Full-color reversible switchable electro-controlled discoloration device, method for manufacturing the same, and use thereof

Abstract

The present application discloses an electrically controlled color-changing device capable of reversibly switching all colors, its manufacturing method and its use. The electrically controlled color-changing device includes a color-changing layer, an electrolyte and a counter electrode, the color-changing layer includes a base, a conductive layer and an active material layer, the active material layer and the conductive layer generate physical interference colors, the electrolyte contacts the conductive layer or the active material layer, and the thickness of the active material layer changes when the electrolyte undergoes an electrochemical reaction with the surface of the conductive layer or the active material layer. The electrically controlled color-changing device according to the present application has a rich variety of adjustable colors, can cover the entire color gamut, and can enable reversible color switching with a small voltage. Furthermore, the electrically controlled color-changing device according to the present application has memory for the controlled color, so no additional energy input is required to maintain the color, it is energy-saving and environmentally friendly, and has the characteristics of high brightness and high saturation, and is expected to be applied in the fields of energy-saving display, decoration, anti-counterfeiting, batteries, etc.

Description

Technical Field

[0001] (Prior Application) This application is based on a Chinese patent application with the application number 202310087178.3 and the invention title "Full-color Reversible Switchable Electrically Controlled Discoloration Device, Its Manufacturing Method, and Its Use", which was filed on February 8, 2023, and claims the priority of the said patent application.

[0002] (Technical Field) This application relates to the technical field of optics, and in particular, to a full-color reversible switchable electrically controlled discoloration device, its manufacturing method, and its use.

Background Art

[0003] With the development of the times and the progress of science and technology, electronic display has become an indispensable part of our daily life. Therefore, the energy-saving technology of electronic display screens has become particularly important in environmental protection projects.

[0004] Conventional electronic display devices, such as LEDs, traditional liquid crystals, rear projection displays, etc., must utilize continuous electrical energy to maintain the display of patterns or colors. Once the supply of electrical energy is lost, the ability to display patterns or colors will be lost in a short time.

[0005] On the other hand, in some fields that do not require dynamic display of patterns or colors, such as billboards and signboards, the switching of their patterns or colors is not frequent. If continuous electrical energy is consumed to maintain the display of patterns or colors, it is obvious that a large amount of unnecessary energy loss will occur, which is disadvantageous to sustainable development for environmental protection.

[0006] Some prior arts attempt to solve the above problems. For example, some conventional techniques represented by Chinese Invention Patent CN1426543A can electrically control and change patterns and colors, and after the color changes, there is no need to continuously consume electrical energy to maintain the pattern or color, providing an electrodeposition type display device. However, among the technical forms provided by these prior arts, some technical forms can only realize the change of black-and-white patterns or the change of one or a few single colors, and cannot realize multi-color control with a wide color gamut. Such devices are essentially pattern display devices, not multi-color control devices.

[0007] On the other hand, for example, other prior art forms represented by Chinese Invention Patent CN113296328A or CN112117442A can obtain a film layer with multiple primary colors through film layer design, and then appropriately adjust the color and / or transparency of the film layer by applying a voltage. However, the color change is still close to the primary color, or only the brightness or transparency changes, or even only the color temperature changes. This is essentially a local adjustment centered on the primary color and cannot achieve a comprehensive adjustment of a wide color gamut in a single material.

[0008] In summary, the electro-controlled color-changing structures or devices provided by the prior art cannot meet the current color display requirements for the diversification and wide color gamut adjustment of electronic displays, and the application effects are not ideal.

Summary of the Invention

Problems to be Solved by the Invention

[0009] The object of this application is to provide an electro-controlled color-changing device capable of full-color reversible switching, its manufacturing method, and its use, in view of the drawbacks of the prior art.

Means for Solving the Problems

[0010] To achieve the above-mentioned invention object, the technical solutions used in this application include the following.

[0011] In a first aspect, the present application provides a color-changing layer and an electrolyte, wherein the color-changing layer includes a base, a conductive layer, and an active material layer, and physical interference occurs between the active material layer and the conductive layer or the base layer to generate structural color, and the electrolyte is in contact with the conductive layer or the active material layer, and when the electrolyte undergoes an electrochemical reaction with the surface of the conductive layer or the active material layer, the thickness of the active material layer changes, thereby providing a full-color reversible switchable electrically controlled color-changing device.

[0012] In a second aspect, the present application also provides a step of forming a conductive layer on a base, bringing the electrolyte into contact with the conductive layer, and forming an active material layer between the electrolyte and the conductive layer by electrochemical deposition to form an electrically controlled color-changing device, or forming an active material layer on the surface of the conductive layer, and then bringing the electrolyte into contact with the active material layer to form an electrically controlled color-changing device, wherein when the electrolyte undergoes an electrochemical reaction with the surface of the conductive layer or the active material layer, the thickness of the active material layer changes, thereby providing a method for manufacturing an electrically controlled color-changing device.

Advantages of the Invention

[0013] According to the above technical solution, compared with the prior art, the beneficial effects of the present application at least include the following.

