CN212873159U - Adjustable reflectivity's electrochromic device and contain its electronic terminal - Google Patents
Adjustable reflectivity's electrochromic device and contain its electronic terminal Download PDFInfo
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- CN212873159U CN212873159U CN202021375865.3U CN202021375865U CN212873159U CN 212873159 U CN212873159 U CN 212873159U CN 202021375865 U CN202021375865 U CN 202021375865U CN 212873159 U CN212873159 U CN 212873159U
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Abstract
The utility model provides an adjustable reflectivity's electrochromic device and contain its electronic terminal. The electrochromic device comprises a first transparent substrate layer, an electrochromic stack, a metal ion stack and a second substrate layer which are sequentially stacked, wherein the electrochromic stack comprises a first transparent conductive layer and an electrochromic functional layer which are stacked, and the metal ion stack comprises a second transparent conductive layer, a metal ion layer and an optional electrodeposition inhibition layer which are stacked; the electrochromic functional layer is adjacent to the metal ion layer or the electrodeposition inhibition layer; or a transparent insulating layer is arranged between the electrochromic stack and the metal ion stack at intervals, the electrochromic stack comprises a first transparent conducting layer, an electrochromic functional layer and a third transparent conducting layer which are laminated, and the metal ion stack comprises a second transparent conducting layer, a metal ion layer, an electrodeposition inhibiting layer and a fourth conducting layer which are laminated. The reflectivity and the transmittance of the electrochromic device are adjustable, and the electrochromic device has stronger and richer visual effects.
Description
Technical Field
The utility model belongs to the technical field of the demonstration that discolours, concretely relates to adjustable reflectivity's electrochromic device and contain its electron terminal.
Background
Electrochromism refers to a phenomenon that the optical properties of a material are subjected to stable and reversible color change under the action of an external electric field, and the electrochromism shows reversible changes of color and transparency in appearance. Materials having electrochromic properties are referred to as electrochromic materials, and devices made with electrochromic materials are referred to as electrochromic devices. The electrochromic device has very important application prospect in the fields of color-changing glasses, electronic display, military hiding, building energy conservation and the like.
A common electrochromic device generally includes 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, which are sequentially stacked. When voltage is applied, ions are conducted from the ion storage layer to the electrochromic layer through the electrolyte layer, and color change is achieved; when a reverse voltage is applied, ions are conducted from the electrochromic layer through the electrolyte layer into the ion storage layer, and color fading is achieved.
Electrochromic materials can be classified into inorganic electrochromic materials and organic electrochromic materials. The inorganic electrochromic material has the advantages of stability and quick response, such as tungsten trioxide, vanadium pentoxide, nickel oxide, titanium dioxide and the like; the organic electrochromic materials have various types and rich colors, and are convenient to design, such as viologen and polythiophene. By selecting different electrochromic materials, electrochromic devices with different colors and different color change ranges can be obtained.
However, in a specific electrochromic device, the color change effect produced according to the change of transmittance is relatively single, and it is difficult to present diversified colorful visual effects. Moreover, even if the pattern layer is added below the device, when the transmittance of the electrochromic device changes, particularly when the electrochromic device is in a colored state, the electrochromic device often looks not bright enough and the color of the pattern layer looks dull when the transmittance is low, so that the electrochromic device is not beautiful in practical application and has poor visual effect.
SUMMERY OF THE UTILITY MODEL
To the deficiency that prior art exists, the utility model aims to provide an electrochromic device of adjustable reflectivity and contain its electronic terminal. The reflectivity and the transmittance of the electrochromic device are adjustable, and the visual effect of the electrochromic device is enhanced and enriched through the cooperation of the transmittance change of the electrochromic stack and the reflectivity change of the metal ion stack.
To achieve the purpose, the utility model adopts the following technical proposal:
in a first aspect, the present invention provides an electrochromic device with adjustable reflectivity, which includes 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 second transparent conductive layer, a metal ion layer, and optionally an electrodeposition inhibition layer, which are stacked; the first electrochromic functional layer is adjacent to the metal ion layer or the electrodeposition inhibition layer;
or comprises a first transparent substrate layer, an electrochromic stack, a transparent insulating layer, a metal ion stack and a second substrate layer which are sequentially stacked; the electrochromic stack comprises a first transparent conducting layer, a second electrochromic functional layer and a third transparent conducting layer which are sequentially stacked; the metal ion stack comprises a second transparent conducting layer, a metal ion layer and a fourth conducting layer which are sequentially stacked.
In the present invention, the term "optionally having an electrodeposition inhibiting layer" means having an electrodeposition inhibiting layer or not having an electrodeposition inhibiting layer. When the electrochromic stack contains an electrodeposition inhibiting layer, the first electrochromic functional layer is adjacent to the electrodeposition inhibiting layer; when the electrochromic stack does not contain an electrodeposition-inhibiting layer, the first electrochromic functional layer is adjacent to the metal ion layer.
