CN220305598U

CN220305598U - All-solid-state electrochromic glass and all-solid-state electrochromic device

Info

Publication number: CN220305598U
Application number: CN202223309231.XU
Authority: CN
Inventors: 赵俊亮; 朱多银; 邹玉君
Original assignee: Shanghai Centaur Enterprise Development Group Co ltd
Current assignee: Shanghai Centaur Enterprise Development Group Co ltd
Priority date: 2022-12-09
Filing date: 2022-12-09
Publication date: 2024-01-05
Anticipated expiration: 2032-12-09

Abstract

The utility model relates to all-solid-state electrochromic glass and an all-solid-state electrochromic device, and relates to the technical field of electrochromic glass. An all-solid-state electrochromic glass comprises a substrate, and a first conductive layer, a first color-changing layer, an ion conductive layer, a second color-changing layer and a second conductive layer which are sequentially arranged on the substrate; the semiconductor device further comprises a first dielectric layer and/or a second dielectric layer; the first dielectric layer is arranged between the first conductive layer and the first color-changing layer; the second dielectric layer is arranged between the second conductive layer and the second color-changing layer. The all-solid-state electrochromic glass can avoid ion loss in the color-changing layer and current loss of the conductive layer, reduce device leakage current, widen the modulation range of the color-changing glass for light, improve the dimming effect and prolong the cycle service life of the color-changing glass.

Description

All-solid-state electrochromic glass and all-solid-state electrochromic device

Technical Field

The utility model relates to the technical field of electrochromic glass, in particular to all-solid-state electrochromic glass and an all-solid-state electrochromic device.

Background

Electrochromic devices can be classified into solution type, gel type, full solid type, etc. according to the morphology of electrochromic materials. Among them, an electrochromic device containing an ion conducting layer in a solid state and having a thin film composition entirely solid is called an all-solid electrochromic device, and is applicable to buildings, automobiles, and the like.

The full solid electrochromic glass generally comprises a cathode, a first color-changing layer, an ion conducting layer, a second color-changing layer and an anode, and the transfer of ions between the first color-changing layer and the second color-changing layer is realized by applying voltage between the anode and the cathode, so that the full solid electrochromic glass is converted between a coloring state and a fading state.

However, interdiffusion is transmitted between the cathode material and the first color-changing layer or between the anode material and the second color-changing layer, so that the loss of ions in the color-changing layer is caused, the modulation range of the color-changing glass to light is narrowed, and the dimming effect is poor.

Disclosure of Invention

The utility model aims to solve the technical problems that: avoiding the loss of ions in the color-changing layer caused by the interdiffusion between the cathode or anode material and the color-changing layer, and improving the dimming effect of the color-changing glass.

The utility model also provides the all-solid-state electrochromic glass, which can avoid ion loss in the color-changing layer and current loss of the conductive layer, widen the modulation range of the color-changing glass for light, improve the dimming effect, effectively reduce the leakage current of devices and prolong the cycle service life of the color-changing glass.

The utility model also provides an all-solid-state electrochromic device, which comprises the all-solid-state electrochromic glass, a voltage control device is adopted to provide power for the all-solid-state electrochromic glass, and meanwhile, a cover plate and a protective layer with supporting and protecting functions are also arranged, so that the device can work stably, and has stability and longer service life.

Specifically, the utility model discloses all-solid-state electrochromic glass which comprises a substrate, and a first conductive layer, a first color-changing layer, an ion conductive layer, a second color-changing layer and a second conductive layer which are sequentially arranged on the substrate;

the semiconductor device further comprises a first dielectric layer and/or a second dielectric layer;

the first dielectric layer is arranged between the first conductive layer and the first color-changing layer; the second dielectric layer is arranged between the second conductive layer and the second color-changing layer.

The first dielectric layer is an insulating material layer and has the thickness of 20-200nm; the insulating material is at least one selected from silicon oxide, silicon nitride, zinc oxide, aluminum oxide, tin oxide, tantalum oxide and zirconium oxide.

Preferably, the second dielectric layer is an insulating material layer with the thickness of 20-200nm; the insulating material is at least one selected from silicon oxide, silicon nitride, zinc oxide, aluminum oxide, tin oxide, tantalum oxide and zirconium oxide.

Preferably, the semiconductor device further comprises a protective layer, wherein the protective layer is arranged on the second conductive layer and is a high light transmission material layer.

Preferably, the first color-changing layer is a cathode color-changing material layer or an anode color-changing material layer; the second color-changing layer corresponds to the first color-changing layer, and when the first color-changing layer is a cathode color-changing material layer, the second color-changing layer is an anode color-changing material layer.

Preferably, in the cathode color-changing material layer, the cathode color-changing material is a transition metal oxide of a VIB group.

Preferably, in the anode color-changing material layer, the anode color-changing material is a transition metal oxide of the VIII group and the Pt group.

Preferably, the ion conducting layer is a layer of lithium ion conducting material selected from at least one of lithium tantalate, lanthanum lithium titanate, lithium silicate, lithium aluminate, lithium aluminum silicate, lithium chromate, lithium boron sulfate, lithium vanadate, or lithium tantalate.

The utility model also discloses an all-solid-state electrochromic device, which comprises a voltage control device and the all-solid-state electrochromic glass; the voltage control device is connected with the all-solid-state electrochromic glass.

Preferably, the device further comprises a cover plate arranged opposite to the all-solid-state electrochromic glass, and the cover plate is positioned above the all-solid-state electrochromic glass.

