte layer is formed by the lithium ions of the lithium ion solid electrolyte thin film deposited on the top surface of the NiO composite film layer reacting at the interface of the WO3 composite thin film color-changing layer. It should be noted that the lithium ions do not need to pass through the WO3 composite thin film color-changing layer. The lithium ions only react with the surface interface of the WO3 composite thin film color-changing layer to form the nickel tungstate electrolyte layer.

[0050] For example, lithium ions can undergo redox reaction with the surface interface of the WO3 composite thin film color-changing layer during high-temperature treatment.

[0051] In some embodiments, the radius of the lithium ions is smaller than the radius of the pores in the NiO composite film. Thus, under the action of an applied electric field (i.e., voltage), the lithium ions can pass through the pores and reach the interface of the WO3 composite film color-changing layer, thereby achieving a yellow light color change.

[0052] In some embodiments, the first transparent substrate layer 11 and the second transparent substrate layer 18 are both made of one or more of ultra-thin transparent glass, polyimide, or PET, so that the entire electrochromic device can have flexible and bendable properties.

[0053] In some embodiments, the first transparent conductive layer 12 and the second transparent conductive layer 16 are both constructed as a combination of transparent ITO (Indium Tin Oxide, conductive film), a transparent nanosilver conductive layer, or a transparent conductive metal grid.

[0054] In some embodiments, the electrochromic device structure 10 further includes a water and oxygen barrier film layer 181 .

[0055] For example, referring to FIG1 , the water and oxygen barrier film layer 181 can be located on the side of the first transparent substrate layer 11 away from air contact. Alternatively, for example, referring to FIG2 , the water and oxygen barrier film layer 181 can also be located on the side of the second transparent substrate layer 18 away from air contact. Alternatively, for example, referring to FIG3 , the water and oxygen barrier film layer 181 can be provided on both the side of the first transparent substrate layer 11 away from air contact and the side of the second transparent substrate layer 18 away from air contact. In this way, the water and oxygen barrier film layer 181 can further extend the service life of the electrochromic device structure 10 according to the disclosed embodiment.

[0056] By using the electrochromic device structure 10 according to the embodiment of the present disclosure, the adhesion of each layer structure is stronger.

[0057] For example, the electrochromic device structure 10 according to the embodiment of the present disclosure may further include an adhesive layer 17 .

[0058] For example, referring to FIG2 , the adhesive layer 17 may be bonded to the side of the second transparent substrate layer 18 having the water and oxygen barrier film layer 181. Alternatively, for example, and not shown in the figure, the adhesive layer 17 may be bonded to the side of the first transparent substrate layer 11 having the water and oxygen barrier film layer 181. Alternatively, for example, and not shown in the figure, the adhesive layer 17 may be bonded to both the side of the second transparent substrate layer 18 having the water and oxygen barrier film layer 181 and the side of the first transparent substrate layer 11 having the water and oxygen barrier film layer 181.

[0059] Alternatively, illustratively, referring to FIG. 3 , the first transparent conductive layer 12 can be directly formed on the side of the first transparent base layer 11 having the water and oxygen barrier film layer 181 by using a coating process.

[0060] Alternatively, illustratively, the second transparent conductive layer 16 and the side of the second transparent base layer 18 with the water and oxygen barrier film layer 181 can be directly formed by using a coating process.

[0061] To further obtain the electrochromic device structure 10 of the embodiment of the present disclosure, it can be prepared in the following manner:

[0062] Exemplarily, the first transparent base layer 11 in the embodiment of the present disclosure can be a clean substrate glass as the base, a high-purity Si target (purity of 99.99%) as the target material, argon and oxygen as the working gases, and a reactive magnetron co-sputtering method is used to prepare the SiO2 substrate layer; the basic parameters are: background vacuum degree of 6*10-4Pa, flow ratio of argon and oxygen of 40:7, working gas pressure of 0.6-1Pa, medium frequency bias, sputtering power of DC150W, and deposition to form a silicon-rich substrate layer.