[0014] The electrically controlled color-changing device according to the present application has a rich variety of adjustable colors, can cover the entire color gamut, can enable reversible switching of colors with a small voltage, and has a voltage window of less than 6V. Further, the electrically controlled color-changing device according to the present application has memory for the controlled color, so it does not require additional energy input to maintain the color, is energy-saving and environmentally friendly, has the characteristics of high brightness and high chroma, and has potential for application in the fields of energy-saving display, decoration, anti-counterfeiting, batteries, etc.

Brief Description of the Drawings

[0015] The above description is only an outline of the technical solution of this application. In order for those skilled in the art to more clearly understand the technical means of this application and be able to implement it based on the content of the specification, the following preferred embodiments of this application will be described as follows in conjunction with detailed drawings.

[0016]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Embodiments for Carrying out the Invention

[0017] In view of the drawbacks of the prior art, the inventors of this case have put forward the technical solution of this application through long-term research and a lot of practice. The following will further explain the technical solution, its implementation process and principle, etc.

[0018] To facilitate a full understanding of this application, many specific details will be described in the following description. However, this application may also be implemented in other ways different from those described in this specification. Therefore, the protection scope of this application is not limited by the specific embodiments disclosed below.

[0019] The present application provides a method for manufacturing a device that can reversibly switch between a plurality of colors by electrical control. This manufacturing method can be applied to various static display scenarios. By applying a small voltage from the outside, a plurality of colors can be switched, and it has a memory characteristic for colors, so it does not require additional energy to maintain the display for a long time, and can meet the demand for colors while achieving energy savings.

[0020] Accordingly, an embodiment of the present application provides a full-color reversible switchable electrically controlled color-changing device including a color-changing layer and an electrolyte. The color-changing layer includes a base, a conductive layer, and an active material layer. The active material layer and the conductive layer generate physical interference colors. The electrolyte is in contact with the conductive layer or the active material layer. When the electrolyte undergoes an electrochemical reaction with the surface of the conductive layer or the active material layer, the thickness of the active material layer changes.

[0021] In some prior arts, technical solutions such as electrochromic electrodes that respond to voltage based on electrochromic materials are provided. However, all of these are based on the color-changing principle of insertion and desorption of metal ions, and realize the indication function by controlling the color in response to voltage. However, such a color-changing principle is still only a local adjustment based on the base color of the electrochromic material itself. Even if the diversification of the base color is achieved through the design of the film layer in such prior arts, the range of electrical color change is insufficient, and various color changes cannot be realized in one device.

[0022] On the other hand, in the present application, by electrically controlling the thickness, the interference parameters of the optical interference structure are changed, thereby enabling electrical control of color changes across the entire color gamut in one device. Also, different from the prior art that controls the tendency of ion insertion and desorption based on voltage, the main electrical control conditions according to the present application are the time of the applied voltage or the amount of electricity passing through in the electrolytic reaction, and these are the most direct variables for determining the thickness parameter.

[0023] In some embodiments, the electro - controlled color - changing device may further include a counter electrode electrically connected to the electrolyte. For ease of use, a counter electrode may be provided in the device. Instead of providing a counter electrode, during use, it may communicate with the electrolyte through an electrode or an electrical contact member.

[0024] In some embodiments, as shown in FIG. 1, the counter electrode and the color - changing layer are laminated in the thickness direction, or as shown in FIG. 2, the counter electrode and the color - changing layer are arranged side - by - side in the width direction. When arranged side - by - side, it is also known as a "side - by - side arrangement". In this case, a non - transparent counter electrode may be used. In this way, while expanding the selection range of the counter electrode, for a non - transparent counter electrode, a denser and more stable electrode, such as a massive metal or a carbon material, etc., may be used, and a more stable device structure can be achieved.

[0025] In some embodiments, the counter electrode is transparent or semi - transparent, which is mainly preferable because the counter electrode and the color - changing layer shown in FIG. 1 are laminated. For example, a metal mesh or a metal thin film is a transparent or semi - transparent material.

[0026] Here, the material of the counter electrode includes, but is not limited to, metals (such as Zn, Ag, Cu, Au, Fe, Ti, V, Pt, W, Pd, etc.), oxides, nitrides, sulfides, carbon materials (such as carbon cloth, carbon fiber, carbon nanotube film, graphene film, etc.), conductive polymers, etc.

[0027] The base may be glass, organic glass, plastic products, fibers, carbon material films, cloth, wooden boards, ceramics, or metal alloys, building outer walls, etc. In the present application, there is no particular limitation on the material of the base, as long as it can reliably support the conductive layer.

[0028] In some embodiments, the electrolyte contains multiple types of cations.

[0029] In some embodiments, the electrolyte contains at least two types of non-ferrous metal ions.

