An electrochromic device with adjustable reflectivity and an electronic terminal containing the same

Abstract

The present invention provides an electrochromic device with adjustable reflectivity and an electronic terminal including the same. The electrochromic device includes a first transparent substrate layer, an electrochromic stack, a metal ion stack, and a second substrate layer stacked in sequence; the electrochromic stack includes a first transparent conductive layer and an electrochromic functional layer stacked in sequence; the metal ion stack includes a second transparent conductive layer, a metal ion layer, and optionally an electrodeposition inhibition layer stacked in sequence; the electrochromic functional layer is adjacent to the metal ion layer or the electrodeposition inhibition layer; or a transparent insulating layer is provided between the electrochromic stack and the metal ion stack; the electrochromic stack includes a first transparent conductive layer, an electrochromic functional layer, and a third transparent conductive layer stacked in sequence; and the metal ion stack includes a second transparent conductive layer, a metal ion layer, an electrodeposition inhibition layer, and a fourth conductive layer stacked in sequence. The electrochromic device provided by the present invention has adjustable reflectivity and transmittance, providing a stronger and richer visual effect.

Description

Technical Field

[0001] The present invention belongs to the technical field of color-changing display, and in particular relates to an electrochromic device with adjustable reflectivity and an electronic terminal comprising the same. Background Art

[0002] Electrochromism refers to the phenomenon in which a material's optical properties undergo a stable, reversible color change under the influence of an applied electric field. This phenomenon manifests itself as a reversible change in color and transparency. Materials exhibiting electrochromic properties are called electrochromic materials, and devices made from them are called electrochromic devices. Electrochromic devices have significant application prospects in areas such as color-changing glasses, electronic displays, military concealment, and building energy conservation.

[0003] Common electrochromic devices generally consist of a transparent substrate layer, a transparent conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, a transparent conductive layer, and a transparent substrate layer stacked in sequence. When a voltage is applied, ions are conducted from the ion storage layer through the electrolyte layer into the electrochromic layer, causing the color to change. When a reverse voltage is applied, ions are conducted from the electrochromic layer through the electrolyte layer into the ion storage layer, causing the color to fade.

[0004] Electrochromic materials can be categorized into inorganic and organic electrochromic materials. Inorganic electrochromic materials, such as tungsten trioxide, vanadium pentoxide, nickel oxide, and titanium dioxide, offer advantages such as stability and fast response. Organic electrochromic materials, such as viologens and polythiophenes, offer a wide variety of colors and facilitate design. By selecting different electrochromic materials, electrochromic devices with varying colors and color ranges can be created.

[0005] However, for a given electrochromic device, the color-changing effect produced by changes in transmittance is relatively simple, making it difficult to present a diverse and colorful visual effect. Moreover, even if a patterned layer is added beneath the device, when the transmittance of the electrochromic device changes, especially when the electrochromic device is in a colored state and the transmittance is low, the electrochromic device often does not appear bright enough, and the color of the patterned layer appears grayish, resulting in a less aesthetically pleasing and poor visual effect in practical applications. Summary of the Invention

[0006] To address the shortcomings of the prior art, the present invention aims to provide an electrochromic device with adjustable reflectivity and an electronic terminal incorporating the same. The reflectivity and transmittance of this electrochromic device are adjustable. By combining the transmittance changes of the electrochromic stack with the reflectivity changes of the metal ion stack, the visual effects of the electrochromic device are enhanced and enriched.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an electrochromic device with adjustable reflectivity, comprising a first transparent substrate layer, an electrochromic stack, a metal ion stack, and a second substrate layer stacked in sequence; the electrochromic stack comprising a second transparent conductive layer, a metal ion layer, and optionally an electrodeposition inhibition layer stacked; the first electrochromic functional layer being adjacent to the metal ion layer or the electrodeposition inhibition layer;

[0009] Or it includes a first transparent base layer, an electrochromic stack, a transparent insulating layer, a metal ion stack and a second base layer stacked in sequence; the electrochromic stack includes a first transparent conductive layer, a second electrochromic functional layer and a third transparent conductive layer stacked in sequence; the metal ion stack includes a second transparent conductive layer, a metal ion layer and a fourth conductive layer stacked in sequence.

[0010] It should be noted that the term "optionally including an electrodeposition-inhibiting layer" as used herein refers to the presence or absence of an electrodeposition-inhibiting layer. When the electrochromic stack includes an electrodeposition-inhibiting layer, the first electrochromic functional layer is adjacent to the electrodeposition-inhibiting layer; when the electrochromic stack does not include an electrodeposition-inhibiting layer, the first electrochromic functional layer is adjacent to the metal ion layer.

[0011] The electrochromic device provided by the present invention has an electrochromic stack and a metal ion stack as its main structure. In the metal ion stack, when a positive voltage is applied to the first transparent conductive layer and a negative voltage is applied to the second transparent conductive layer, or when a positive voltage is applied to the fourth conductive layer and a negative voltage is applied to the second transparent conductive layer, the metal ions in the metal ion layer are reduced to metal and deposited on the surface of the second transparent conductive layer, thereby increasing the reflectivity of the metal ion stack; when a negative voltage is applied to the first transparent conductive layer and a positive voltage is applied to the second transparent conductive layer, or when a negative voltage is applied to the fourth conductive layer and a positive voltage is applied to the second transparent conductive layer, the deposited metal is oxidized to metal ions and enters the metal ion layer, thereby reducing the reflectivity of the metal ion stack. By adjusting the applied voltage, the metal ion stack can be controlled to switch between transparency and total reflection, or to be in any reflectivity state between transparency and total reflection.