The beneficial effects are that:

(1) The all-solid-state electrochromic glass comprises a substrate, a first conductive layer, a first color-changing layer, an ion conductive layer, a second color-changing layer, a second conductive layer and a first dielectric layer and/or a second dielectric layer; the ion conducting layer is solid and is used for conducting ions between the first color-changing layer and the second color-changing layer; the first color-changing layer and the second color-changing layer are used for generating electrochromic reaction with ions under the action of an electric field; the first medium layer and/or the second medium layer can avoid ion loss in the color-changing layer, can conduct current, avoid current loss of the conductive layer, widen the modulation range of the color-changing glass to light, and prolong the cycle service life of the color-changing glass; a protective layer for protection and support may also be provided on the second conductive layer. The all-solid-state electrochromic glass can avoid ion loss in the color-changing layer and current loss of the conductive layer, widen the light modulation range of the color-changing glass, improve the light modulation effect and prolong the cycle service life of the color-changing glass.

(2) The all-solid-state electrochromic device comprises the all-solid-state electrochromic glass, a voltage control device and a cover plate; the voltage control device is connected with the first conductive layer and/or the second conductive layer and is used for providing power supply voltage for the all-solid-state electrochromic glass; the cover plate is used for protecting or packaging the all-solid-state electrochromic glass; a protective layer can be arranged between the cover plate and the all-solid-state electrochromic glass, so that the protective layer has the protection and supporting functions. The all-solid-state electrochromic device adopts the voltage control device to provide power for the all-solid-state electrochromic glass, and meanwhile, the cover plate and the protective layer with supporting and protecting functions are also arranged, so that leakage current of the device can be reduced, the device can work stably, and the device has stability and long service life.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present utility model, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present utility model, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a schematic view of an all-solid electrochromic glazing of example 1 of the utility model;

FIG. 2 is a schematic view of an all-solid electrochromic glazing according to example 2 of the utility model;

FIG. 3 is a schematic view of an all-solid electrochromic glazing of example 3 of the utility model;

FIG. 4 is a schematic diagram of an all-solid-state electrochromic device according to example 5 of the present utility model;

FIG. 5 is a graph showing the transmission spectrum of the all-solid electrochromic glass prepared in example 4 of the present utility model;

FIG. 6 is a reflectance spectrum of the all-solid electrochromic glass prepared in example 4 of the present utility model;

FIG. 7 is a graph showing the transmittance of the all-solid electrochromic glass prepared in example 4 according to the voltage response;

fig. 8 is a Scanning Electron Microscope (SEM) image of a cross-section of a reflective all-solid electrochromic glass in an all-solid electrochromic device of example 6 of the utility model.

The figure identifies the description:

Detailed Description

The following description of the embodiments of the present utility model will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the utility model. All other embodiments, which can be made by those skilled in the art based on the embodiments of the utility model without making any inventive effort, are intended to be within the scope of the utility model.

It should be understood that the terms "comprises" and "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

It is also to be understood that the terminology used in the description of the utility model herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the utility model. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

It should be further understood that the term "and/or" as used in the present specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.

In the description of the present utility model, it should be noted that, directions or positional relationships indicated by terms such as "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., are directions or positional relationships based on those shown in the drawings, or are directions or positional relationships conventionally put in use of the inventive product, are merely for convenience of describing the present utility model and simplifying the description, and are not indicative or implying that the apparatus or element to be referred to must have a specific direction, be constructed and operated in a specific direction, and thus should not be construed as limiting the present utility model.

The terms "first," "second," and the like are used merely to distinguish between descriptions and are not to be construed as indicating or implying relative importance.

The terms "horizontal," "vertical," "overhang," and the like do not denote that the component is required to be absolutely horizontal, vertical, or overhang, but may be slightly inclined. As "horizontal" merely means that its direction is more horizontal than "vertical", and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.

In the description of the present utility model, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present utility model will be understood in specific cases by those of ordinary skill in the art.

An all-solid-state electrochromic glass,

comprising the following steps: the substrate 100 includes a first conductive layer 110, a first color-changing layer 120, an ion conductive layer 130, a second color-changing layer 140, a second conductive layer 150, and a first dielectric layer 160 and/or a second dielectric layer 170 disposed between the first conductive layer 110 and the first color-changing layer 120 and/or between the second conductive layer 150 and the second color-changing layer 140, which are sequentially disposed on the substrate 100.

Wherein the ion conducting layer 130 is solid for conducting ions between the first color-changing layer 120 and the second color-changing layer 140.

The first color-changing layer 120 and the second color-changing layer 140 are used to perform electrochromic reaction with ions under the action of an electric field.

The substrate 100 may be glass, polymer, or the like. The first conductive layer 110 and the second conductive layer 150 may be transparent conductive materials respectively functioning as an anode and a cathode of electrochromic glass for applying a forward voltage or a reverse voltage.

The first color-changing layer 120 is a cathode color-changing material layer or an anode color-changing material layer; the second color-changing layer 140 corresponds to the first color-changing layer 120, and when the first color-changing layer 120 is a cathode color-changing material layer, the second color-changing layer 140 is an anode color-changing material layer. That is, the first color-changing layer 120 may be an anodic color-changing material and the second color-changing layer 140 may be a cathodic color-changing material; alternatively, the first color-changing layer 120 may be an anodic color-changing material and the second color-changing layer 140 may be a cathodic color-changing material. The cathode color-changing material is mainly a transition metal oxide of a VIB group, such as tungsten oxide, and is in a color-fading state in a high-valence oxidation state and in a color-coloring state in a reduction state. Anodic color-changing materials, mainly oxides or hydrates of VIII and Pt group metals, such as nickel oxide, are colored in the oxidized state and discolored in the reduced state, which are opposite to the cathodic color-changing materials.