The utility model provides an electrochromic device uses electrochromic stack and metal ion stack as major structure, in the metal ion stack, when adding the malleation to first transparent conducting layer, when the transparent conducting layer of second adds the negative pressure, or when adding the malleation to fourth conducting layer, when the transparent conducting layer of second adds the negative pressure, the metal ion in the metal ion layer can be reduced into the metal, the deposit is on the transparent conducting layer surface of second, makes the reflectivity of metal ion stack increase; when adding the negative pressure to first transparent conducting layer, when the transparent conducting layer of second adds the malleation, or when adding the negative pressure to fourth conducting layer, the transparent conducting layer of second adds the malleation, and sedimentary metal can become metal ion, gets into in the metal ion layer, makes the reflectivity of metal ion stack reduce. By adjusting the applied voltage, the metal ion stack can be controlled to switch between transparent and total reflection, or be in any reflectivity state between transparent and total reflection.
In the electrochromic stack, the first electrochromic functional layer or the second electrochromic functional layer can be switched between a colored state and a faded state, or in any transmittance state between the colored state and the faded state, by adjusting the voltage applied to the first electrochromic functional layer or the second electrochromic functional layer. The colour of the first electrochromic functional layer or the second electrochromic functional layer in the coloured state depends on the type of electrochromic material chosen.
Compare with current electrochromic device, the utility model discloses a transmissivity of electrochromic stack changes and the reflectivity of metal ion stack changes's cooperation, has strengthened the visual effect of electrochromic device (especially when coloring), makes electrochromic device demonstrate dazzling various visual effect more, can also make the product surface feel like metal under some scenes to satisfy the demand of multiple use scene.
The utility model discloses in, when the electrochromic functional layer of electrochromic storehouse and the metal ion layer of metal ion storehouse were adjacent, first transparent conducting layer and the transparent conducting layer of second were two electrodes of drive electrochromic device. The transmittance of the electrochromic stack and the reflectivity of the metal ion stack change simultaneously when the applied voltage is changed.
When the electrochromic stack and the metal ion stack are separated by the transparent insulating layer, the first transparent conducting layer and the third transparent conducting layer are electrodes for driving the electrochromic stack, and the second transparent conducting layer and the fourth conducting layer are electrodes for driving the metal ion stack. The electrochromic stack and the metal ion stack are independent from each other, and the change of the transmittance of the electrochromic stack and the change of the reflectivity of the metal ion stack are not influenced with each other. At this time, the metal ion stack may be disposed such that the second transparent conductive layer is close to the second substrate layer, or may be disposed such that the fourth conductive layer is close to the second substrate layer.
In the present invention, "transparent" means completely transparent or partially transparent, and the first transparent substrate layer may be completely transparent or partially transparent, so that the electrochromic device exhibits a specific pattern. The second substrate layer may be fully transparent, partially transparent or opaque.
The transparent substrate layer may be a rigid transparent substrate layer or a flexible transparent substrate layer. The utility model has no special limitation on the material of the basal layer, and the hard transparent basal layer can be made of glass for example; the material of the flexible transparent substrate layer includes, but is not limited to, polyethylene terephthalate (PET), cyclic olefin copolymer, and cellulose triacetate, any one of which or a combination of at least two of which may be selected, and typical but non-limiting combinations include combinations of PET and cyclic olefin copolymer, cyclic olefin copolymer and cellulose triacetate, PET and cellulose triacetate, and PET, cyclic olefin copolymer, and cellulose triacetate.
In one embodiment of the present invention, the first electrochromic functional layer is an anodic electrochromic material layer or a cathodic electrochromic material layer; 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.
In the utility model, the material of the first electrochromic functional layer is an anode electrochromic material or a cathode electrochromic material; cathode electrochromic materialThe material can be subjected to reduction reaction by electrons, and the transmittance is changed between a colored state and a discolored state; the anode electrochromic material can lose electrons to generate oxidation reaction, and the transmittance of the anode electrochromic material is changed between a colored state and a faded state. The material of the first electrochromic functional layer may in particular be chosen from the prior art discolouring materials capable of forming solid thin films, such as NiO in inorganic materials, WO3，Nb2O5，TiO2Etc.; polythiophene derivatives and copolymer systems in organic materials, and the like; metal conjugated systems, such as prussian blue, and the like. The color change of the first electrochromic functional layer can be adjusted according to the type of the electrochromic material. When the anode electrochromic material or the cathode electrochromic material is selected as the material of the first electrochromic functional layer, the anode electrochromic material or the cathode electrochromic material can be matched with the initial state of the corresponding metal ion stack according to the requirements of the product on transmittance and reflectivity to serve as the basis for material type selection.
The second electrochromic functional layer is a structural unit with an electrochromic function, and can be a flexible or rigid sheet layer or a sheet layer with adjustable transmittance made of a combination of multiple layers of materials. For example, a PDLC (Polymer Dispersed Liquid Crystal) layer, an SPD (Suspended Particle Device) layer, or an EC (Electrochromic) layer may be used. The EC layer is a composite layer of an anode electrochromic material, an electrolyte and a cathode electrochromic material. The utility model discloses in, the EC layer can be the liquid composite material layer or the gel state composite material layer that form after mixing by anodal electrochromic material, electrolyte and negative pole electrochromic material, also can be the solid-state composite bed of the three layer construction that comprises anodal electrochromic material layer, solid electrolyte layer and the negative pole electrochromic material layer that stacks gradually.