[0012] In an electrochromic stack, by adjusting the voltage applied to the first or second electrochromic functional layer, the first or second electrochromic functional layer can be switched between a colored state and a faded state, or to any transmittance state between the colored and faded states. The color of the first or second electrochromic functional layer in the colored state depends on the type of electrochromic material selected.

[0013] Compared with existing electrochromic devices, the present invention enhances the visual effect of the electrochromic device (especially when colored) by coordinating the transmittance change of the electrochromic stack and the reflectivity change of the metal ion stack, making the electrochromic device present a more colorful visual effect. In some scenarios, it can also make the product surface have a metal-like texture, thereby meeting the needs of various usage scenarios.

[0014] In the present invention, when the electrochromic functional layer of an electrochromic stack and the metal ion layer of a metal ion stack are adjacent, the first transparent conductive layer and the second transparent conductive layer serve as the two electrodes that drive the electrochromic device. When the applied voltage is varied, the transmittance of the electrochromic stack and the reflectivity of the metal ion stack change simultaneously.

[0015] When the electrochromic stack and the metal ion stack are separated by a transparent insulating layer, the first and third transparent conductive layers serve as electrodes driving the electrochromic stack, while the second and fourth transparent conductive layers serve as electrodes driving the metal ion stack. The electrochromic stack and the metal ion stack are independent of each other, and changes in the transmittance of the electrochromic stack and the reflectivity of the metal ion stack do not affect each other. In this case, the metal ion stack can be positioned with the second transparent conductive layer close to the second substrate layer, or with the fourth conductive layer close to the second substrate layer.

[0016] In the present invention, "transparent" means fully transparent or partially transparent. The first transparent substrate layer can be fully transparent or partially transparent to enable the electrochromic device to present a specific pattern. The second substrate layer can be fully transparent, partially transparent, or opaque.

[0017] The transparent substrate layer may be a hard transparent substrate layer or a flexible transparent substrate layer. The present invention has no particular limitation on the material of the substrate layer. For example, the material of the hard transparent substrate layer may be glass; the material of the flexible transparent substrate layer includes, but is not limited to, polyethylene terephthalate (PET), cyclic olefin copolymer, and triacetyl cellulose. Any one or a combination of at least two of these may be selected. Typical but non-limiting combinations include a combination of PET and cyclic olefin copolymer, a combination of cyclic olefin copolymer and triacetyl cellulose, a combination of PET and triacetyl cellulose, and a combination of PET, cyclic olefin copolymer, and triacetyl cellulose.

[0018] In one embodiment of the present invention, the first electrochromic functional layer is an anode electrochromic material layer or a cathode electrochromic material layer.

[0019] In one embodiment of the present invention, the second electrochromic functional layer is a polymer dispersed liquid crystal layer, a suspended particle device layer, or a composite layer of an anode electrochromic material, an electrolyte, and a cathode electrochromic material.

[0020] In the present invention, the material of the first electrochromic functional layer is an anodic electrochromic material or a cathodic electrochromic material. The cathodic electrochromic material can gain electrons to undergo a reduction reaction, causing the transmittance to change between a colored state and a faded state; the anodic electrochromic material can lose electrons to undergo an oxidation reaction, causing the transmittance to change between a colored state and a faded state. Specifically, the material of the first electrochromic functional layer can be selected from existing color-changing materials that can form solid thin films, such as inorganic materials such as NiO, WO3, Nb2O5, and TiO2; organic materials such as polythiophene derivatives and copolymer systems; and metal conjugated systems such as Prussian blue. The color change of the first electrochromic functional layer can be adjusted based on the type of electrochromic material. When selecting the anodic electrochromic material or the cathodic electrochromic material for the first electrochromic functional layer, the material type can be selected based on the product's transmittance and reflectance requirements and the initial state of the corresponding metal ion stack.

[0021] The second electrochromic functional layer is a structural unit with electrochromic function, which can be a sheet with adjustable transmittance made of a combination of one or more flexible or rigid layers of materials. For example, it can be a PDLC (Polymer Dispersed Liquid Crystal) layer, an SPD (Suspended Particle Device) layer or an EC (Electrochromic) layer. The EC layer is a composite layer of an anode electrochromic material, an electrolyte and a cathode electrochromic material. In the present invention, the EC layer can be a liquid composite material layer or a gel composite material layer formed by mixing an anode electrochromic material, an electrolyte and a cathode electrochromic material, or it can be a solid composite layer with a three-layer structure consisting of an anode electrochromic material layer, a solid electrolyte layer and a cathode electrochromic material layer stacked in sequence.

[0022] For the sake of convenience, the process of adjusting the transmittance of the electrochromic layer is illustrated by taking an EC with a specific structure (composed of an anode electrochromic material layer, an electrolyte layer and a cathode electrochromic material layer stacked in sequence) as an example: the voltage applied to both ends of the anode electrochromic material layer and the cathode electrochromic material layer causes ions to move between the anode electrochromic material layer and the cathode electrochromic material layer, and to embed / de-embed, or de-embed / embed in the anode electrochromic material layer and the cathode electrochromic material layer, thereby changing the optical state of the electrochromic material in the anode electrochromic material layer and the cathode electrochromic material layer, and then changing the transmittance of the EC layer, causing it to change between a colored state, an intermediate state and a faded state.