Ion conducting layer 130 may be used to conduct ions, such as lithium ions; in some embodiments, the ion conducting layer 130 is a lithium ion conducting material layer, and the material (lithium ion conducting material) of the ion conducting layer 130 may be lithium tantalate, lanthanum lithium titanate, lithium silicate, lithium aluminate, aluminum lithium silicate, lithium chromate, lithium boron sulfate, lithium vanadate, lithium tantalate, or the like. The ion conducting layer 130 may be an amorphous structure.

For example, the first color-changing layer 120 is nickel oxide, the ion conducting layer 130 is lithium tantalate, and the second color-changing layer 140 is tungsten oxide. When the second conductive layer 150 applies a forward voltage, the lithium ions are located in the nickel oxide, the nickel oxide layer is in a transparent state, the tungsten oxide layer without the lithium ions is in a yellowish transparent state, light in the environment can penetrate through each layer, and the electrochromic glass has higher transmittance to light; when the first conductive layer 110 is applied with a reverse voltage, the tungsten oxide is colored in a blue state, and the nickel oxide layer is free of lithium ions, is brown-yellow, and has low transmittance to light. The reflectivity of the electrochromic glass is dynamically adjusted by controlling the direction of the voltage applied to the electrochromic glass and the voltage application time and controlling the migration of lithium ions between the nickel oxide layer and the tungsten oxide.

It should be noted that, in the embodiment of the present utility model, the forward voltage refers to the voltage applied when the first color-changing layer 120 and the second color-changing layer 140 are both in the color-fading state; conversely, the reverse voltage refers to a voltage applied when both the first color-changing layer 120 and the second color-changing layer 140 are in a colored state.

In an embodiment of the present utility model, when the first color-changing layer 120 or the second color-changing layer 140 is a tungsten oxide layer, the tungsten oxide layer is formed by amorphous nano particles, the surface sheet resistance is greater than 100kΩ, and the thickness is 200-600nm. The tungsten oxide film is in a porous and loose amorphous state, and has a smooth and uniform surface and good combination with the conductive layer or the dielectric layer. The tungsten oxide layer is in a colored state when ion implantation, the visible light transmittance is less than 10%, and the tungsten oxide layer is in a high visible light transmittance reaching more than 70% when in a fading state (transparent state).

In an embodiment of the present utility model, the first dielectric layer 160 and/or the second dielectric layer 170 are insulating material layers, that is, the first dielectric layer 160 and/or the second dielectric layer 170 are insulating materials, and may include at least one of silicon oxide, silicon nitride, zinc oxide, aluminum oxide, tin oxide, tantalum oxide, zirconium oxide, and the like. Wherein the thickness of the first dielectric layer 160 and/or the second dielectric layer 170 is 20-200nm. It will be appreciated that the first dielectric layer 160 may avoid interdiffusion between the first conductive layer 110 and the first color shifting layer 120, the second dielectric layer 170 may avoid interdiffusion between the second conductive layer 150 and the second color shifting layer 140, thereby ensuring independence between the various layers of the all-solid electrochromic glass,

in an embodiment of the present utility model, the all-solid electrochromic glass is a reflective all-solid electrochromic glass, wherein the material of the first conductive layer 110 or the second conductive layer 150 is metal, such as aluminum, silver-aluminum alloy or chromium, which is used for reflecting the light path and is used as an electrode, the thickness of which is greater than 100nm, and the visible light reflectivity of which is greater than 80%. For example, the material of the second conductive layer 150 is metal, and the first conductive layer 110 is a transparent conductive layer. When forward voltage is applied, the nickel oxide layer and the tungsten oxide layer are in transparent states, and the environment light irradiates onto the metal reflecting layer at the bottom layer after passing through the nickel oxide layer and the tungsten oxide layer and exits through the tungsten oxide layer. When reverse voltage is applied, ions are migrated from the nickel oxide layer to the tungsten oxide layer through voltage control, at the moment, the nickel oxide layer is free of ions, tungsten oxide is provided with ions, the nickel oxide layer is brownish yellow, the tungsten oxide layer is blue, the light transmittance of a light path is reduced, the overall reflectivity of the color-changing glass is reduced, and the migration of an ion part between the nickel oxide layer and the tungsten oxide can be achieved by controlling the voltage applied to the color-changing glass and the voltage application time, so that the reflectivity of the color-changing glass is dynamically adjusted. The maximum visible light reflectivity of the color-changing glass is adjusted to be 10-70%.

Optionally, when the second conductive layer 150 is a metal layer, a second dielectric layer 170 may be included between the second conductive layer 150 and the second color-changing layer 140 to avoid poor color-changing effect of the second color-changing layer 140 caused by atomic interdiffusion between the metal layer and the second color-changing layer 140.

Whether the first conductive layer 110 or the second conductive layer 150 of the reflective all-solid electrochromic glass is a metal layer is related to the installation direction of the reflective all-solid electrochromic glass in actual use.