For convenience of explanation, the process of adjusting the transmittance of the electrochromic layer is described by taking as an example EC (composed of an anodic electrochromic material layer, an electrolyte layer, and a cathodic electrochromic material layer which are sequentially stacked) of a specific structure: and a voltage applied to the two ends of the anode electrochromic material layer and the cathode electrochromic material layer promotes ions to move between the anode electrochromic material layer and the cathode electrochromic material layer and to be embedded/extracted or to be extracted/embedded in the anode electrochromic material layer and the cathode electrochromic material layer, so that the optical states of the electrochromic materials in the anode electrochromic material layer and the cathode electrochromic material layer are changed, and further, the transmittance of the EC layer is changed to change the EC layer from a coloring state, an intermediate state to a fading state.
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.
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.
In an embodiment of the present invention, the fourth conductive layer is formed by metal lines staggered or spaced, and/or metal strips located at the edge of a plane where the fourth conductive layer is located.
It should be noted that, the utility model discloses in the material of the transparent conducting layer of second occupy its planar whole region in place, when adding the malleation to the fourth conducting layer, the second conducting layer adds the negative pressure, and the metal ion in the metal ion layer can be at the metal level of second conducting layer surface deposit whole face to the reflectivity that makes the metal ion storehouse increases. The fourth conducting layer is composed of a thin metal wire and/or a metal strip at the edge, when negative pressure is applied to the fourth conducting layer and positive pressure is applied to the second conducting layer, the metal layer deposited on one side of the second conducting layer is oxidized into metal ions, and the metal ions enter the metal ion layer; the metal ions on one side of the fourth conductive layer are reduced into metal and deposited on the metal wires or the edge metal strips of the fourth conductive layer, and light can still pass through the area without the metal, so that the reflectivity of the metal ion stack is reduced.
Preferably, the width of the metal line is 100 μm or less, for example, 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 or less.
Preferably, the spacing between two adjacent spaced metal lines is 10 μm or more, such as 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.
Preferably, the width of the metal strip is ≦ 3cm, and may be, for example, 3cm, 2.5cm, 2cm, 1.5cm, 1cm, 0.5cm, or 0.3cm, etc.
The utility model discloses in, the size of metal wire or metal strip is preferred in above-mentioned within range, can guarantee like this that the fourth conducting layer does not obviously shelter from light, does not influence the regulation of metal ion storehouse reflectivity.
In an embodiment of the present invention, a metal layer is further disposed between the metal ion layer and the second transparent conductive layer.
Preferably, the metal element of the metal layer comprises one or a combination of at least two of silver, bismuth, copper and zinc.
The utility model discloses in, to the electrochromic device that electrochromic storehouse and metal ion stack link to each other, the utility model discloses it is right the material of the transparent conducting layer of second does not have special restriction.
For an electrochromic device with a transparent insulating layer disposed between the electrochromic stack and the metal ion stack: when the metal layer is not contained in the metal ion stack, the material of at least one of the second transparent conductive layer and the fourth conductive layer comprises one or a combination of at least two of metal silver, bismuth, copper and zinc; when the metal ion stack contains the metal layer, the utility model discloses it is right the material of second transparent conducting layer and fourth conducting layer does not have special restriction.
The utility model discloses in, if the metal ion layer surface does not the metal level, then when the reflectivity of electrochromic device is adjusted to needs, need add the negative pressure to the transparent conducting layer of second earlier, first transparent conducting layer or fourth conducting layer add the malleation, make the metal ion in the metal ion layer restore into the metal, go out the metal level at the transparent conducting layer surface deposition of second. If the metal layer is arranged on the surface of the metal ion layer, when the reflectivity of the electrochromic device needs to be adjusted, negative pressure can be firstly applied to the second transparent conductive layer, and positive pressure can be applied to the first transparent conductive layer or the fourth conductive layer; or the second transparent conductive layer may be applied with positive voltage, and the first transparent conductive layer or the fourth conductive layer may be applied with negative voltage.
In an embodiment of the present invention, the electrodeposition inhibiting layer is a triazole derivative material layer.
The electrodeposition inhibiting layer has the function of converting metal ions into sub-ions by utilizing the reaction of the triazole ring structure and the metal ions to jointly form the oligomer of the metal triazole ring derivative, so that the metal ions are prevented from forming deposition on the surface, the metal ions are reduced into metal and then deposited on the surface of the second conductive layer, and the metal is prevented from depositing on the first electrochromic functional layer.
In an embodiment of the present invention, the triazole derivative material layer is a benzotriazole material layer, a 1- (methoxymethyl) -1H-benzotriazole material layer, a 1- (formamidomethyl) -1H-benzotriazole material layer, or an N5-benzyl-1H-1, 2, 4-triazole-3, 5-diamine material layer.
In an 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 nanowire, graphene, carbon nanotube, metal mesh, and silver nanoparticle.