[0023] In one embodiment of the present invention, the metal ion layer is a liquid electrolyte layer containing metal ions or a gel electrolyte layer containing metal ions.

[0024] Preferably, the metal ions in the metal ion layer include one or a combination of at least two of silver ions, bismuth ions, copper ions, and zinc ions.

[0025] In one embodiment of the present invention, the fourth conductive layer is composed of staggered or spaced metal lines, and / or metal strips located at the edge of the plane where the fourth conductive layer is located.

[0026] It should be noted that the material of the second transparent conductive layer in the present invention occupies the entire area of ​​the plane in which it is located. When a positive pressure is applied to the fourth conductive layer and a negative pressure is applied to the second conductive layer, the metal ions in the metal ion layer can deposit a metal layer on the surface of the second conductive layer as a whole surface, thereby increasing the reflectivity of the metal ion stack. The fourth conductive layer is composed of thinner metal wires and / or metal strips at the edges. When a negative pressure is applied to the fourth conductive layer and a positive pressure is applied to the second conductive layer, the metal layer deposited on one side of the second conductive layer is oxidized into metal ions and enters the metal ion layer; the metal ions on one side of the fourth conductive layer are reduced to metal and deposited on the metal wires or edge metal strips of the fourth conductive layer. Light can still pass through the area without metal, thereby reducing the reflectivity of the metal ion stack.

[0027] Preferably, the width of the metal wire is ≤100 μm, for example, it can be 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, 20 μm, 15 μm, 10 μm, 5 μm, 3 μm or 1 μm, etc., preferably ≤20 μm.

[0028] Preferably, the spacing between two adjacent mutually spaced metal wires is ≥10 μm, for example, it can be 10 μm, 20 μm, 50 μm, 80 μm, 100 μm, 150 μm, 200 μm, 300 μm, 500 μm, 1000 μm, 2000 μm or 5000 μm.

[0029] Preferably, the width of the metal strip is ≤3 cm, for example, it can be 3 cm, 2.5 cm, 2 cm, 1.5 cm, 1 cm, 0.5 cm or 0.3 cm.

[0030] In the present invention, the size of the metal wire or metal strip is preferably within the above range, so as to ensure that the fourth conductive layer does not significantly block light and does not affect the adjustment of the reflectivity of the metal ion stack.

[0031] In one embodiment of the present invention, a metal layer is further provided between the metal ion layer and the second transparent conductive layer, and the metal element of the metal layer includes one or a combination of at least two of silver, bismuth, copper, and zinc.

[0032] In the present invention, for the electrochromic device in which the electrochromic stack and the metal ion stack are connected, the present invention has no special limitation on the material of the second transparent conductive layer.

[0033] For an electrochromic device having a transparent insulating layer disposed between an electrochromic stack and a metal ion stack: when the metal ion stack does not contain the metal layer, the material of at least one of the second transparent conductive layer and the fourth conductive layer includes one or a combination of at least two of metals selected from silver, bismuth, copper, and zinc; when the metal ion stack contains the metal layer, the present invention has no special restrictions on the materials of the second transparent conductive layer and the fourth conductive layer.

[0034] In the present invention, if the metal layer is not present on the surface of the metal ion layer, then when adjusting the reflectivity of the electrochromic device, it is necessary to first apply a negative voltage to the second transparent conductive layer and a positive voltage to the first transparent conductive layer or the fourth conductive layer, thereby reducing the metal ions in the metal ion layer to metal and depositing a metal layer on the surface of the second transparent conductive layer. If the metal layer is present on the surface of the metal ion layer, then when adjusting the reflectivity of the electrochromic device, it is possible to first apply a negative voltage to the second transparent conductive layer and a positive voltage to the first transparent conductive layer or the fourth conductive layer, or to first apply a positive voltage to the second transparent conductive layer and a negative voltage to the first transparent conductive layer or the fourth conductive layer.

[0035] In one embodiment of the present invention, the material of the electrodeposition inhibition layer is selected from triazole derivatives. The electrodeposition inhibition layer functions by utilizing the triazole ring structure to react with metal ions, converting the metal ions into subions, which together form oligomers of metal triazole ring derivatives. This prevents metal ions from depositing on the surface, allowing the metal ions to be reduced to metal and then deposited on the surface of the second conductive layer, thereby preventing metal deposition on the first electrochromic functional layer.

[0036] In one embodiment of the present invention, the triazole derivative is selected from one or a combination of at least two of benzotriazole, 1-(methoxymethyl)-1H-benzotriazole, 1-(formylaminomethyl)-1H-benzotriazole, and N5-benzyl-1H-1,2,4-triazole-3,5-diamine.

[0037] In one embodiment of the present invention, the first transparent conductive layer and the third transparent conductive layer are each independently formed of one or at least two of indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, silver nanowires, graphene, carbon nanotubes, metal grids and silver nanoparticles.

[0038] In one embodiment of the present invention, the transparent insulating layer is a hollow layer, a transparent base layer, or a composite layer formed by bonding multiple transparent base layers via an adhesive layer.

[0039] In the present invention, the hollow layer refers to the space between the electrochromic stack and the metal ion stack that is not filled with solid or liquid materials and can be an air layer or a vacuum layer. The transparent insulating layer can be composed of a single transparent substrate layer or multiple transparent substrate layers bonded together by adhesive layers.