In an embodiment of the present utility model, the first conductive layer 110 and the second conductive layer 150 are transparent conductive materials, and the transparent conductive materials are one of indium tin oxide, aluminum doped zinc oxide, fluorine doped tin oxide, or lithium silver alloy. The surface sheet resistance is less than 50 omega, and the thickness is 50-150nm.

In an embodiment of the present utility model, the first color-changing layer 120 or the second color-changing layer 140 is a nickel oxide-chromium oxide mixture. The content of the chromium oxide in the nickel oxide-chromium oxide mixture is not more than 50%. The nickel oxide and chromium oxide mixture has a nano amorphous or crystalline structure; the thickness of the first color-changing layer 120 or the second color-changing layer 140 formed by the nickel oxide-chromium oxide mixture is 100-200nm, the visible light transmittance is more than 70% in a transparent state, the visible light transmittance is less than 20% in a coloring state, and the surface sheet resistance is not less than 100kΩ/m ² 。

In an embodiment of the present utility model, the all-solid electrochromic glass further includes a protective layer 180, where the protective layer 180 is disposed on the second conductive layer 150, so as to play a role in protection. The protective layer 180 is a high light-transmitting material layer, i.e., the protective layer 180 is a high light-transmitting material such as resin, silicon oxide, etc.

The all-solid-state electrochromic glass avoids the loss of ions in the color-changing layer through the first dielectric layer 160 or the second dielectric layer 170, and improves the light modulation range of the color-changing glass.

The all-solid-state electrochromic glass comprises a substrate, a first conductive layer, a first color-changing layer, an ion conductive layer, a second color-changing layer, a second conductive layer and a first dielectric layer and/or a second dielectric layer; the ion conducting layer is solid and is used for conducting ions between the first color-changing layer and the second color-changing layer; the first color-changing layer and the second color-changing layer are used for generating electrochromic reaction with ions under the action of an electric field; the first medium layer and/or the second medium layer can avoid ion loss in the color-changing layer, can conduct current, avoid current loss of the conductive layer, widen the modulation range of the color-changing glass to light, and prolong the cycle service life of the color-changing glass; a protective layer for protection and support may also be provided on the second conductive layer.

The all-solid-state electrochromic glass can avoid ion loss in the color-changing layer and current loss of the conductive layer, widen the light modulation range of the color-changing glass and prolong the cycle service life of the color-changing glass.

It should be noted that, in the present utility model, the lamination sequence of each conductive layer, the color-changing layer and the dielectric layer is fixed, and it is difficult to achieve good effects of avoiding ion loss in the color-changing layer and widening the modulation range of the color-changing glass to light without the lamination sequence; meanwhile, the thicknesses of the conductive layers, the color-changing layers and the dielectric layers are limited, and because of the differences of different materials in the aspects of conductivity, surface sheet resistance, light transmittance, ion movement prevention and the like, the thicknesses are required to be adjusted according to the materials, otherwise, the prepared color-changing glass cannot have a wider light modulation range and a better light modulation effect; meanwhile, the addition of the dielectric layer is necessary, the dielectric layer has the effect of preventing ion movement, the ion loss between the conductive layer and the color-changing layer can be avoided, the modulation range of the color-changing glass to light is widened, the light adjusting effect is improved, the effect of conducting current is also achieved, electric leakage can be prevented, and the recycling service life of the color-changing glass is prolonged.

Example 1

An all-solid-state electrochromic glass,

comprising the following steps: the substrate 100 includes a first conductive layer 110, a first color-changing layer 120, an ion conductive layer 130, a second color-changing layer 140, a second conductive layer 150, and a first dielectric layer 160 disposed between the first conductive layer 110 and the first color-changing layer 120.

Wherein the substrate 100 may be glass, polymer, or the like. The first and second conductive layers 110 and 150 may be transparent conductive materials respectively functioning as an anode and a cathode of electrochromic glass for applying a forward voltage or a reverse voltage; specifically, the first conductive layer 110 and the second conductive layer 150 are transparent conductive materials, and the transparent conductive materials are one of indium tin oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide or lithium silver alloy, and the like, and have a surface sheet resistance of less than 50Ω and a thickness of 50-150nm.

The first color shifting layer 120 is a nickel oxide-chromium oxide mixture. The content of chromium oxide in the nickel oxide-chromium oxide mixture is not more than 50%. The nickel oxide and chromium oxide mixture has a nano amorphous or crystalline structure; the thickness of the first color-changing layer 120 formed by the nickel oxide-chromium oxide mixture is 100-200nm, the visible light transmittance is more than 70% in a transparent state, the visible light transmittance is less than 20% in a coloring state, and the surface sheet resistance is not less than 100kΩ/m ² 。

The second color-changing layer 140 is a tungsten oxide layer which is formed by amorphous nano particles, the surface sheet resistance is more than 100KΩ, and the thickness is 200-600nm.

Ion conductive layer 130 may be used to conduct ions, such as lithium ions, and the ion conductive layer 130 material may be lithium tantalate, lanthanum lithium titanate, lithium silicate, lithium aluminate, lithium aluminum silicate, lithium chromate, lithium boron sulfate, lithium vanadate, lithium tantalate, or the like. The ion conducting layer 130 is an amorphous structure.

The first dielectric layer 160 is an insulating material and may include at least one of silicon oxide, silicon nitride, zinc oxide, aluminum oxide, tin oxide, tantalum oxide, zirconium oxide, and the like. Wherein the thickness of the first dielectric layer 160 is 20-200nm. The first dielectric layer 160 may prevent ion interdiffusion between the first conductive layer 110 and the first color shifting layer 120.