[0063] Illustratively, the first transparent conductive layer 12 of the disclosed embodiment can use argon and oxygen as working gases, and utilize indium tin oxide ceramic targets to deposit a layer of ITO transparent conductive film with a thickness of 20-400nm on the underlying substrate layer by DC reactive sputtering; the basic parameters are: background vacuum degree of 6*10-4Pa, flow ratio of argon and oxygen of 49.5:0.5, working gas pressure of 0.3-1.0Pa, sputtering power of DC130W, and substrate temperature of room temperature to form the underlying ITO.

[0064] Exemplarily, the electrochromic layer 13 of the embodiment of the present disclosure can be made of metal tungsten and niobium oxide targets, with argon and oxygen as working gases, and the basic parameters are: background vacuum is 6*10-4Pa, the flow ratio of argon and oxygen is 3:0.8, the working gas pressure is 2-3Pa, the sputtering power is DC220W, and when the substrate temperature is 350°C, deposition is performed once to obtain the first WO3 composite thin film color-changing layer, that is, the first electrochromic layer 13; when the substrate temperature is 20°C, deposition is performed a second time to obtain the second WO3 composite thin film color-changing layer, that is, the second electrochromic layer 13; and then a niobium-containing cathode electrochromic WO3 composite thin film color-changing layer with a thickness of 200nm-600nm is obtained.

[0065] In the embodiment of the present disclosure, argon can be used as the working gas, and a NiO composite film layer with a thickness of 100-500 μm can be deposited on the top surface of the electrochromic layer 13 by reactive sputtering using a niobium oxide composite alloy nickel target; the basic parameters are: background vacuum degree is 6*10-4 Pa, the flow ratio of argon and methane is 50:1, the working gas pressure is 0.6-1 Pa, the sputtering power is DC300 W, and the substrate temperature is 300°C. Afterwards, a solid electrolyte film with a thickness of 50-100 nm is further deposited on the NiO composite film layer using a lithium target using argon and oxygen as working gases. The basic parameters are: background vacuum of 6*10-4 Pa, flow ratio of argon and oxygen of 5:0.2, working pressure of 2-3 Pa, and substrate temperature of 100-200°C. The film structure formed at this time is not an inorganic electrolyte layer: the WO3 composite thin film color-changing layer formed in the electrochromic layer 13 has a dense structure at the interface, and the NiO composite film layer formed in the ion storage layer 15 has a three-dimensional network pore structure, the pore radius of which is larger than the radius of lithium ions, and lithium ions can easily pass through the layer and enter the interface of the aforementioned WO3 composite thin film color-changing layer. At this interface layer, a high-temperature annealing of 350-450°C can be performed, and the lithium ions form a nickel tungstate lithium electrolyte layer with a thickness of 10-150 nm with the WO3 composite thin film color-changing layer at the interface. This layer is the electrolyte layer 14 of the electrochromic device structure 10.

[0066] Illustratively, the second transparent conductive layer 16 of the disclosed embodiment can use argon and oxygen as working gases, and utilize indium tin oxide ceramic targets to deposit a layer of ITO transparent conductive film with a thickness of 20-400 nm on the ion storage layer 15 by DC reactive sputtering; the basic parameters are: background vacuum of 6*10-4Pa, flow ratio of argon and oxygen of 49.5:0.5, working gas pressure of 0.3-1.0Pa, sputtering power of DC130W, and substrate temperature of room temperature to form a top layer of ITO.

[0067] Exemplarily, the second transparent base layer 18 of the embodiment of the present disclosure can be based on the above-mentioned coated glass as the base, with a high-purity Si target (purity of 99.99%) as the target material, argon and oxygen as the working gases, and a reactive magnetron co-sputtering method is used to prepare the SiO2 substrate layer; the basic parameters are: background vacuum degree is 6*10-4Pa, the flow ratio of argon and oxygen is 40:7, the working gas pressure is 0.6-1Pa, the medium frequency bias, the sputtering power is DC150W, and a silicon-rich substrate layer is deposited.