[0030] In some embodiments, the cations in the electrolyte are H + , Li + , Al 3+ , Na + , K + , Rb + , Ag + , Ni 2+ , Ca 2+ , Mo 6+ , Mn 2+ , Ti 4+ , V 4+ , Zn 2+ , W 6+ , Ta 5+ , Cu 2+ , Bi 3+ , Sn 4+ , Mg 2+ , Cs + including any one or a combination of two or more thereof, but not limited to the cations listed above.

[0031] Preferably, the electrolyte may preferably contain a zinc salt compound.

[0032] In some embodiments, the zinc salt compound may include, for example, any one or a combination of two or more of Zn(ClO4)2, Zn(NO3)2, ZnSO4, ZnCl2, or Zn(Ac)2.

[0033] In some embodiments, the electrolyte may be liquid, gel, or solid.

[0034] Specifically, the solute in the electrolyte is, for example, H + , Li + , Al 3+ , Na + , K + , Rb + , Ag + , Ni 2+ , Ca 2+ , Mo 6+ , Mn 2+ , Ti4+ 、 V 4+ 、 Zn 2+ 、 W 6+ 、 Ta 5+ 、 Cu 2+ 、 Bi 3+ 、 Sn 4+ 、 Mg 2+ or Cs + may also be a compound of. In one embodiment, the electrolyte layer may contain a zinc salt compound, for example, Zn(ClO4)2, Zn(NO3)2, ZnSO4, ZnCl2 or Zn(Ac)2. The ions contained in the electrolyte cause insertion / desorption and precipitation / dissolution in the discoloration layer according to the polarity of the applied voltage, and act on the discoloration of the device or the change in light transmittance. In some embodiments, the electrolyte used contains a plurality of mixed ions, which makes the color change of the device richer and the stability better compared to the case of a single ion.

[0035] In some embodiments, the material of the active material layer includes any one or a combination of two or more of metal oxides, metals, and polymers.

[0036] In some embodiments, the material of the active material layer includes any one or a combination of two or more of ZnO, MnO2, MoO3, WO3, Fe3O4, Fe2O3, NiO, VO2, V2O5, TiO2, CuO, Cu2O, Al2O3, Ta2O5, Ag2O, Ag, Cu, Al, Ni, Zn, Bi, Au, Pt, polyaniline, polythiophene, polypyrrole. Specifically, the active material may be selected from metal oxides, metals, polymers, etc. For example, the active material may include ZnO, MnO2, MoO3, WO3, Fe3O4, Fe2O3, NiO, VO2, V2O5, TiO2, CuO, Cu2O, Al2O3, Ta2O5, Ag2O, Ag, Cu, Al, Ni, Zn, Bi, Au, Pt, polyaniline, polythiophene, polypyrrole, etc., but is not limited thereto.

[0037] Furthermore, the active material layer may be a single layer, for example, it may be directly formed by an electrodeposition reaction of an electrolytic solution. Specifically, it may be formed by plating one or more kinds of metals, particularly non-ferrous metals, on the surface of the conductive layer. In many cases, the active material layer formed in this way is a single layer. Also, first, a metal oxide is deposited on the surface of the conductive layer as a seed layer (which may be regarded as a sub-layer of the active material layer), and then a metal or a polymer (constituting another sub-layer) is electrodeposited in one layer by an electrolytic solution to form an active material layer having a two-layer structure.

[0038] Therefore, in some possible embodiments, the active material layer may include a first sub-layer and a second sub-layer arranged in a stack. The first sub-layer is in close contact with the conductive layer and may include the above metal oxide. The second sub-layer may include the above metal and / or polymer. In such an embodiment, due to the presence of the seed layer, the electrodeposition uniformity is excellent, the crystal grains are fine, the discoloration response is faster, and the color retention property is better. Due to the presence of the seed layer, the active material starts to grow directly without going through the nucleation stage, thereby making the growth more uniform, the growth rate faster, and obtaining a faster discoloration response and more uniform full-color discolorability.

[0039] In some embodiments, the material of the conductive layer may include, but is not limited to, any one or a combination of two of a metal and a non-metal conductive material.

[0040] In some embodiments, the material of the conductive layer may include, but is not limited to, any one or a combination of two or more of Cu, Ag, W, Ti, V, Fe, Cr, Ni, Zn, Al, Mo, Au, Pd, Co, Ta, Pt, Mg, carbon materials, conductive metal oxides, and conductive polymer materials. Specifically, the conductive layer may use a metal or other conductive material. The metal materials include, but are not limited to, Cu, Ag, W, Ti, V, Fe, Cr, Ni, Zn, Al, Mo, Au, Pd, Co, Ta, Pt, Mg, etc. The conductive materials include carbon materials (such as carbon cloth, carbon fiber, carbon nanotube film, graphene film, etc.), metal oxides (such as AZO, ITO, FTO), and other conductive polymer materials (such as polyaniline, polyacetylene), etc., but are not limited to these.

[0041] In some embodiments, the conductive layer is any one of a one-dimensional thin film, a two-dimensional photonic crystal, a three-dimensional photonic crystal, or a nanoparticle structure.

[0042] In some embodiments, the thickness of the conductive layer is preferably 0 to 1 cm, and more preferably 50 to 1000 nm in the following examples.