Example 2

An all-solid-state electrochromic glass,

comprising the following steps: the substrate 100 includes a first conductive layer 110, a first color-changing layer 120, an ion conductive layer 130, a second color-changing layer 140, a second conductive layer 150, and a second dielectric layer 170 disposed between the second conductive layer 150 and the second color-changing layer 140, which are sequentially disposed on the substrate 100.

Wherein the substrate 100 may be glass, polymer, or the like. The first and second conductive layers 110 and 150 may be transparent conductive materials respectively functioning as an anode and a cathode of electrochromic glass for applying a forward voltage or a reverse voltage; specifically, the second conductive layer 150 is made of metal, such as aluminum, silver-aluminum alloy, or chromium, and functions as a reflective light path and an electrode, and has a thickness of more than 100nm and a visible light reflectivity of more than 80%; the first conductive layer 110 is a transparent conductive layer, and the transparent conductive material is one of indium tin oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide or lithium silver alloy, and the like, and has a surface sheet resistance of less than 50Ω and a thickness of 50-150nm.

The first color-changing layer 120 is nickel chromium oxide with the thickness of 100nm-200nm; ion conducting layer 130 is lithium tantalate, an amorphous porous loose film; the second color-changing layer 140 is made of tungsten oxide, the tungsten oxide layer is made of amorphous nano particles, the surface sheet resistance is larger than 100KΩ, and the thickness is 200-600nm.

The second dielectric layer 170 is an insulating material and may include at least one of silicon oxide, silicon nitride, zinc oxide, aluminum oxide, tin oxide, tantalum oxide, zirconium oxide, and the like. Wherein the thickness of the second dielectric layer 170 is 20-200nm. The second dielectric layer 170 may prevent ion interdiffusion between the second conductive layer 150 and the second color shifting layer 140.

Example 3

An all-solid electrochromic glazing differs from example 1 in that it further comprises a second dielectric layer 170 and a protective layer 180.

The second dielectric layer 170 is disposed between the second conductive layer 150 and the second color-changing layer 140, and is an insulating material, and may include at least one of silicon oxide, silicon nitride, zinc oxide, aluminum oxide, tin oxide, tantalum oxide, zirconium oxide, and the like. Wherein the thickness of the second dielectric layer 170 is 20-200nm. The second dielectric layer 170 may prevent ion interdiffusion between the second conductive layer 150 and the second color shifting layer 140.

The protective layer 180 is disposed on the second conductive layer 150, and is made of a material with high light transmittance, such as resin, silicon oxide, etc., and the thickness thereof can be selected according to the actual situation.

That is, compared with embodiment 1, the embodiment further has the second dielectric layer 170 and the protective layer 180, so that the effect of preventing the ion loss is better, i.e. the embodiment has a wider modulation range of light and a better dimming effect; at the same time, the color-changing glass of the embodiment is more stable,

the following describes the preparation method of the all-solid electrochromic glass, which may include some or all of the following steps:

step S1: a substrate 100 is provided.

The substrate 100 may be a common glass substrate, a quartz glass substrate, a plastic substrate such as PET, or the like, for carrying a thin film layer.

Step S2: a first conductive layer 110 is formed on the substrate 100.

Wherein the first conductive layer 110 may be a metal thin film such as an Al, ag, mg, pd layer, or the like; but may also be a transparent conductive material such as a conventional transparent conductive layer, for example ITO, FTO, ATO, AZO.

Specifically, the first conductive layer 110 may be formed on the substrate by deposition through a physical vapor deposition method.

S3: a first dielectric layer 160 is formed on the first conductive layer 110.

Specifically, the first dielectric layer 160 is an insulating material, and may include at least one of silicon oxide, silicon nitride, zinc oxide, aluminum doped zinc oxide, and the like.

Specifically, the first dielectric layer 160 may be formed on the first conductive layer 110 by a physical vapor deposition method.

It is understood that physical vapor deposition methods include magnetron sputtering, pulsed laser deposition, thermal vapor deposition, and the like.

S4: a first color shifting layer 120 is formed on the first dielectric layer 160.

The first color-changing layer 120 may be a cathode color-changing material or an anode color-changing material, where the cathode color-changing material is mainly a transition metal oxide of group VIB, such as tungsten oxide, and the material is in a color-fading state in a high-valence oxidation state and is in a color-coloring state in a reduction state. Anodic color-changing materials, mainly oxides or hydrates of VIII and Pt group metals, such as nickel oxide, are in the oxidized state, in the colored state, in the reduced state, in the color-changing state opposite to that of the cathodic color-changing material.

Specifically, the first color change layer 120 is deposited on the substrate by a physical vapor deposition method.

S5: an ion conductive layer 130 is formed on the first color-changing layer 120.

Among them, the ion conductive layer 130 may be used to conduct ions, such as lithium ions, and the ion conductive layer 130 may be lithium tantalate, lanthanum lithium titanate, lithium silicate, lithium aluminate, lithium aluminum silicate, lithium chromate, lithium boron sulfate, lithium vanadate, lithium tantalate, or the like. The ion conducting layer 130 may be an amorphous structure.

Specifically, the ion conductive layer 130 may be formed on the first color change layer 120 by a physical vapor deposition method or a chemical vapor deposition method.

S6: a second color-changing layer 140 is formed on ion conducting layer 130.

Wherein, opposite to the first color-changing layer 120, the second color-changing layer 140 may be an anodic color-changing material or a cathodic color-changing material.