In an embodiment of the present invention, the transparent insulating layer is a hollow layer, a transparent substrate layer, or a composite layer formed by bonding a plurality of transparent substrate layers through an adhesive layer.
In the utility model discloses in, the hollow layer is that the space between electrochromic stack and the metal ion stack does not have solid or liquid material to fill, and it can be air bed or vacuum layer etc.. The transparent insulating layer may be formed by a transparent substrate layer, or may be a plurality of transparent substrate layers bonded by adhesive layers.
The utility model discloses an embodiment in one side or both sides of first transparent substrate layer, second substrate layer and/or transparent insulating layer, and/or still be provided with the functional layer between transparent insulating layer's the layer, the functional layer is pattern layer, texture layer, anti-reflection layer, color layer, printing ink layer, filter layer, photonic crystal layer, liquid crystal layer or glue film, so that electrochromic device obtains the effect that the functional layer corresponds.
In the present invention, the functional layer may be disposed on one or both surfaces of the first transparent substrate layer, the second substrate layer and/or the transparent insulating layer; when the transparent insulating layer is a multilayer structure, a functional layer can also be arranged between layers of the multilayer structure, so that the electrochromic device can obtain corresponding functions.
In an embodiment of the present invention, a substrate supporting layer is further disposed outside the first transparent substrate layer and/or the second substrate layer.
In an embodiment of the invention, the first transparent substrate layer and/or the second substrate layer are connected to the substrate support layer by a tie layer.
In the present invention, the above-mentioned outside is the side of the first transparent substrate layer and the second substrate layer away from the electrochromic stack and the metal ion stack. The substrate supporting layer is made of hard materials or flexible materials, the hard materials comprise glass, hard plastics and metal, and the flexible materials comprise flexible plastic films. The substrate supporting layer close to the first transparent substrate layer is preferably made of transparent materials; the substrate supporting layer close to the second substrate layer may be a fully transparent material, or may also be a partially transparent material or an opaque material, and the material may be selected according to a specific application scenario.
In a second aspect, the present invention provides an electronic terminal, wherein the electrochromic device of the first aspect is contained in the electronic terminal.
The electronic terminal can be a wearable electronic product, a mobile electronic product terminal, architectural glass, laminated glass, hollow glass, a decorative film layer and the like. When the electrochromic device is applied to the electronic terminal, the electrochromic device can be arranged on the surface or inside of the terminal and at any required position, and the effects of diversified appearance, privacy shielding, state display, information distinguishing, environment brightness adjustment, light filtering/transmission of different preset wavelengths and the like are achieved according to specific application scenes.
Compared with the prior art, the utility model discloses following beneficial effect has:
the utility model provides an among the electrochromic device, the transmissivity of electrochromic stack and the reflectivity of metal ion stack can be adjusted through the size of adjusting applied voltage, it is long, direction isoparametric, the transmissivity through the electrochromic stack changes and the reflectivity of metal ion stack changes's cooperation, the visual effect of current electrochromic device has been strengthened, make electrochromic device surface obtain rich and varied colour and reflection effect, can also make the device surface demonstrate the feel like metal under some scenes, thereby satisfy the demand of multiple use scene.
Drawings
Fig. 1 is a schematic cross-sectional view of an electrochromic device provided in embodiment 1 of the present invention;
fig. 2 is a schematic cross-sectional structure diagram of an electrochromic device provided in embodiment 2 of the present invention;
fig. 3 is a schematic cross-sectional structure diagram of an electrochromic device provided in embodiment 4 of the present invention;
fig. 4 is a schematic cross-sectional view of an electrochromic device provided in embodiment 5 of the present invention;
fig. 5 is a schematic cross-sectional view of an electrochromic device according to embodiment 6 of the present invention;
fig. 6 is a schematic cross-sectional view of an electrochromic device according to embodiment 7 of the present invention;
fig. 7 is a schematic cross-sectional view of a second electrochromic functional layer according to embodiment 7 of the present invention;
fig. 8 is a schematic structural view of a fourth conductive layer in embodiment 7 of the present invention;
fig. 9 is a schematic cross-sectional view of an electrochromic device according to embodiment 8 of the present invention;
fig. 10 is a schematic structural view of a fourth conductive layer in embodiment 8 of the present invention;
fig. 11 is a schematic cross-sectional view of an electrochromic device according to embodiment 11 of the present invention;
fig. 12 is a schematic cross-sectional view of an electrochromic device according to embodiment 12 of the present invention;
the transparent substrate comprises a substrate 1, an electrochromic stack 2, a metal ion stack 3, a second substrate 4, a functional layer 5, a first substrate supporting layer 6, a second substrate supporting layer 7 and a transparent insulating layer 8, wherein the first transparent substrate layer, the electrochromic stack 2, the metal ion stack 4 and the transparent insulating layer 8 are arranged in sequence;
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;
221 is a cathode electrochromic material layer, 222 is an electrolyte layer, and 223 is an anode electrochromic material layer;
31 is a second transparent conductive layer, 32 is a metal ion layer, 33 is an electrodeposition inhibiting layer, 34 is a metal layer, and 35 is a fourth conductive layer;
reference numeral 81 denotes a third transparent base layer, 82 denotes a functional layer, and 83 denotes a fourth transparent base layer.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments with reference to the accompanying drawings. It should be understood by those skilled in the art that the specific embodiments described are merely to aid in understanding the present invention and should not be considered as specific limitations of the present invention.