[0043] In some embodiments, the active material layer may be any one of a one-dimensional thin film, a two-dimensional photonic crystal, a three-dimensional photonic crystal, or a nanoparticle structure.

[0044] In some embodiments, the thickness of the active material layer is 0 to 1 mm, preferably 0 to 800 nm, and more preferably 0 to 200 nm. Note that the thickness of the active material layer may be 0. In this case, it may be understood that the active material layer does not yet exist. For example, in the following examples, the electrolyte was injected, but electrodeposition was not started. At this time, the device has the inherent color of the conductive layer and is included in the scope of the electro-controlled color-changing device described in the present application. The color-changing device of the present application is not limited only to those in which the active material layer is formed. That is, the presence or absence of the active material layer is related to the electro-controlled state. In the initial state or when the color change is repeatedly and reversibly returned to the initial state, the active material layer may not exist (the electro-controlled color-changing device selectively includes the active material layer). That is, the thickness of the active material layer is 0.

[0045] In that case, the second aspect of the embodiments of the present application also provides a method for manufacturing an electro-controlled color-changing device including the following steps.

[0046] Form a conductive layer on the base.

[0047] Contact the electrolyte with the conductive layer and form an active material layer between the electrolyte and the conductive layer by electrochemical deposition to form an electro-controlled color-changing device. Alternatively, form an active material layer on the surface of the conductive layer, and then contact the electrolyte with the active material layer to form an electro-controlled color-changing device.

[0048] Here, when the electrolyte undergoes an electrochemical reaction with the surface of the conductive layer or the active material layer, the thickness of the active material layer changes.

[0049] As some typical examples of the above technical solutions, the manufacturing method according to the present application may be implemented in the following steps.

[0050] A discoloration layer is obtained by physical or chemical deposition, and a conductive layer, which may be a metal, metal oxide, nitride, sulfide, carbon material, or conductive polymer, is deposited on the base. Next, an active material is optionally coated on the conductive layer by physical or chemical deposition. At this time, the thickness of the active material layer may be between 0 and 800 nm.

[0051] The discoloration layer and the counter electrode are assembled in a face-to-face or side-by-side manner, and the two electrodes are connected by an electrolyte. The form of the electrolyte may be liquid, gel, or solid. The electrolyte may be a mixed electrolyte, for example, a mixed electrolyte combining two or more of salts such as aqueous ZnCl2, H2SO4, MnSO4, MnCl2, ZnSO4, etc.

[0052] By an electrochemical method, an active material layer is deposited or dissolved on the conductive layer or the discoloration layer. When the thickness of the active material layer is different, the color of the corresponding device is different, whereby a device capable of reversibly switching between a plurality of colors is obtained.

[0053] A third aspect of the embodiments of the present application further provides a method for controlling the color of an electro-optically controlled discoloration device, including the following steps.

[0054] An electro-optically controlled discoloration device according to any of the above embodiments is provided.

[0055] A voltage is applied between the conductive layer and the electrolyte, and by adjusting the application time of the applied voltage, the electro-optically controlled discoloration device is made to exhibit various colors.

[0056] In some embodiments, the color control method is to apply a reverse voltage between the conductive layer and the electrolyte to reversibly reduce the color exhibited by the electro-optically controlled discoloration device.

[0057] In some embodiments, the applied voltage is 6 V or less, preferably 1.2 to 2 V.

[0058] In some embodiments, the application time is 0 to 160 s.

[0059] In some embodiments, by adjusting the application time, the colors that the electro-controlled color-changing device can exhibit include any one of red, orange, yellow, green, blue, indigo, and violet, whereby all colors can be obtained. Of course, the all colors described in this application also refer to at least the above seven colors that can be generated in one device. This is a wide color gamut that could not be achieved by the local color change of electrochromic materials in the prior art.

[0060] The fourth aspect of the embodiments of this application also provides for the use of an electro-controlled color-changing device according to any of the above embodiments in all fields of display, decoration, anti-counterfeiting, batteries, and energy-saving building materials.

[0061] Hereinafter, several examples will be used to further describe the technical solution of this application in detail with reference to the drawings. However, the examples used are only for the description of this application and do not limit the scope of this application.

[0062] (Example 1) This example provides a device that can reversibly switch between multiple colors by electro-control, including a color-changing layer (base, conductive layer, active material layer), an electrolyte, and a counter electrode layer, and its structure is shown in FIG. 1.

[0063] The manufacturing method of the device that can reversibly switch between multiple colors by electro-control in this example is as follows. A conductive layer is deposited on a clean PET plastic plate. Specifically, an AZO film with a thickness of 200 nm is magnetron sputtered. A transparent Cu metal mesh is used for the counter electrode. Between the two electrodes, multiple types of cations: Cu 2+ , Mn 2+ , H + , Bi 3+A liquid electrolyte containing [the relevant substance] was injected. The working electrode (conductive layer) and the counter electrode were respectively connected to both electrodes of an electrochemical workstation, and the voltage was kept constant. Preferably, the voltage was set to 1.2 V, and by applying the voltage to the device for various lengths of time, that is, by controlling the application time of the voltage, active materials of various thicknesses were formed on the conductive layer, and a device capable of changing among multiple colors was obtained. Also, when a reverse current was applied, the color recovered reversibly according to a similar rule. The electro-optically variable device according to the present application can reversibly switch between seven colors in the same device by controlling the voltage application time.