[0040] In one embodiment of the present invention, a functional layer is further provided on one side or both sides of the first transparent substrate layer, the second substrate layer and / or the transparent insulating layer, and / or between the layers of the transparent insulating layer, and the functional layer includes a pattern layer, a texture layer, an anti-reflection layer, a color layer, an ink layer, a filter layer, a photonic crystal layer, a liquid crystal layer and a glue layer, or a combination of at least two layers, so that the electrochromic device obtains the effect corresponding to the functional layer.

[0041] In the present invention, the above-mentioned functional layer can be arranged on one or both sides of the first transparent substrate layer, the second substrate layer and / or the transparent insulating layer; when the transparent insulating layer has a multi-layer structure, the functional layer can also be arranged between the layers of the multi-layer structure to enable the electrochromic device to obtain the corresponding function.

[0042] In one embodiment of the present invention, a substrate support layer is further provided on the outer side of the first transparent substrate layer and / or the second substrate layer.

[0043] In one embodiment of the present invention, the first transparent substrate layer and / or the second substrate layer are connected to the substrate support layer via an adhesive layer.

[0044] In the present invention, the outer side refers to the side of the first transparent substrate layer and the second substrate layer that is away from the electrochromic stack and the metal ion stack. The substrate support layer can be made of either a rigid or flexible material. Rigid materials include glass, rigid plastic, and metal, while flexible materials include flexible plastic film. The substrate support layer adjacent to the first transparent substrate layer is preferably transparent; the substrate support layer adjacent to the second substrate layer can be fully transparent, partially transparent, or opaque, depending on the specific application scenario.

[0045] In a second aspect, the present invention provides an electronic terminal comprising the electrochromic device according to the first aspect.

[0046] The electronic terminal can be a wearable electronic product, a mobile electronic product terminal, architectural glass, laminated glass, insulating glass, decorative film, etc. When the electrochromic device is applied to such an electronic terminal, it can be installed at any desired location, such as on the surface or inside the terminal, to achieve various effects such as appearance diversification, privacy protection, status display, information differentiation, ambient light adjustment, and filtering / transmitting light of different preset wavelengths, depending on the specific application scenario.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] In the electrochromic device provided by the present invention, the transmittance of the electrochromic stack and the reflectance of the metal ion stack can be adjusted by adjusting parameters such as the size, duration, and direction of the applied voltage. By coordinating the changes in the transmittance of the electrochromic stack and the reflectance of the metal ion stack, the visual effect of the existing electrochromic device is enhanced, and the surface of the electrochromic device has rich and colorful colors and reflection effects. In some scenarios, the surface of the device can also present a metal-like texture, thereby meeting the needs of various usage scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 A schematic cross-sectional view of the electrochromic device provided in Example 1 of the present invention;

[0050] Figure 2 A schematic cross-sectional view of the electrochromic device provided in Example 2 of the present invention;

[0051] Figure 3 A schematic cross-sectional view of the electrochromic device provided in Example 4 of the present invention;

[0052] Figure 4 A schematic cross-sectional view of the electrochromic device provided in Example 5 of the present invention;

[0053] Figure 5 A schematic cross-sectional view of the electrochromic device provided in Example 6 of the present invention;

[0054] Figure 6 A schematic cross-sectional view of the electrochromic device provided in Example 7 of the present invention;

[0055] Figure 7 Schematic diagram of the cross-sectional structure of the second electrochromic functional layer in Example 7 of the present invention;

[0056] Figure 8 Schematic diagram of the structure of the fourth conductive layer in Example 7 of the present invention;

[0057] Figure 9 A schematic cross-sectional view of the electrochromic device provided in Example 8 of the present invention;

[0058] Figure 10 Schematic diagram of the structure of the fourth conductive layer in Example 8 of the present invention;

[0059] Figure 11 A schematic cross-sectional view of the electrochromic device provided in Example 11 of the present invention;

[0060] Figure 12 A schematic cross-sectional view of the electrochromic device provided in Example 12 of the present invention;

[0061] Among them, 1 is the first transparent substrate layer, 2 is the electrochromic stack, 3 is the metal ion stack, 4 is the second substrate layer, 5 is the functional layer, 6 is the first substrate support layer, 7 is the second substrate support layer, and 8 is the transparent insulating layer;

[0062] 21 is a first transparent conductive layer, 22 is a first electrochromic functional layer, 23 is a second electrochromic functional layer, and 24 is a third transparent conductive layer;

[0063] 221 is a cathode electrochromic material layer, 222 is an electrolyte layer, and 223 is an anode electrochromic material layer;

[0064] 31 is a second transparent conductive layer, 32 is a metal ion layer, 33 is an electrodeposition inhibition layer, 34 is a metal layer, and 35 is a fourth conductive layer;

[0065] 81 is the third transparent base layer, 82 is the functional layer, and 83 is the fourth transparent base layer. DETAILED DESCRIPTION

[0066] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific embodiments. It should be understood by those skilled in the art that the specific embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0067] Example 1

[0068] This embodiment provides an electrochromic device with adjustable reflectivity, such as Figure 1 As shown, it includes a first transparent substrate layer 1, an electrochromic stack 2, a metal ion stack 3 and a second substrate layer 4 stacked in sequence;

[0069] The electrochromic stack 2 includes a first transparent conductive layer 21 and a first electrochromic functional layer 22 stacked together;

[0070] The metal ion stack 3 includes a second transparent conductive layer 31, a metal ion layer 32 and an electrodeposition inhibition layer 33 stacked in sequence, and the first electrochromic functional layer 22 and the electrodeposition inhibition layer 33 are adjacent to each other;

[0071] Among them, the first transparent conductive layer 21 and the second transparent conductive layer 31 serve as a pair of electrodes for driving the electrochromic device, the second substrate layer 4 is completely transparent, the material of the first electrochromic functional layer 22 is NiO, the material of the metal ion layer 32 is a colloid formed by dissolving 3.0wt% hydroxyethyl cellulose in a 10mM AgNO3 aqueous solution, and the material of the electrodeposition inhibition layer 33 is N5-benzyl-1H-1,2,4-triazole-3,5-diamine.