Example 1
The embodiment provides an electrochromic device with adjustable reflectivity, as shown in fig. 1, which includes a first transparent substrate layer 1, an electrochromic stack 2, a metal ion stack 3, and a second substrate layer 4, which are sequentially stacked;
the electrochromic stack 2 comprises a first transparent conductive layer 21 and a first electrochromic functional layer 22, which are laminated;
the metal ion stack 3 comprises a second transparent conductive layer 31, a metal ion layer 32 and an electrodeposition inhibition layer 33 which are sequentially laminated, wherein the first electrochromic functional layer 22 is adjacent to the electrodeposition inhibition layer 33;
wherein the first transparent conductive layer 21 and the second transparent conductive layer 31 are used as a pair of electrodes for driving the electrochromic device, the second substrate layer 4 is completely transparent, the first electrochromic functional layer 22 is made of NiO, the metal ion layer 32 is made of 3.0 wt% hydroxyethyl cellulose dissolved in 10mM AgNO3The material of the electrodeposition inhibiting layer 33 is N5-benzyl-1H-1, 2,4-triazole-3, 5-diamine.
The following describes an exemplary adjustment process of transmittance and reflectance of the electrochromic device provided in this embodiment:
the initial state: the electrochromic stack 2 is colorless initially, the metal ion stack 3 is transparent initially, and the appearance of the electrochromic device is colorless and transparent;
forward voltage (+2.0V) applied: applying a forward voltage to the electrochromic device in the initial state, and carrying out oxidation reaction on NiO electron losing electrons to change from colorless to brown; ag in the metal ion layer 32+The electrons are reduced, and a metal Ag layer with a reflection effect is deposited on the surface of the second transparent conducting layer 31; when the electrochromic stack 2 is in a colored state, the electrochromic stack has a certain transmittance, and light rays are reflected by the reflecting mirror surface after passing through the electrochromic stack, so that the appearance of the electrochromic device is a tan mirror surface with a reflecting effect;
reverse voltage (-1.2V) was applied: the NiO electron is reduced, and the color is recovered to be colorless; the deposited metallic Ag layer is oxidized to Ag+Entering the metal ion layer 32, and the metal ion stack is restored to a transparent state; the electrochromic device returns to the initial state, and the appearance of the electrochromic device is in a colorless transparent state;
in the present 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 referred to as a forward direction; when the potential of the first transparent conductive layer 21 is lower than the potential of the second transparent conductive layer 31, the direction of the voltage is referred to as reverse.
In the process of applying voltage to the electrochromic device, parameters such as the magnitude, the duration and the direction of the applied voltage can be adjusted to adjust the transmittance of the electrochromic stack 2 to be in any preset transmittance state between a coloring state and a fading state, and adjust the reflectance of the metal ion stack 3 to be in any semi-transparent semi-reflective state between transparent state and total reflection state, so that the appearance effect of the electrochromic device is enriched and enhanced. The electrochromic device can be used in electronic terminal products such as wearable electronic products, mobile electronic product terminals, building glass, laminated glass, hollow glass, decorative film layers and the like.
Example 2
The present embodiment provides an electrochromic device with adjustable reflectivity, whose structure is shown in fig. 2, and the difference from embodiment 1 is that a 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, which are sequentially stacked;
the material of the first electrochromic functional layer 22 is WO3The metal layer 34 is made of Cu, and the metal ion layer 32 is made of 3.0 wt% hydroxyethyl cellulose dissolved in Cu (Cl) of 20mM210mM HCl and 1M LiBr, and the material of the electrodeposition inhibition layer 33 is benzotriazole.
The adjustment process of the transmittance and the reflectance of the electrochromic device provided by the embodiment is as follows:
the initial state: the electrochromic stack 2 is colorless initially, the metal ion stack 3 is in a reflective state initially, and the appearance of the electrochromic device is in a reflective copper mirror effect;
reverse voltage (-2.0V) was applied: applying a reverse voltage to the electrochromic device in the initial state, WO3The electrons are reduced and change from colorless to blue; the Cu in the metal layer 34 is oxidized to Cu by electron loss2+Entering the metal ion layer 32, the metal ion stack 3 changes from the mirror surface state to the transparent state; the appearance of the electrochromic device appears as blue with a certain transmittance;
forward voltage (+1.0V) applied: the first electrochromic functional layer 22 is oxidized and the color returns to colorless; the metal ions in the metal ion layer 32 are reduced, and a metal layer 34 with a reflection effect is deposited on the surface of the second transparent conductive layer 31; the electrochromic device returns to the initial state, and the effect of the reflecting copper mirror is recovered;
in the present 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 referred to as a forward direction; when the potential of the first transparent conductive layer 21 is lower than the potential of the second transparent conductive layer 31, the direction of the voltage is referred to as reverse.