[0064] Of course, the aforementioned conductive AZO film may be manufactured by a method known in the art such as electron beam evaporation or thermal evaporation, and the obtained effect of color change was the same.

[0065] (Example 2) As shown in FIG. 1, this example illustrates a device that includes a color-changing layer (base, conductive layer, active material layer), an electrolyte, and a counter electrode layer and can reversibly switch between multiple colors by electrical control.

[0066] The manufacturing method of the device that can reversibly switch between multiple colors by electrical control in this example is as follows. A conductive layer was deposited on a clean glass, and preferably, a 50-nm-thick Au film was magnetron sputtered. For the counter electrode, a 200-nm-thick transparent ITO was used. An electrolyte in which PVA was added as a skeleton-forming gel with a content of 20% was injected between the two electrodes. The working electrode and the counter electrode were respectively connected to both electrodes of an electrochemical workstation, and the voltage was kept constant. Preferably, the voltage was set to 2 V, and by applying the voltage to the device for various lengths of time, active materials of various thicknesses were formed on the conductive layer, and a device capable of changing among multiple colors was obtained. The range of its color change also covered three colors, and the change was stable and reversible.

[0067] Of course, the aforementioned conductive Au and ITO films may be manufactured by a method known in the art such as electron beam evaporation or thermal evaporation, and the obtained effect of color change was the same.

[0068] (Example 3) This example illustrates a device that reversibly switches between multiple colors by electrical control, including a color-changing layer (base, conductive layer, active material layer), an electrolyte, and a counter electrode layer, as shown in FIG. 1.

[0069] The manufacturing method of the device that reversibly switches between multiple colors by electrical control in this example is as follows. A conductive layer was deposited on a clean carbon nanotube film, and preferably, a polyaniline film with a thickness of 1 μm was screen-printed. Next, MnO2 with a thickness of 100 nm was electrochemically deposited on the polyaniline film to serve as one of the active material layers. For the counter electrode, metal Zn, preferably, a plain Zn metal mesh was used. Between the two electrodes, preferably, a liquid electrolyte containing multiple types of cations: Zn 2+ , Mn 2+ , H + and monomers, cross-linking agents, and a photoinitiator for UV curing was injected to obtain a hydrogel electrolyte. The working electrode and the counter electrode were respectively connected to both poles of an electrochemical workstation, the voltage was kept constant, preferably, the voltage was set to 1.8 V, and the voltage was applied to the device for various periods of time to form active materials with various thicknesses on the conductive layer, thereby obtaining a device that can change between multiple colors. The range of the color change also covers three types of colors, and the change is stable and reversible.

[0070] Of course, the aforementioned conductive polyaniline film may be manufactured by a method known in the art, such as electron beam evaporation or thermal evaporation, and the obtained effect of color change was the same.

[0071] Furthermore, there is a one-to-one correspondence between the thickness and color of the manganese dioxide deposited in this example, and the corresponding color can be obtained by changing the deposition thickness. For example, a thickness of 130 nm corresponds to yellow, and a thickness of 210 nm corresponds to green, etc.

[0072] (Example 4) As shown in FIG. 2, this example illustrates a device that includes a discoloration layer (base, conductive layer, active material layer), an electrolyte, and a counter electrode layer, and assembles these side by side to form a device, which can reversibly switch between multiple colors by electrical control. The reflectance curves and optical photographs at the thickness of each active material layer of the device are shown in FIGS. 3 and 4.

[0073] The manufacturing method of the device that can reversibly switch between multiple colors by electrical control in this example is as follows. A conductive layer is deposited on a clean PET transparent thin film. Preferably, Pt with a thickness of 80 nm is magnetron sputtered. A carbon nanotube film is used for the counter electrode, and these are assembled side by side to form a device. A liquid electrolyte containing a plurality of components such as Cr(NO3)3, MnCl2, HCl, monomers, crosslinking agents, and photoinitiators for ultraviolet curing is injected between the two electrodes to obtain a hydrogel electrolyte. The working electrode and the counter electrode are respectively connected to both poles of an electrochemical workstation, the voltage is kept constant, preferably the voltage is set to 1.8 V, and the voltage is applied to the device for various periods of time to form active materials with various thicknesses on the conductive layer, obtaining a device that can change between multiple colors. As shown in FIGS. 3 and 4, the thickness of a general active material layer may be 0 - 200 nm. In this range, the range of color change also covers three types of colors, and the change is stable and reversible.

[0074] Of course, the aforementioned conductive Pt film may be manufactured by a method known in the art such as electron beam evaporation or thermal evaporation, and the obtained effect of color change is the same.