[0072] The following is an exemplary description of the process of adjusting the transmittance and reflectance of the electrochromic device provided in this embodiment:

[0073] Initial state: the electrochromic stack 2 is initially colorless, the metal ion stack 3 is initially transparent, and the appearance of the electrochromic device is colorless and transparent;

[0074] Apply forward voltage (+2.0V): When a forward voltage is applied to the electrochromic device in the initial state, NiO loses electrons and undergoes oxidation reaction, changing from colorless to brown; Ag in the metal ion layer 32 + The electrons are reduced, and a reflective metal Ag layer is deposited on the surface of the second transparent conductive layer 31. When the electrochromic stack 2 is in the colored state, it still has a certain transmittance. After the light passes through the electrochromic stack, it is reflected by the reflective mirror surface, making the appearance of the electrochromic device appear as a reflective brown mirror surface.

[0075] Apply reverse voltage (-1.2V): NiO is reduced by electrons and its color returns to colorless; the deposited metal Ag layer is oxidized to Ag + , enters the metal ion layer 32, and the metal ion stack returns to a transparent state; the electrochromic device returns to its initial state, and its appearance appears colorless and transparent;

[0076] In this embodiment, when the potential of the first transparent conductive layer 21 is higher than the potential of the second transparent conductive layer 31, the voltage direction is called forward; when the potential of the first transparent conductive layer 21 is lower than the potential of the second transparent conductive layer 31, the voltage direction is called reverse.

[0077] During the application of voltage to the electrochromic device, the transmittance of the electrochromic stack 2 can be adjusted to any preset transmittance state between the tinted state and the faded state, and the reflectance of the metal ion stack 3 can be adjusted to any preset transflective state between transparency and total reflection by adjusting parameters such as the magnitude, duration, and direction of the applied voltage. This enriches and enhances the appearance of the electrochromic device. This electrochromic device can be used in electronic terminal products such as wearable electronic products, mobile electronic product terminals, architectural glass, laminated glass, insulating glass, and decorative film layers.

[0078] Example 2

[0079] This embodiment provides an electrochromic device with adjustable reflectivity, the structure of which is as follows: Figure 2 As shown, the difference from Example 1 is that the metal ion stack 3 includes a second transparent conductive layer 31, a metal layer 34, a metal ion layer 32 and an electrodeposition inhibition layer 33 stacked in sequence;

[0080] The material of the first electrochromic functional layer 22 is WO3, the material of the metal layer 34 is Cu, the material of the metal ion layer 32 is a colloid formed by dissolving 3.0wt% hydroxyethyl cellulose in an aqueous solution containing 20mM Cu(Cl)2, 10mM HCl and 1M LiBr, and the material of the electrodeposition inhibition layer 33 is benzotriazole.

[0081] The process of adjusting the transmittance and reflectance of the electrochromic device provided in this embodiment is as follows:

[0082] Initial state: The electrochromic stack 2 is initially colorless, the metal ion stack 3 is initially reflective, and the appearance of the electrochromic device presents a reflective copper mirror effect;

[0083] Apply reverse voltage (-2.0V): Apply reverse voltage to the electrochromic device in the initial state, WO3 gains electrons and is reduced, changing from colorless to blue; Cu in the metal layer 34 loses electrons and is oxidized to Cu 2+ , enters the metal ion layer 32, and the metal ion stack 3 changes from a reflective mirror state to a transparent state; the appearance of the electrochromic device appears blue with a certain transmittance;

[0084] Applying a forward voltage (+1.0V): the first electrochromic functional layer 22 is oxidized and its color returns to colorless; the metal ions in the metal ion layer 32 are reduced, and a metal layer 34 with a reflective effect is deposited on the surface of the second transparent conductive layer 31; the electrochromic device returns to its initial state, restoring the reflective copper mirror effect;

[0085] In this embodiment, when the potential of the first transparent conductive layer 21 is higher than the potential of the second transparent conductive layer 31, the voltage direction is called forward; when the potential of the first transparent conductive layer 21 is lower than the potential of the second transparent conductive layer 31, the voltage direction is called reverse.

[0086] During the application of voltage to the electrochromic device, the transmittance of the electrochromic stack 2 can be adjusted to any preset transmittance state between the tinted state and the faded state, and the reflectance of the metal ion stack 3 can be adjusted to any preset transflective state between transparency and total reflection by adjusting parameters such as the magnitude, duration, and direction of the applied voltage. This enriches and enhances the appearance of the electrochromic device. This electrochromic device can be used in electronic terminal products such as wearable electronic products, mobile electronic product terminals, architectural glass, laminated glass, insulating glass, and decorative film layers.