Specifically, the second color change layer 140 is deposited on the ion conductive layer 130 by a physical vapor deposition method.

S7: a second conductive layer 150 is formed on the second color change layer 140.

In an embodiment of the present utility model, step S7 may include forming a second dielectric layer 170 on the second color-changing layer 140, and forming a second conductive layer 150 on the second dielectric layer 170. The second dielectric layer 170 is an insulating material, and may include at least one of silicon oxide, silicon nitride, zinc oxide, aluminum doped zinc oxide, and the like. Specifically, the second dielectric layer 170 may be formed on the second color change layer 140 by a physical vapor deposition method.

It will be appreciated that in practical applications, the first conductive layer 110 and the second conductive layer 150 are not metal films at the same time.

Specifically, the second conductive layer 150 may be formed on the second dielectric layer 170 or the second color change layer 140 by physical vapor deposition. Wherein the second conductive layer 150 may be a metal thin film such as an Al, ag, mg, pd layer, or the like; but may also be a transparent conductive material such as a conventional transparent conductive layer, for example ITO, FTO, ATO, AZO.

In an embodiment of the present utility model, the preparation method of the all-solid electrochromic glass may further include: providing a substrate 100; forming a first conductive layer 110 on a substrate 100; forming a first color change layer 120 on the first conductive layer 110; forming an ion conductive layer 130 on the first color-changing layer 120; forming a second color-changing layer 140 on ion conductive layer 130; a second dielectric layer 170 is formed on the second color-changing layer 140 and a second conductive layer 150 is formed on the second dielectric layer 170. See in particular the relevant description of the steps above.

In an embodiment of the present utility model, after forming the second conductive layer 150, the preparation method may further include: the protective layer 180 is formed on the second conductive layer 150 to protect it. The protective layer 180 is a high light-transmitting material such as resin, silicon oxide, or the like. The method of forming the protective layer 180 may include spin coating, physical vapor deposition, chemical vapor deposition, or the like. The choice of preparation method depends on the material of the protective layer.

Example 4

A method of preparing an all-solid electrochromic glazing comprising:

the common glass substrate (substrate 100) is ultrasonically cleaned for ten minutes by using a detergent, then is washed by using clear water, is put into a hot air drying box for drying, and is checked to see whether the surface of the glass has visible hidden damages, unevenness and the like, so that the surface of the glass is clean.

Preparation of transparent conductive film (first conductive layer 110): a transparent conductor film is prepared by adopting a magnetron sputtering method, a glass substrate is placed into a magnetron sputtering cavity, an ITO target is selected as the target, a direct current power supply is adopted as a sputtering power supply, the power density is 1w/cm < 2 >, the atmosphere is pure argon, the pressure is 0.3Pa, the room-temperature sputtering time is ten minutes, the ITO conductive film with a flat surface is obtained, and the surface sheet resistance is measured and is smaller than 50 omega.

Pins are arranged at the edges of the ITO film, and conductive wires are paved.

Preparation of nickel oxide color-changing layer (first color-changing layer 120): the nickel oxide film is prepared by a magnetron sputtering method, a glass substrate with the ITO film is placed in a sputtering cavity, a metal nickel target is selected as a target material, the purity is better than 99%, a direct current power supply is adopted as a sputtering power supply, and the power density is 1w/cm ² The atmosphere adopts argon-oxygen mixture, wherein the oxygen proportion is 10%, the air pressure is controlled to be 1Pa, the sputtering time is 10 minutes, and the nickel oxide-chromium oxide mixture film with the thickness of 150nm is obtained.

It will be appreciated that in another embodiment of the method of making an all solid state electrochromic glass, a nickel chromium oxide layer may be substituted for the nickel oxide layer. Specifically, a magnetron sputtering method is adopted to prepare a nickel-chromium oxide film, ITO glass is placed in a sputtering cavity, a metal nickel-chromium target (Cr 20%) is selected as a target material, the purity is better than 99%, a direct current power supply is adopted as a sputtering power supply, and the power density is 1w/cm ² The atmosphere adopts argon-oxygen mixture, wherein the oxygen proportion is 10%, the air pressure is controlled to be 1Pa, the sputtering time is 10 minutes, and the nickel-chromium oxide film with the thickness of 150nm is obtained.

First dielectric film (first dielectric layer 160) is prepared: preparing a first dielectric film by using a magnetron sputtering method, putting a glass substrate with a nickel oxide and chromium oxide film into a magnetron sputtering cavity, wherein a metal zinc target is adopted as a target material, the purity is better than 99%, a direct current power supply is adopted as a sputtering power supply, and the power density is 1w/cm ² The atmosphere adopts argon-oxygen mixture, wherein the oxygen proportion is 20%, the air pressure is controlled to be 1Pa, the sputtering time is 2 minutes, and the zinc oxide film with the thickness of 20nm is obtained.

Ion conducting layer 130 is prepared: the magnetic control sputtering method is adopted for preparation, the target material is lithium tantalate target material, the purity is better than 99%, the sputtering power supply is radio frequency power supply, and the power density is 3w/cm ² The atmosphere was pure argon, the air pressure was controlled at 1Pa, and the sputtering time was 20 minutes, to obtain an ion conducting layer having a thickness of 700 nm.