[0075] (Example 5) As shown in FIG. 2, this example illustrates a device that includes a discoloration layer (base, conductive layer, active material layer), an electrolyte, and a counter electrode layer, and assembles these side by side to form a device, which can reversibly switch between multiple colors by electrical control. Each H + The optical photographs at the concentration are shown in FIG. 5.

[0076] The manufacturing method of a device that reversibly switches between multiple colors by electrical control in this embodiment is as follows. A conductive layer is deposited on a clean PET transparent thin film. Preferably, ITO with a thickness of 200 nm is magnetron sputtered. For the counter electrode, a carbon nanotube film is used, and these are assembled side by side to form a device. Between the two electrodes, a liquid electrolyte containing preferably a plurality of components such as BiCl3, ZnCl2, HCl, monomers, crosslinking agents, and photoinitiators for ultraviolet curing is injected to obtain a hydrogel electrolyte. The working electrode and the counter electrode are respectively connected to both poles of an electrochemical workstation, the voltage is kept constant, preferably the voltage is set to 1.5 V, and by changing the hydrogen ion concentration in the electrolyte of the device, the response time of color conversion is controlled, and active materials with various thicknesses are formed on the conductive layer to obtain a device that can change between multiple colors. At the same time, devices with each hydrogen ion concentration are manufactured, and the discoloration rules are shown in FIG. 5. From FIG. 5, in the range where the hydrogen ion concentration is 100 - 160 mM, there is no impact on the achievement of full-color performance, and mainly the discoloration speed is affected.

[0077] Of course, the aforementioned conductive ITO film may also be manufactured by methods known in the art such as electron beam evaporation or thermal evaporation, and the obtained color change effect and the rule of influence by the hydrogen ion concentration are the same.

[0078] (Example 6) As shown in FIG. 2, this Example 6 discloses a device that reversibly switches between multiple colors by electrical control, which includes a color-changing layer (base, conductive layer, active material layer), an electrolyte, and a counter electrode layer, and these are assembled side by side to form a device. Optical photographs at each total ion concentration of the device are shown in FIG. 6.

[0079] The manufacturing method of a device that reversibly switches between multiple colors by electrical control in this embodiment is as follows. A conductive layer is deposited on a clean transparent glass, preferably Ag with a thickness of 200 nm is magnetron sputtered. A Pt sheet is used for the counter electrode, and these are assembled side by side to form a device. A liquid electrolyte containing a plurality of components such as CuCl2, ZnCl2, and H2SO4 is preferably injected between the two electrodes. The working electrode and the counter electrode are respectively connected to both poles of an electrochemical workstation, the voltage is kept constant, preferably the voltage is set to 1.5 V, and by changing the ion concentration in the electrolyte of the device, the response time of color conversion is controlled, an active material with various thicknesses is formed on the conductive layer, a device that can change between multiple colors is obtained, and devices with each hydrogen ion concentration are manufactured. Even when the ion concentration is in the range of 0.1 - 0.5 M, there is no significant influence on the discoloration range, and mainly the speed of discoloration is affected.

[0080] Of course, the aforementioned conductive Ag film may also be manufactured by a method known in the art such as electron beam evaporation or thermal evaporation, and the rules of the obtained color change effect and the influence by the total hydrogen ion concentration are the same.

[0081] It is obvious from the above embodiments that the embodiments of the present application provide a manufacturing method of a device that reversibly switches between multiple colors by electrical control, and can be applied to the fields of display, decoration, anti-counterfeiting, batteries, or energy-saving building materials. By applying a small voltage from the outside, the color change of the device can be diversified, such a change is reversible, and it also has memory characteristics, that is, the color can be maintained without the application of voltage or energy from the outside. Thereby, it can meet various needs for colors, realize high-quality energy-saving displays, and is expected to be applied in the field of static displays.

[0082] Note that the above embodiments are only for explaining the technical concept and features of the present application, and are intended to enable those skilled in the art to understand and implement the content of the present application, and the protection scope of the present application is not limited thereby. Equivalent changes or modifications made based on the spiritual essence of the present application shall be included within the protection scope of the present application.

[0083] (Addendum) (Addendum 1) Comprising a color-changing layer and an electrolyte, The color-changing layer includes a base, a conductive layer, and an active material layer, and physical interference occurs between the active material layer and the conductive layer or the base layer to generate structural color. The electrolyte is in contact with the conductive layer or the active material layer, and when the electrolyte undergoes an electrochemical reaction with the surface of the conductive layer or the active material layer, the thickness of the active material layer changes. A full-color reversible switchable electrically controlled color-changing device characterized by this.

[0084] (Addendum 2) Further comprising a counter electrode electrically connected to the electrolyte, Preferably, the counter electrode and the color-changing layer are laminated in a thickness direction layer or arranged side by side in a width direction. Preferably, the counter electrode is transparent or translucent. The electrically controlled color-changing device according to Addendum 1, characterized by this.