[0087] Example 3

[0088] This embodiment provides an electrochromic device with adjustable reflectivity. The difference from Embodiment 1 is that the second substrate layer 4 is partially transparent or completely opaque and is made of a material with a preset color, texture or pattern.

[0089] Example 4

[0090] This embodiment provides an electrochromic device with adjustable reflectivity, the structure of which is as follows: Figure 3 As shown, the difference from Example 1 is that a functional layer 5 is provided on the side of the first transparent substrate layer 1 close to the electrochromic stack 2; the functional layer 5 is a pattern layer, a texture layer, an anti-reflection layer, a color layer, an ink layer, a filter layer, a photonic crystal layer or a liquid crystal layer.

[0091] In an alternative embodiment of this embodiment, the functional layer 5 can also be arranged on the side of the first transparent substrate layer 1 away from the electrochromic stack 2, and / or on the side of the second substrate layer 4 close to the metal ion stack 3, away from the metal ion stack 3, or on both sides.

[0092] Example 5

[0093] This embodiment provides an electrochromic device with adjustable reflectivity, the structure of which is as follows: Figure 4 As shown, the difference from Example 1 is that a first base support layer 6 is provided on the outside of the first transparent base layer 1 (the first transparent base layer 1 and the first base support layer 6 are bonded by an adhesive layer, and the adhesive layer is Figure 5 The second base layer 4 is not shown), and a second base support layer 7 is provided on the outside of the second base layer 4 (the second base layer 4 and the second base support layer 7 are bonded by an adhesive layer. Figure 5 not shown).

[0094] In an alternative embodiment of this embodiment, the first base supporting layer 6 may be provided only on the outside of the first transparent base layer 1 , or the second base supporting layer 7 may be provided only on the outside of the second base layer 4 .

[0095] Example 6

[0096] This embodiment provides an electrochromic device with adjustable reflectivity, such as Figure 5 As shown, it includes a first transparent substrate layer 1, an electrochromic stack 2, a metal ion stack 3 and a second substrate layer 4 stacked in sequence;

[0097] The electrochromic stack 2 includes a first transparent conductive layer 21 and a first electrochromic functional layer 22 stacked together;

[0098] The metal ion stack 3 includes a second transparent conductive layer 31 and a metal ion layer 32 stacked in sequence, and the first electrochromic functional layer 22 and the metal ion layer 32 are adjacent;

[0099] Among them, the first transparent conductive layer 21 and the second transparent conductive layer 31 serve as a pair of electrodes for driving the electrochromic device, the second base layer 4 is completely transparent, the material of the first electrochromic functional layer 22 is poly 2-[(2-ethylhexyloxy)methyl]3,4-thieno-1,4-dioxane, and the material of the metal ion layer 32 is Bi(Cl)3.

[0100] The following is an exemplary description of the process of adjusting the transmittance and reflectance of the electrochromic device provided in this embodiment:

[0101] Initial state: the electrochromic stack 2 is initially blue, the metal ion stack 3 is initially transparent, and the appearance of the electrochromic device is transparent blue;

[0102] Apply forward voltage (+1.6V): Apply forward voltage to the electrochromic device in the initial state, poly 2-[(2-ethylhexyloxy)methyl]3,4-thieno-1,4-dioxane loses electrons and undergoes oxidation reaction, changing from blue to colorless; Bi in the metal ion layer 32 3+ The electrons are reduced, and a metal Bi layer with a reflective effect is deposited on the surface of the second transparent conductive layer 31; the appearance of the electrochromic device appears as a silver mirror with a reflective effect;

[0103] Applying reverse voltage (-1.6V): Poly (2-[(2-ethylhexyloxy)methyl]3,4-thieno-1,4-dioxane) is reduced by electrons and its color returns to blue; the deposited metal Bi layer is oxidized to Bi 3+ , enters the metal ion layer 32, and the metal ion stack returns to a transparent state; the electrochromic device returns to its initial state, and its appearance appears to be a transparent blue state.

[0104] In this embodiment, when the potential of the first transparent conductive layer 21 is higher than the potential of the second transparent conductive layer 31, the voltage direction is called forward; when the potential of the first transparent conductive layer 21 is lower than the potential of the second transparent conductive layer 31, the voltage direction is called reverse.

[0105] During the application of voltage to the electrochromic device, the transmittance of the electrochromic stack 2 can be adjusted to any preset transmittance state between the tinted state and the faded state, and the reflectance of the metal ion stack 3 can be adjusted to any preset transflective state between transparency and total reflection by adjusting parameters such as the magnitude, duration, and direction of the applied voltage. This enriches and enhances the appearance of the electrochromic device. This electrochromic device can be used in electronic terminal products such as wearable electronic products, mobile electronic product terminals, architectural glass, laminated glass, insulating glass, and decorative film layers.

[0106] However, since this embodiment does not use an electrodeposition inhibition layer, some metal Bi will gradually be deposited on the first electrochromic functional layer 22 as charging and discharging proceeds, affecting the long-term cycle performance of the electrochromic device and the appearance.