Preparation of tungsten oxide color-changing layer (second color-changing layer 140): the nickel oxide film is prepared by a magnetron sputtering method, a sample is placed in a sputtering cavity, a target material is a metal tungsten target, the purity is better than 99%, a sputtering power supply is a direct current power supply, and the power density is 1w/cm ² The atmosphere adopts argon-oxygen mixture, wherein the oxygen ratio is 6%, the air pressure is controlled to be 2Pa, the sputtering time is 20 minutes, and the tungsten oxide film with the thickness of 500nm is obtained.

Preparation of reflective metal layer (second conductive layer 150): preparing a metal aluminum film by using a magnetron sputtering method, placing a sample into a sputtering cavity, selecting a metal aluminum target as a target material, wherein the purity is better than 99%, and adopting a direct current power supply as a sputtering power supply with the power density of 1w/cm ² The atmosphere is pure argon, the air pressure is controlled to be 0.5Pa, the sputtering time is 5 minutes, and the metal film with the thickness of 200nm is obtained.

The transparent conductive film (the first conductive layer 110) and the reflective metal layer (the second conductive layer 150) are connected as electrodes to a power supply voltage.

Referring to fig. 5, fig. 5 is a transmission spectrum of an all-solid electrochromic glass prepared in this example. It can be seen that the maximum modulation range of the all-solid electrochromic glass for visible light transmittance in a transparent state and an absorption state (also called a coloring state) can reach about 60 percent.

Referring to fig. 6, fig. 6 is a reflection spectrum of an all-solid electrochromic glass prepared in this example. It can be seen that the maximum modulation range of the all-solid electrochromic glass on visible light reflectivity in a transparent state and a coloring state can reach about 60 percent.

Referring to fig. 7, fig. 7 is a graph showing the transmittance versus voltage response of an all-solid electrochromic glass prepared in this example. It can be seen that the transmittance of an all-solid electrochromic glass in the colored state can be dynamically changed with changes in voltage. Devices made from all-solid electrochromic glazing can have their transmittance controlled by controlling the voltage applied across the all-solid electrochromic glazing.

Device of all-solid-state electrochromic glass

An all-solid-state electrochromic device may include: all-solid electrochromic glazing 10 and voltage control device 11 described in examples 1-3. Wherein the voltage control device 11 is connected to the first conductive layer 110 and/or the second conductive layer 150, and is used for providing a power supply voltage to the all-solid electrochromic glass 10.

In an embodiment of the present utility model, the cover plate 190 is similar to the substrate 100, and is disposed above the all-solid electrochromic glass 10, and may be a common glass substrate, a quartz glass substrate, or a plastic substrate such as PET, etc., for supporting and protecting the all-solid electrochromic glass 10.

In one embodiment of the utility model, the all-solid-state electrochromic device can be applied to smart windows in buildings, has an energy-saving effect, can also be used as an indoor dazzling mirror, and is applied to indoor decoration.

In this embodiment, the first conductive layer 110 or the second conductive layer 150 may be a metal layer, so that the formed reflective all-solid electrochromic device may be used as an automobile rearview mirror, and when the external light intensity is high, the rearview mirror may be controlled to change from a high reflection state to a low reflection state, so as to reduce the influence of glare on the driver and ensure the driving safety.

The all-solid-state electrochromic device comprises the all-solid-state electrochromic glass, a voltage control device and a cover plate; the voltage control device is connected with the first conductive layer and/or the second conductive layer and is used for providing power supply voltage for the all-solid-state electrochromic glass; the cover plate is used for protecting or packaging the all-solid-state electrochromic glass; a protective layer can be arranged between the cover plate and the all-solid-state electrochromic glass, so that the protective layer has the protection and supporting functions. The all-solid-state electrochromic device adopts the voltage control device to provide power for the all-solid-state electrochromic glass, and meanwhile, the cover plate and the protective layer with supporting and protecting functions are also arranged, so that the device can work stably, and has stability and longer service life.

Example 5

Referring to fig. 4, fig. 4 is a schematic structural diagram of an all-solid-state electrochromic device according to the present embodiment.

An all-solid-state electrochromic device comprising: an all-solid electrochromic glazing 10 and a voltage control device 11. Wherein the all-solid electrochromic glazing 10 comprises: the substrate 100, the first conductive layer 110, the first dielectric layer 160, the first color-changing layer 120, the ion conductive layer 130, the second color-changing layer 140 and the second conductive layer 150 sequentially disposed on the substrate 100, optionally, the all-solid electrochromic device further includes a cover plate 190 disposed opposite to the all-solid electrochromic glass 10, and a protective layer 180 having protection and support functions, where the cover plate 190 may be a glass sheet for protecting or encapsulating the all-solid electrochromic glass 10.

It should be noted that, the structure of each layer in the all-solid electrochromic device provided by the embodiment of the present utility model may be referred to the related description in the above all-solid electrochromic glass, and the disclosure is not repeated herein.

Example 6

A method of making an all-solid-state electrochromic device, the method comprising:

the glass substrate (substrate 100) was cleaned, put into a magnetron sputtering apparatus, and sputtered to form a metal reflective layer (first conductive layer 110): the reflecting layer can be aluminum, chromium and alloys thereof, silver and alloys thereof, and the metal reflecting layer can be obtained by using the metal and the alloy targets thereof through a magnetron sputtering method, and the thickness is limited to 100nm-800nm.

A nichrome thin film (first color change layer 120) was formed by sputtering on the metal reflective layer (first conductive layer 110): and preparing a nickel-chromium oxide film by a thermal evaporation coating method at the room temperature of 300 ℃ to form a transparent nickel-chromium oxide layer, wherein the transmittance is more than 70%.