[0085] (Addendum 3) The electrolyte contains a plurality of types of cations. Preferably, the electrolyte contains at least two types of cations, and / or The cations in the electrolyte are H + , Li + , Al 3+ , Na + , K + , Rb + , Ag + , Ni 2+ , Ca 2+ , Mo 6+ , Mn 2+ , Ti 4+ , V 4+ , Zn2+ 、W 6+ 、Ta 5+ 、Cu 2+ 、Bi 3+ 、Sn 4+ 、Mg 2+ 、Cs + The electro - controlled color - changing device according to appended note 1, characterized by containing any one or a combination of two or more of the following:

[0086] (Appended note 4) The electrolyte contains a zinc salt compound, Preferably, the zinc salt compound contains any one or a combination of two or more of Zn(ClO4)2, Zn(NO3)2, ZnSO4, ZnCl2, or Zn(Ac)2, Preferably, the electrolyte is a liquid, gel, or solid. The electro - controlled color - changing device according to appended note 3, characterized by this.

[0087] (Appended note 5) The material of the active material layer contains any one or a combination of two or more of metal oxides, metals, and polymers, Preferably, the material of the active material layer contains any one or a combination of two or more of ZnO, MnO2, MoO3, WO3, Fe3O4, Fe2O3, NiO, VO2, V2O5, TiO2, CuO, Cu2O, Al2O3, Ta2O5, Ag2O, Ag, Cu, Al, Ni, Zn, Bi, Au, Pt, polyaniline, polythiophene, and polypyrrole. The electro - controlled color - changing device according to appended note 1, characterized by this.

[0088] (Appended note 6) The material of the conductive layer contains any one or a combination of two of metals and non - metal conductive materials, Preferably, the material of the conductive layer contains any one or a combination of two or more of Cu, Ag, W, Ti, V, Fe, Cr, Ni, Zn, Al, Mo, Au, Pd, Co, Ta, Pt, Mg, carbon materials, conductive metal oxides, and conductive polymer materials. The electro - controlled color - changing device according to appended note 1, characterized by this.

[0089] (Supplementary Note 7) The conductive layer is any one of a one-dimensional thin film, a two-dimensional photonic crystal, a three-dimensional photonic crystal, or a nanoparticle structure, and / or The thickness of the conductive layer is 0 to 1 cm, and the electro-optically controllable color-changing device according to Supplementary Note 1 is characterized in that.

[0090] (Supplementary Note 8) The active material layer is any one of a one-dimensional thin film, a two-dimensional photonic crystal, a three-dimensional photonic crystal, or a nanoparticle structure, and / or The thickness of the active material layer is 0 to 1 mm, and the electro-optically controllable color-changing device according to Supplementary Note 1 is characterized in that.

[0091] (Supplementary Note 9) A step of forming a conductive layer on a base, Bringing an electrolyte into contact with the conductive layer, and forming an active material layer between the electrolyte and the conductive layer by electrochemical deposition to form an electro-optically controllable color-changing device, or Forming an active material layer on the surface of the conductive layer, and then bringing the electrolyte into contact with the active material layer to form an electro-optically controllable color-changing device, and a method for manufacturing an electro-optically controllable color-changing device, characterized in that When the electrolyte undergoes an electrochemical reaction with the surface of the conductive layer or the active material layer, the thickness of the active material layer changes.

[0092] (Supplementary Note 10) A step of providing an electro-optically controllable color-changing device according to any one of Supplementary Notes 1 to 8, Applying a voltage between the conductive layer and the electrolyte, and adjusting the application time of the applied voltage so that the electro-optically controllable color-changing device exhibits various colors, and a method for controlling the color of an electro-optically controllable color-changing device, characterized in that.

[0093] (Supplementary Note 11) The method for color control according to appended claim 10, further comprising the step of applying a reverse voltage between the conductive layer and the electrolyte to reversibly reduce the color presented by the electro-control discoloration device.

[0094] (Appended claim 12) The voltage to be applied is 6V or less, preferably 1.2 - 2V. The method for color control according to appended claim 10.

[0095] (Appended claim 13) The application time is 0 - 160s. The method for color control according to appended claim 10.

[0096] (Appended claim 14) By adjusting the application time, the color that the electro-control discoloration device can present includes any one of red, orange, yellow, green, blue, indigo, and violet. The method for color control according to appended claim 13.

[0097] (Appended claim 15) Use of the electro-control discoloration device according to any one of appended claims 1 - 8 in all fields of display, decoration, forgery prevention, batteries, and energy-saving building materials.

Claims

1. Comprising a color-changing layer and an electrolyte, The color-changing layer includes a base, a conductive layer, and an active material layer, and physical interference occurs between the active material layer and the conductive layer or the base layer to generate structural color. The electrolyte is in contact with the conductive layer or the active material layer. When the electrolyte undergoes an electrochemical reaction with the surface of the conductive layer or the active material layer, the thickness of the active material layer changes. A full-color reversibly switchable electrically controlled color-changing device characterized by this.