[0107] Example 7

[0108] This embodiment provides an electrochromic device with adjustable reflectivity, such as Figure 6 As shown, it includes a first transparent substrate layer 1, an electrochromic stack 2, a transparent insulating layer 8, a metal ion stack 3 and a second substrate layer 4 stacked in sequence;

[0109] The electrochromic stack 2 includes a first transparent conductive layer 21, a second electrochromic functional layer 23 and a third transparent conductive layer 24 stacked in sequence, wherein the first transparent conductive layer 21 is close to the first transparent substrate layer 1;

[0110] The metal ion stack 3 includes a second transparent conductive layer 31, a metal ion layer 32 and a fourth conductive layer 35 stacked in sequence, and the second transparent conductive layer 31 is close to the second substrate layer 4;

[0111] The structure of the second electrochromic functional layer 23 is as follows Figure 7 As shown, it is composed of a cathode electrochromic material layer 231, an electrolyte layer 232 and an anode electrochromic material layer 233 stacked in sequence, and the cathode electrochromic material layer 231 is close to the first transparent conductive layer 21;

[0112] The first transparent conductive layer 21 and the third transparent conductive layer 24 are the counter electrodes for driving the electrochromic stack 2; the second transparent conductive layer 31 and the fourth conductive layer 35 are the pair of electrodes for driving the metal ion stack 3;

[0113] The second substrate layer 4 is completely transparent, the transparent insulating layer 8 is a transparent substrate layer, the cathode electrochromic material layer 231 is made of tungsten oxide, the electrolyte layer is made of LiClO4-propylene carbonate, the anode electrochromic material layer 233 is made of nickel oxide, and the metal ion layer 32 is made of a colloid formed by dissolving 3.0 wt% hydroxyethyl cellulose in an aqueous solution containing 10 mM CuCl2, 10 mM BiCl3, 10 mM HCl, and 1 M LiBr.

[0114] The shape of the fourth conductive layer 35 is as follows: Figure 8 As shown, it is a metal mesh composed of Cu / Bi alloy metal wires arranged in a staggered manner, the width of the metal wires is 10 μm, and the spacing between the metal wires is 80 μm.

[0115] The following is an exemplary description of the process of adjusting the transmittance and reflectance of the electrochromic device provided in this embodiment:

[0116] Initial State: Electrochromic stack 2 is initially colorless, and metal ion stack 3 is transparent. The electrochromic device is transparent. No power is applied to electrochromic stack 2 and metal ion stack 3, allowing incident light to pass through them.

[0117] Adjustment of the transmittance of the electrochromic stack 2: When a -2V reverse voltage is applied to the electrochromic stack alone (the potential of the first transparent conductive layer 21 is lower than the potential of the third transparent conductive layer 24), the cathode electrochromic material layer 231 is reduced and changes from colorless to blue, and the anode electrochromic material layer 233 is oxidized and changes from colorless to brown. When a +1.5V forward voltage is applied (the potential of the first transparent conductive layer 21 is higher than the potential of the third transparent conductive layer 24), the cathode electrochromic material layer 231 is oxidized and changes from blue to colorless, and the anode electrochromic material layer 233 is reduced and changes from brown to colorless. By adjusting parameters such as the magnitude, duration, and direction of the applied voltage, the transmittance of the electrochromic stack 2 can be adjusted to any preset transmittance state between a colorless faded state and a dark blue (a superimposed color of blue and brown) colored state.

[0118] Adjustment of the reflectivity of the metal ion stack 3: Applying a +1.0V reverse voltage to the metal ion stack alone (the potential of the second transparent conductive layer 31 is lower than the potential of the fourth conductive layer 35), the metal Cu and Bi in the metal grid of the fourth conductive layer 35 lose electrons and are oxidized to Cu 2+ and Bi 3+ , enters the metal ion layer 32; the metal ions in the metal ion layer 32 are reduced, and a mixed metal layer of Cu and Bi with a reflective effect is deposited on the surface of the second transparent conductive layer 31, and the metal ion stack 3 is in a total reflection state. Applying a -1.0V voltage (the potential of the second transparent conductive layer 31 is higher than the potential of the fourth conductive layer 35), the deposited mixed metal layer of Cu and Bi is oxidized into metal ions and enters the metal ion layer 32; the metal ions in the metal ion layer 32 gain electrons at the metal mesh position of the fourth conductive layer 35 and are reduced to metal, and deposited on the metal mesh. Since light can pass through the mesh, the metal ion stack 3 is in a transparent state. By adjusting the parameters such as the size, duration, and direction of the applied voltage, the reflectivity of the metal ion stack 3 can be adjusted to a semi-transparent and semi-reflective state with any preset reflectivity between transparency and total reflection.

[0119] In the electrochromic device provided in this embodiment, the electrochromic stack 2 and the metal ion stack 3 are independently controlled, so the number of layers is greater than that of Example 1. However, the states of the electrochromic stack 2 and the metal ion stack 3 are not constrained by each other, and a richer appearance display effect can be produced by adjusting the voltage separately.

[0120] Example 8

[0121] This embodiment provides an electrochromic device with adjustable reflectivity, the structure of which is as follows: Figure 9 As shown, the difference from Example 7 is that the metal ion stack 3 is set as the fourth conductive layer 35 close to the second base layer 4, the second transparent conductive layer 31 is close to the transparent insulating layer 8, and the shape of the fourth conductive layer 35 is as follows: Figure 10 As shown, it is a metal frame composed of four Ag / Bi alloy metal strips located at the edge of the layer plane, and the width of the metal strip is 2 cm.

[0122] Example 9

[0123] This embodiment provides an electrochromic device with adjustable reflectivity. The difference from Example 7 is that the second electrochromic functional layer is a polymer dispersed liquid crystal layer, and the material of the polymer dispersed liquid crystal layer is composed of 15wt% polymethyl methacrylate polymer and 75wt% 4-(trans-4-n-hexylcyclohexyl)-4'-cyanobiphenyl liquid crystal small molecules.