Forming a lithium tantalate or lanthanum lithium titanate film (ion conductive layer 130) on the nichrome oxide film (first color-changing layer 120): the target material is lithium tantalate or lithium lanthanum titanate. Sputtering at room temperature to obtain amorphous porous lithium tantalate or lanthanum lithium titanate film.

A tungsten oxide film (second color-changing layer 140) is formed on a lithium tantalate or lithium lanthanum titanate film (ion conductive layer 130), and the film is obtained by a reactive magnetron sputtering method or an electron beam evaporation method at room temperature, having an amorphous porous loose film.

Forming a transparent conductive layer (second conductive layer 150) on the tungsten oxide thin film (second color change layer 140): the transparent conductor film can be prepared by a magnetron sputtering method.

Optionally, a dielectric layer (i.e., the second dielectric layer 170) may be formed on the tungsten oxide film (the second color-changing layer 140) before forming the transparent conductive layer (the second conductive layer 150) on the tungsten oxide film, or a dielectric layer (i.e., the first dielectric layer 160) may be formed before sputtering forming the nichrome oxide film (the first color-changing layer 120) on the metal reflective layer (the first conductive layer 110) to prevent the phenomenon that the excessive energization causes the diffusion of ions in the transparent conductor. The dielectric film may be silicon oxide, aluminum oxide, zinc oxide, silicon nitride, tin oxide, tantalum oxide, zirconium oxide, or the like. Obtained by magnetron sputtering or electron beam evaporation, and has a thickness of 50nm-200 nm.

May further include: the protective layer 180 is formed on the transparent conductive layer (the second conductive layer 150) to play a protective role. The protective layer 180 is a high light-transmitting material such as resin, silicon oxide, or the like. The method of forming the protective layer 180 may include spin coating, physical vapor deposition, chemical vapor deposition, or the like. The choice of preparation method depends on the material of the protective layer.

The shape of each layer can be controlled through a mask plate so as to prepare the reflective all-solid-state electrochromic devices in various forms.

Then, the voltage control device 11 was connected to the metal reflective layer (first conductive layer 110) and the transparent conductive layer (second conductive layer 150) as electrodes, and an all-solid-state electrochromic device was fabricated.

Referring to fig. 8, fig. 8 is a Scanning Electron Microscope (SEM) image of a cross section of the reflective all-solid electrochromic glass in the all-solid electrochromic device prepared in this example.

The embodiment is merely a method for preparing an all-solid electrochromic device, wherein specific choices of a substrate, a conductive layer, a dielectric layer, a color-changing layer and the like can refer to the all-solid electrochromic device or the all-solid electrochromic glass, and the preparation method can be adjusted according to specific choices of the substrate, the conductive layer, the dielectric layer and the color-changing layer according to the implementation.

The foregoing description is only an example to further illustrate the technical content of the present utility model, so that the reader can easily understand the technical content, but the embodiments of the present utility model are not limited thereto, and any technical extension or recreating according to the present utility model is protected by the present utility model.

Claims

1. The all-solid-state electrochromic glass is characterized by comprising a substrate, and a first conductive layer, a first color-changing layer, an ion conductive layer, a second color-changing layer and a second conductive layer which are sequentially arranged on the substrate;

the semiconductor device further comprises a first dielectric layer or a second dielectric layer;

the first dielectric layer is arranged between the first conductive layer and the first color-changing layer; the second dielectric layer is arranged between the second conductive layer and the second color-changing layer;

the first dielectric layer is an insulating material layer and has the thickness of 20-200nm; the insulating material is selected from one of silicon oxide, silicon nitride, zinc oxide, aluminum oxide, tin oxide, tantalum oxide and zirconium oxide;

the second dielectric layer is an insulating material layer and has the thickness of 20-200nm; the insulating material is selected from one of silicon oxide, silicon nitride, zinc oxide, aluminum oxide, tin oxide, tantalum oxide and zirconium oxide;

the first color-changing layer is a cathode color-changing material layer or an anode color-changing material layer; the second color-changing layer corresponds to the first color-changing layer, and when the first color-changing layer is a cathode color-changing material layer, the second color-changing layer is an anode color-changing material layer;

in the cathode color-changing material layer, the cathode color-changing material is a transition metal oxide of a VIB group;

in the anode color-changing material layer, the anode color-changing material is transition metal oxide of VIII group and Pt group;

when the first color-changing layer or the second color-changing layer is a tungsten oxide layer, the tungsten oxide layer is formed by amorphous nano particles, the surface sheet resistance is more than 100KΩ, and the thickness is 200-600nm;

the ion conducting layer is a lithium ion conducting material layer, and the lithium ion conducting material is selected from one of lithium tantalate, lanthanum lithium titanate, lithium silicate, lithium aluminate, lithium aluminum silicate, lithium chromate, lithium boron sulfate, lithium vanadate or lithium tantalate.

2. The all-solid electrochromic glass of claim 1 further comprising a protective layer disposed on the second conductive layer, the protective layer being a layer of high light transmission material.

3. An all-solid electrochromic device comprising voltage control means and an all-solid electrochromic glazing according to any one of claims 1 to 2; the voltage control device is connected with the all-solid-state electrochromic glass.

4. The all-solid-state electrochromic device according to claim 3, further comprising a cover plate disposed opposite the all-solid-state electrochromic glass, the cover plate being located above the all-solid-state electrochromic glass.