In the process of applying voltage to the electrochromic device, parameters such as the magnitude, the duration and the direction of the applied voltage can be adjusted to adjust the transmittance of the electrochromic stack 2 to be in any preset transmittance state between a coloring state and a fading state, and adjust the reflectance of the metal ion stack 3 to be in any semi-transparent semi-reflective state between transparent state and total reflection state, so that the appearance effect of the electrochromic device is enriched and enhanced. The electrochromic device can be used in electronic terminal products such as wearable electronic products, mobile electronic product terminals, building glass, laminated glass, hollow glass, decorative film layers and the like.
Example 3
This embodiment provides an electrochromic device with adjustable reflectivity, which is different from embodiment 1 in that the second substrate layer 4 is partially transparent or completely opaque, and is made of a material with a predetermined color, texture or pattern.
Example 4
The present embodiment provides an electrochromic device with adjustable reflectivity, whose structure is shown in fig. 3, and the difference from embodiment 1 is that a functional layer 5 is disposed on one side of a first transparent substrate layer 1 close to an 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.
In alternative embodiments of the present embodiment, the functional layer 5 may also be disposed on a side of the first transparent substrate layer 1 away from the electrochromic stack 2, and/or on a 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.
Example 5
The present embodiment provides an electrochromic device with adjustable reflectivity, whose structure is shown in fig. 4, and the difference from embodiment 1 is that a first substrate support layer 6 is disposed outside a first transparent substrate layer 1 (the first transparent substrate layer 1 is bonded to the first substrate support layer 6 through an adhesive layer, which is not shown in fig. 5), and a second substrate support layer 7 is disposed outside a second substrate layer 4 (the second substrate layer 4 is bonded to the second substrate support layer 7 through an adhesive layer, which is not shown in fig. 5).
In alternative embodiments of this embodiment, it is also possible to provide the first base support layer 6 only outside the first transparent substrate layer 1, or to provide the second base support layer 7 only outside the second substrate layer 4.
Example 6
The embodiment provides an electrochromic device with adjustable reflectivity, as shown in fig. 5, which includes a first transparent substrate layer 1, an electrochromic stack 2, a metal ion stack 3, and a second substrate layer 4, which are sequentially stacked;
the electrochromic stack 2 comprises a first transparent conductive layer 21 and a first electrochromic functional layer 22, which are laminated;
the metal ion stack 3 comprises a second transparent conductive layer 31 and a metal ion layer 32 which are sequentially laminated, and the first electrochromic functional layer 22 and the metal ion layer 32 are adjacent;
wherein the first transparent conductive layer 21 and the second transparent conductive layer 31 are used as a pair of electrodes for driving the electrochromic device, the second substrate layer 4 is completely transparent, and the material of the first electrochromic functional layer 22 is poly 2- [ (2-ethylhexyloxy) methyl]3, 4-thieno 1, 4-dioxane, the material of the metal ion layer 32 is Bi (Cl)3。
The following describes an exemplary adjustment process of transmittance and reflectance of the electrochromic device provided in this embodiment:
the 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 in a transparent blue state;
forward voltage (+1.6V) applied: applying a forward voltage to the electrochromic device in the initial state, poly 2- [ (2-ethylhexyloxy) methyl]The 3, 4-thieno 1, 4-dioxane loses electrons to generate oxidation reaction, and the color is changed from blue to colorless; bi in the metal ion layer 323+The electrons are reduced, and a metal Bi layer with a reflection 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;
reverse voltage (-1.6V) was applied: poly 2- [ (2-ethylhexyloxy) methyl group]The electrons obtained by the 3, 4-thieno 1, 4-dioxane are reduced, and the color is restored to blue; the deposited metallic Bi layer is oxidized to Bi3+Into the metal ionIn the sublayer 32, the metal ions are stacked to restore the transparent state; the electrochromic device returns to the initial state and appears as a transparent blue state.
In the present 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 referred to as a forward direction; when the potential of the first transparent conductive layer 21 is lower than the potential of the second transparent conductive layer 31, the direction of the voltage is referred to as reverse.
In the process of applying voltage to the electrochromic device, parameters such as the magnitude, the duration and the direction of the applied voltage can be adjusted to adjust the transmittance of the electrochromic stack 2 to be in any preset transmittance state between a coloring state and a fading state, and adjust the reflectance of the metal ion stack 3 to be in any semi-transparent semi-reflective state between transparent state and total reflection state, so that the appearance effect of the electrochromic device is enriched and enhanced. The electrochromic device can be used in electronic terminal products such as wearable electronic products, mobile electronic product terminals, building glass, laminated glass, hollow glass, decorative film layers and the like.
However, since the embodiment does not use the electrodeposition inhibiting layer, as the charging and discharging progresses, some metal Bi is gradually deposited on the first electrochromic functional layer 22, so that the long-term cycle performance of the electrochromic device is affected, and the appearance effect is affected.