2. Further comprising a counter electrode electrically connected to the electrolyte. The electrically controlled color-changing device according to claim 1, characterized by this.

3. The counter electrode and the color-changing layer are stacked and installed in a layer in the thickness direction or arranged side by side in the width direction. The electrically controlled color-changing device according to claim 2, characterized by this.

4. The counter electrode is transparent or translucent. The electrically controlled color-changing device according to claim 2, characterized by this.

5. The electrolyte contains multiple types of cations. The electrically controlled color-changing device according to claim 1, characterized by this.

6. The electrolyte contains at least two types of cations, and / or The cations in the electrolyte include any one or a combination of two or more of H⁺, Li⁺, Al³⁺, Na⁺, K⁺, Rb⁺, Ag⁺, Ni²⁺, Ca²⁺, Mo⁶⁺, Mn²⁺, Ti⁴⁺, V⁴⁺, Zn²⁺, W⁶⁺, Ta⁵⁺, Cu²⁺, Bi³⁺, Sn⁴⁺, Mg²⁺, Cs⁺. The electrically controlled color-changing device according to claim 5, characterized by this.

7. The electrolyte contains a zinc salt compound. The electrically controlled color-changing device according to claim 5, characterized by this.

8. The zinc salt compound includes any one or a combination of two or more of Zn(ClO₄)₂, Zn(NO₃)₂, ZnSO₄, ZnCl₂, or Zn(Ac)₂. The electrically controlled color-changing device according to claim 7, characterized by this.

9. The electrolyte is a liquid, gel, or solid. The electrically controlled color-changing device according to claim 7, characterized by this.

10. The material of the active material layer includes any one or a combination of two or more of metal oxides, metals, and polymers. The electrically controlled color-changing device according to claim 1, characterized by this.

11. The material of the active material layer includes any one or a combination of two or more of ZnO, MnO₂, MoO₃, WO₃, Fe₃O₄, Fe₂O₃, NiO, VO₂, V₂O₅, TiO₂, CuO, Cu₂O, Al₂O₃, Ta₂O₅, Ag₂O, Ag, Cu, Al, Ni, Zn, Bi, Au, Pt, polyaniline, polythiophene, polypyrrole. The electro - controlled color - changing device according to claim 10 is characterized by this.

12. The material of the conductive layer includes any one or a combination of two of metal and non - metal conductive materials. The electro - controlled color - changing device according to claim 1 is characterized by this.

13. The material of the conductive layer includes any one or a combination of two or more of Cu, Ag, W, Ti, V, Fe, Cr, Ni, Zn, Al, Mo, Au, Pd, Co, Ta, Pt, Mg, carbon materials, conductive metal oxides and conductive polymer materials. The electro - controlled color - changing device according to claim 12 is characterized by this.

14. The conductive layer is any one of the structures of one - dimensional thin film, two - dimensional photonic crystal, three - dimensional photonic crystal or nanoparticles, and / or The thickness of the conductive layer is greater than 0 cm and less than or equal to 1 cm. The electro - controlled color - changing device according to claim 1 is characterized by this.

15. The active material layer is any one of the structures of one - dimensional thin film, two - dimensional photonic crystal, three - dimensional photonic crystal or nanoparticles, and / or The thickness of the active material layer is greater than 0 mm and less than or equal to 1 mm. The electro - controlled color - changing device according to claim 1 is characterized by this.

16. The step of forming a conductive layer on a base, Bringing an electrolyte into contact with the conductive layer and forming an active material layer between the electrolyte and the conductive layer by electrochemical deposition to form an electro - controlled color - changing device, or The step of forming an active material layer on the surface of the conductive layer, and then bringing the electrolyte into contact with the active material layer to form an electro - controlled color - changing device, The step of causing the electrolyte to undergo an electrochemical reaction with the surface of the conductive layer or the active material layer and changing the thickness of the active material layer. A method for manufacturing an electro - controlled color - changing device is characterized by including these steps.

17. The step of providing an electro - controlled color - changing device according to any one of claims 1 to 15 Applying a voltage between the conductive layer and the electrolyte and adjusting the application time of the applied voltage so that the electrochromic device exhibits various colors, and a method for controlling the color of an electrochromic device, characterized in that it includes this step.

18. The method for controlling color according to claim 17, further comprising applying a reverse voltage between the conductive layer and the electrolyte to reversibly reduce the color exhibited by the electrochromic device.

19. The method for controlling color according to claim 17, characterized in that the applied voltage is 6V or less.

20. The method for controlling color according to claim 17, characterized in that the applied voltage is 1.2 to 2V.

21. The method for controlling color according to claim 17, characterized in that the application time is longer than 0s and 160s or less.

22. The method for controlling color according to claim 21, characterized in that the color that the electrochromic device can exhibit by adjusting the application time includes any one of red, orange, yellow, green, blue, indigo, and purple.

23. Use of the electrochromic device according to any one of claims 1 to 15 in all fields of display, decoration, forgery prevention, batteries, and energy-saving building materials.

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