[0068] Exemplarily, after the electrochromic device prepared in the above steps is made into electrodes through laser and silk screen printing processes, it is bonded and packaged together with a second transparent base layer 18 (organic transparent substrate such as CPI, PET, etc.) with a water and oxygen barrier film layer 181 through a vacuum bonding process. In particular, the sealant 19 is water-sealed between the second transparent base layer 18 and the first transparent base layer 11 (the functional film layer at the sealing position of the two transparent substrates is removed by laser), instead of encapsulating the sealant 19 on the film layer. This structure can make the sealant 19 more firmly and tightly bonded to the two substrates, thereby increasing its bonding and sealing performance.

[0069] For example, the water and oxygen barrier layer of the second transparent substrate layer 18 may be a structure selected from SiO 2 , Al 2 O 3 , or organic acrylate, or a multilayer combination of multiple structures.

[0070] It should be understood that the various forms of the processes shown above can be used to reorder, add, or delete steps. For example, the steps described in this disclosure can be performed in parallel, sequentially, or in a different order, as long as the desired results of the technical solutions of this disclosure can be achieved. This is not a limitation herein.

[0071] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features being referred to. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. Throughout the present disclosure, "plurality" means two or more, unless otherwise specifically defined.

[0072] The above description is merely a specific embodiment of the present disclosure, but the scope of protection of the present disclosure is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in this disclosure should be included in the scope of protection of the present disclosure. Therefore, the scope of protection of the present disclosure should be based on the scope of protection of the claims.

Claims

1. An electrochromic device structure, wherein: include: A first transparent substrate layer, wherein the first transparent substrate layer is configured as a flexible substrate; A first transparent conductive layer, wherein the first transparent conductive layer is located on a top surface of the first transparent substrate layer; An electrochromic layer, the electrochromic layer being located on the top surface of the first transparent conductive layer; An electrolyte layer, the electrolyte layer being located on the top surface of the electrochromic layer; an ion storage layer, the ion storage layer being located on a top surface of the electrolyte layer; a second transparent conductive layer, wherein the second transparent conductive layer is located on a top surface of the ion storage layer; A second transparent substrate layer, wherein the second transparent substrate layer is located on the top surface of the second transparent conductive layer, and the second transparent substrate layer is configured as a flexible substrate; The electrochromic layer and the ion storage layer are configured to have at least two superimposed color changes under the action of voltage.

2. The electrochromic device structure according to claim 1, wherein: The electrochromic layer includes: a first electrochromic layer and a second electrochromic layer covering the top surface of the first electrochromic layer.

3. The electrochromic device structure according to claim 2, wherein: The overall thickness of the first electrochromic layer and the second electrochromic layer is 200nm-1600nm.

4. The electrochromic device structure according to claim 1, wherein: The ion storage layer is constructed as a NiO composite film layer with a three-dimensional mesh hole structure.

5. The electrochromic device structure according to claim 4, wherein: The electrolyte layer is a nickel-tungstate lithium electrolyte layer, which is made by the lithium ions of the lithium-ion solid electrolyte film deposited on the top surface of the NiO composite film layer reacting at the interface of the WO3 composite film color-changing layer.

6. The electrochromic device structure according to claim 5, wherein: The radius size of the lithium ions is smaller than the radius size of the holes in the NiO composite film layer.

7. The electrochromic device structure according to claim 1, wherein: The first transparent substrate layer and the second transparent substrate layer are both made of one of ultra-thin transparent glass, polyimide or PET.

8. The electrochromic device structure according to claim 1, wherein: The first transparent conductive layer and the second transparent conductive layer are both constructed of one of transparent ITO, transparent nanosilver conductive layer or transparent conductive metal grid.

9. The electrochromic device structure according to claim 1, wherein: The electrochromic device structure further includes: a water and oxygen barrier film layer; The water and oxygen barrier film layer is located on the side of the first transparent substrate layer away from contact with air; and / or The water and oxygen barrier film layer is located on a side of the second transparent substrate layer away from contact with air.

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