Example 7
The embodiment provides an electrochromic device with adjustable reflectivity, as shown in fig. 6, which 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, which are sequentially stacked;
the electrochromic stack 2 comprises a first transparent conductive layer 21, a second electrochromic functional layer 23 and a third transparent conductive layer 24 which are sequentially laminated, wherein the first transparent conductive layer 21 is close to the first transparent substrate layer 1;
the metal ion stack 3 comprises a second transparent conductive layer 31, a metal ion layer 32 and a fourth conductive layer 35 which are sequentially stacked, wherein the second transparent conductive layer 31 is close to the second substrate layer 4;
the second electrochromic functional layer 23 has a structure as shown in fig. 7, and is formed by sequentially stacking a cathode electrochromic material layer 231, an electrolyte layer 232, and an anode electrochromic material layer 233, wherein the cathode electrochromic material layer 231 is adjacent to the first transparent conductive layer 21;
wherein, the first transparent conductive layer 21 and the third transparent conductive layer 24 are counter electrodes for driving the electrochromic stack 2; the second transparent conductive layer 31 and the fourth conductive layer 35 are a pair of electrodes for driving the metal ion stack 3;
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, and the electrolyte layer is made of LiClO4Propylene carbonate, the material of the anodic electrochromic material layer 233 was nickel oxide, and the material of the metal ion layer 32 was 3.0 wt% hydroxyethyl cellulose dissolved in 10mM CuCl2、10mM BiCl3A colloid formed in an aqueous solution of 10mM HCl and 1M LiBr;
the fourth conductive layer 35 is a metal mesh line formed by alternating Cu/Bi alloy metal lines, as shown in fig. 8, and has a width of 10 μm and a pitch of 80 μm.
The following describes an exemplary adjustment process of transmittance and reflectance of the electrochromic device provided in this embodiment:
the initial state: the electrochromic stack 2 is colorless initially, and the metal ion stack 3 is in a transparent state; the electrochromic device is in a transparent state. The electrochromic stack 2 and the metal ion stack 3 are not energized so that incident light can pass through the electrochromic stack 2 and the metal ion stack 3.
Adjustment of the transmittance of the electrochromic stack 2: a reverse voltage of-2V 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 tan; applying a positive voltage of +1.5V (the potential of the first transparent conductive layer 21 is higher than that of the third transparent conductive layer 24), the cathode electrochromic material layer 231 is oxidized and changed from blue to colorless, and the anode electrochromic material layer 233 is reduced and changed from tan to colorless; by adjusting parameters such as the magnitude, duration, direction of the applied voltage, the transmittance of the electrochromic stack 2 can be adjusted to be in any preset transmittance state between the colorless faded state and the dark blue (blue and tan superimposed) colored state.
Adjustment of the reflectivity of the metal ion stack 3: a reverse voltage of +1.0V is applied to the metal ion stack alone (the potential of the second transparent conductive layer 31 is lower than that of the fourth conductive layer 35), and the metal Cu and Bi in the metal grid of the fourth conductive layer 35 are oxidized into Cu2+And Bi3+Into the metal ion layer 32; the metal ions in the metal ion layer 32 are reduced, a mixed metal layer of Cu and Bi having a reflection 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 voltage of-1.0V (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, entering the metal ion layer 32; the electrons of the metal ions in the metal ion layer 32 at the metal mesh line position of the fourth conductive layer 35 are reduced to metal, deposited on the metal mesh line, and the metal ion stack 3 is in a transparent state because light can pass through the mesh hole. By adjusting parameters such as the magnitude, duration and direction of the applied voltage, the reflectivity of the metal ion stack 3 can be adjusted to be in a semi-transparent and semi-reflective state with any preset reflectivity between transparent and total reflection.
In the electrochromic device provided in this embodiment, the electrochromic stack 2 and the metal ion stack 3 are independently controlled, respectively, and thus the number of layers is larger than that in embodiment 1, but the states of the electrochromic stack 2 and the metal ion stack 3 are not constrained with each other, and a richer appearance display effect can be produced by adjusting the voltages respectively.
Example 8
This embodiment provides an electrochromic device with adjustable reflectivity, whose structure is shown in fig. 9, and the difference from embodiment 7 is that a metal ion stack 3 is disposed such that a fourth conductive layer 35 is close to a second substrate layer 4, a second transparent conductive layer 31 is close to a transparent insulating layer 8, and the shape of the fourth conductive layer 35 is shown in fig. 10, which is a metal frame formed by four Ag/Bi alloy metal strips located at the edge of the plane of the layer, and the width of the metal strips is 2 cm.
Example 9
This example provides an electrochromic device with adjustable reflectivity, which is different from example 7 in 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 15 wt% of polymethyl methacrylate macromolecules and 75 wt% of liquid crystal small molecules of 4- (trans-4-n-hexylcyclohexyl) -4' -cyanobiphenyl.
In an alternative embodiment of this embodiment, the second electrochromic functional layer is a suspended particle device layer.
Example 10
The present embodiment provides an electrochromic device with adjustable reflectivity, which is different from embodiment 7 in that the second substrate layer 4 is partially transparent or completely opaque, and is made of a material with a predetermined color, texture or pattern, and 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.