[0124] In an alternative embodiment of this embodiment, the second electrochromic functional layer is a suspended particle device layer.

[0125] Example 10

[0126] This embodiment provides an electrochromic device with adjustable reflectivity. The difference from Example 7 is that the second substrate layer 4 is partially transparent or completely opaque, and uses a material with a preset color, texture or pattern. The second electrochromic functional layer 23 is a composite material layer formed by mixing a cathode electrochromic material, an electrolyte and an anode electrochromic material.

[0127] Example 11

[0128] This embodiment provides an electrochromic device with adjustable reflectivity, the structure of which is as follows: Figure 11 As shown, the difference from Example 7 is that the transparent insulating layer 8 is composed of a third transparent base layer 81, a functional layer 82 and a fourth transparent base layer 83 stacked in sequence; the functional layer 82 is a pattern layer, a texture layer, an anti-reflection layer, a color layer, an ink layer, a filter layer, a photonic crystal layer or a liquid crystal layer.

[0129] Example 12

[0130] This embodiment provides an electrochromic device with adjustable reflectivity, the structure of which is as follows: Figure 12 As shown, the difference from Example 7 is that a first base support layer 6 is provided on the outside of the first transparent base layer 1 (the first transparent base layer 1 and the first base support layer 6 are bonded by an adhesive layer, and the adhesive layer is Figure 9 The second base layer 4 is not shown), and a second base support layer 7 is provided on the outside of the second base layer 4 (the second base layer 4 and the second base support layer 7 are bonded by an adhesive layer. Figure 12not shown).

[0131] In an alternative embodiment of this embodiment, the first base supporting layer 6 may be provided only on the outer side of the first transparent base layer 1 , or the second base supporting layer 7 may be provided only on the outer side of the second base layer 4 .

[0132] In the electrochromic device provided by the embodiments of the present invention, the transmittance of the electrochromic stack and the reflectance of the metal ion stack can be adjusted by adjusting parameters such as the magnitude, duration, and direction of the applied voltage. This coordinated change in the transmittance of the electrochromic stack and the reflectance of the metal ion stack enhances the visual effects of existing electrochromic devices, resulting in a rich variety of colors and reflective effects on the device surface. This electrochromic device can be used in electronic terminal products such as wearable electronic products, mobile electronic product terminals, architectural glass, laminated glass, insulating glass, and decorative film layers.

[0133] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. An electrochromic device with adjustable reflectivity, characterized in that: The electrochromic device comprises a first transparent substrate layer, an electrochromic stack, a metal ion stack, and a second substrate layer stacked in sequence; the electrochromic stack comprises a first transparent conductive layer and a first electrochromic functional layer stacked in sequence; the metal ion stack comprises a second transparent conductive layer and a metal ion layer stacked in sequence, the first electrochromic functional layer being adjacent to the metal ion layer; or the metal ion stack comprises a second transparent conductive layer, a metal ion layer, and an electrodeposition inhibiting layer stacked in sequence, the first electrochromic functional layer being adjacent to the electrodeposition inhibiting layer; The first electrochromic functional layer is used to change the transmittance state according to voltage, and the metal ion layer is used to change the reflectivity state according to voltage.

2. The electrochromic device according to claim 1, characterized in that The first electrochromic functional layer is an anode electrochromic material layer or a cathode electrochromic material layer; and / or The metal ions in the metal ion layer include one or a combination of at least two of silver ions, bismuth ions, copper ions, and zinc ions; and / or The metal ion layer is a liquid electrolyte layer containing metal ions or a gel electrolyte layer containing metal ions.

3. The electrochromic device according to claim 1 or 2, characterized in that: A metal layer is further provided between the metal ion layer and the second transparent conductive layer. The metal elements of the metal layer include one or a combination of at least two of silver, bismuth, copper, and zinc.

4. The electrochromic device according to claim 1 or 2, characterized in that: The material of the electrodeposition inhibition layer is selected from triazole derivatives.

5. The electrochromic device according to claim 4, characterized in that: The triazole derivative is selected from one or a combination of at least two of benzotriazole, 1-(methoxymethyl)-1H-benzotriazole, 1-(formylaminomethyl)-1H-benzotriazole and N5-benzyl-1H-1,2,4-triazole-3,5-diamine.

6. The electrochromic device according to claim 1 or 2, characterized in that: The first transparent conductive layer is formed of one or at least two of indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, silver nanowires, graphene, carbon nanotubes, metal grids and silver nanoparticles.

7. The electrochromic device according to claim 1 or 2, characterized in that: A functional layer is further provided on one or both sides of the first transparent substrate layer, and / or a functional layer is further provided on one or both sides of the second substrate layer, and the functional layer includes one or a combination of at least two layers selected from the group consisting of a pattern layer, a texture layer, an anti-reflection layer, a color layer, an ink layer, a filter layer, a photonic crystal layer, a liquid crystal layer and a glue layer.

8. The electrochromic device according to claim 7, characterized in that: A substrate support layer is further provided on the outer side of the first transparent substrate layer and / or the second substrate layer.

9. The electrochromic device according to claim 8, characterized in that: The first transparent substrate layer and / or the second substrate layer are connected to the substrate support layer via an adhesive layer.

10. An electronic terminal, characterized in that: The electronic terminal contains the electrochromic device according to any one of claims 1 to 9.

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