Example 11
This example provides an electrochromic device with adjustable reflectance, whose structure is shown in fig. 11, and is different from example 7 in that a transparent insulating layer 8 is composed of a third transparent substrate layer 81, a functional layer 82, and a fourth transparent substrate layer 83 which are sequentially laminated; 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.
Example 12
This embodiment provides an electrochromic device with adjustable reflectivity, whose structure is shown in fig. 12, and differs from embodiment 7 in that a first substrate support layer 6 is disposed outside a first transparent substrate layer 1 (the first transparent substrate layer 1 is bonded to the first substrate support layer 6 through an adhesive layer, which is not shown in fig. 9), and a second substrate support layer 7 is disposed outside a second substrate layer 4 (the second substrate layer 4 is bonded to the second substrate support layer 7 through an adhesive layer, which is not shown in fig. 12).
In alternative embodiments of this embodiment, it is also possible to provide the first base support layer 6 only outside the first transparent substrate layer 1, or to provide the second base support layer 7 only outside the second substrate layer 4.
The embodiment of the utility model provides an among the electrochromic device, the reflectivity of the transmissivity of electrochromic stack and metal ion stack can be adjusted through adjusting the size of applying voltage, long, orientation isoparametric, and the cooperation of the reflectivity change of transmissivity change and metal ion stack through the electrochromic stack has strengthened current electrochromic device's visual effect, makes electrochromic device surface obtain rich and varied colour and reflection effect. The electrochromic device can be used in electronic terminal products such as wearable electronic products, mobile electronic product terminals, building glass, laminated glass, hollow glass, decorative film layers and the like.
The applicant states that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and those skilled in the art should understand that any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure scope of the present invention.
Claims (15)
1. The electrochromic device with the adjustable reflectivity is characterized by comprising a first transparent substrate layer, an electrochromic stack, a metal ion stack and a second substrate layer which are sequentially stacked; the electrochromic stack comprises a first transparent conducting layer and a first electrochromic functional layer which are stacked; the metal ion stack comprises a second transparent conductive layer, a metal ion layer and an optional electrodeposition inhibition layer which are sequentially stacked; the first electrochromic functional layer is adjacent to the metal ion layer or the electrodeposition inhibition layer;
or comprises a first transparent substrate layer, an electrochromic stack, a transparent insulating layer, a metal ion stack and a second substrate layer which are sequentially stacked; the electrochromic stack comprises a first transparent conducting layer, a second electrochromic functional layer and a third transparent conducting layer which are sequentially stacked; the metal ion stack comprises a second transparent conducting layer, a metal ion layer and a fourth conducting layer which are sequentially stacked.
2. The tunable reflectance electrochromic device according to claim 1, wherein the first electrochromic functional layer is an anodic electrochromic material layer or a cathodic electrochromic material layer.
3. The tunable reflectance electrochromic device according to claim 1, wherein the second electrochromic functional layer is any one of a polymer dispersed liquid crystal layer, a suspended particle device layer, or an electrochromic layer.
4. The tunable reflectance electrochromic device according to claim 1, wherein the metal ion layer is a liquid electrolyte layer containing metal ions or a gel electrolyte layer containing metal ions.
5. The tunable reflectance electrochromic device according to claim 1, wherein the fourth conductive layer is formed by metal lines which are staggered or spaced, and/or metal strips which are located at the edges of the plane in which the fourth conductive layer is located.
6. The tunable reflectance electrochromic device according to claim 5, wherein the metal line has a width of 100 μm or less.
7. The device of claim 5, wherein the spacing between two adjacent spaced metal lines is greater than or equal to 10 μm.
8. The tunable reflectance electrochromic device according to claim 5, wherein the width of the metal strip is less than or equal to 3 cm.
9. The tunable reflectance electrochromic device according to claim 1, wherein a metal layer is further disposed between the metal ion layer and the second transparent conductive layer.
10. The tunable reflectance electrochromic device according to claim 1, wherein the electrodeposition inhibition layer is a triazole derivative material layer.
11. The electrochromic device with the adjustable reflectivity of claim 10, wherein the triazole derivative material layer is a benzotriazole material layer, a 1- (methoxymethyl) -1H-benzotriazole material layer, a 1- (formamidomethyl) -1H-benzotriazole material layer, or an N5-benzyl-1H-1, 2, 4-triazole-3, 5-diamine material layer.
12. The device of claim 1, wherein the transparent insulating layer is a hollow layer, a transparent substrate layer, or a composite layer formed by bonding a plurality of transparent substrate layers through an adhesive layer.
13. The device of claim 1, wherein a functional layer is further disposed on one or both sides of the first transparent substrate layer, the second substrate layer, and/or the transparent insulating layer, and/or between the transparent insulating layers, and the functional layer is 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, or a glue layer.
14. The tunable reflectance electrochromic device according to claim 1, wherein a substrate support layer is further disposed on an outer side of the first transparent substrate layer and/or the second substrate layer.
15. An electronic terminal comprising the tunable reflectance electrochromic device according to any one of claims 1 to 14.
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