WO2021197268A1 - 一种电致变色器件及其变色方法 - Google Patents

一种电致变色器件及其变色方法 Download PDF

Info

Publication number
WO2021197268A1
WO2021197268A1 PCT/CN2021/083600 CN2021083600W WO2021197268A1 WO 2021197268 A1 WO2021197268 A1 WO 2021197268A1 CN 2021083600 W CN2021083600 W CN 2021083600W WO 2021197268 A1 WO2021197268 A1 WO 2021197268A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrochromic
layer
color
materials
electrochromic layer
Prior art date
Application number
PCT/CN2021/083600
Other languages
English (en)
French (fr)
Inventor
程窍
何嘉智
曹超月
Original Assignee
深圳市光羿科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳市光羿科技有限公司 filed Critical 深圳市光羿科技有限公司
Priority to JP2022544672A priority Critical patent/JP2023512976A/ja
Priority to EP21780291.7A priority patent/EP4083699A4/en
Priority to KR1020227028551A priority patent/KR20220129053A/ko
Priority to US17/798,516 priority patent/US20230063383A1/en
Publication of WO2021197268A1 publication Critical patent/WO2021197268A1/zh

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1524—Transition metal compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G02F1/15165—Polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G02F2001/1518—Ferrocene compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F2001/164—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect the electrolyte is made of polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/44—Arrangements combining different electro-active layers, e.g. electrochromic, liquid crystal or electroluminescent layers

Definitions

  • This application belongs to the technical field of color changing devices, and specifically relates to an electrochromic device and a color changing method thereof.
  • Electrochromism refers to the phenomenon that the optical properties of materials undergo stable and reversible color changes under the action of an external electric field, which is manifested as reversible changes in color and transparency in appearance.
  • Materials with electrochromic properties are called electrochromic materials, and devices made of electrochromic materials are called electrochromic devices. Electrochromic devices have very important application prospects in the fields of color-changing glasses, electronic displays, military concealment, and building energy conservation.
  • Existing electrochromic devices generally adopt a laminated structure of conductive layer-electrochromic layer-electrolyte layer-ion storage layer (electrochromic layer)-conductive layer.
  • the electrochromic layer is one of the cores of the electrochromic device, and the electrochromic materials constituting the electrochromic layer can be divided into inorganic electrochromic materials and organic electrochromic materials.
  • Inorganic electrochromic materials have the advantages of stability and fast response, such as tungsten trioxide (WO 3 ), vanadium pentoxide (V 2 O 5 ), nickel oxide (NiO), and titanium dioxide (TiO 2 ).
  • electrochromic materials can be divided into cathode electrochromic materials and anode electrochromic materials.
  • Cathodic electrochromic materials can obtain electrons to undergo a reduction reaction to switch colors between coloring and fading; anode electrochromic materials can lose electrons to cause oxidation reactions, and switch colors between coloring and fading.
  • the prior art selects the cathode electrochromic material and the anode electrochromic material that can match each other in color change to assemble the electrochromic device. For example, a cathode electrochromic material with a color change range from red to colorless and an anode electrochromic material with a color change range from colorless to blue are used to assemble the device to realize the switch of the electrochromic device from red to blue.
  • CN 105278198A discloses a complementary inorganic all-solid-state electrochromic device and a preparation method thereof.
  • the device includes a substrate, a transparent conductive layer, an anode electrochromic layer, an ion storage layer, and a fast ion transport layer sequentially arranged from bottom to top , Cathode electrochromic layer and transparent conductive layer.
  • CN 105607375A discloses an electrochromic device for high-throughput screening of solid inorganic electrochromic materials and a preparation method thereof, wherein each electrochromic device unit is sequentially plated with cathode electrodes from the lower transparent conductive layer from the inside to the outside. The chromic layer, the solid electrolyte layer, the anode electrochromic layer and the upper transparent layer.
  • CN 110109311A discloses an all-solid-state electrochromic device and a preparation method thereof.
  • the device is composed of a substrate A, a transparent conductive layer A, an anode electrochromic layer, a solid electrolyte layer, a cathode electrochromic layer, and a transparent conductive layer arranged in sequence.
  • the layer B and the substrate B are combined, the cathode electrochromic layer is a tungsten oxide film doped with metal atoms, and the anode electrochromic layer is a nickel oxide film doped with metal atoms.
  • These electrochromic devices all adopt the structure of the cathode electrochromic layer and the anode electrochromic layer.
  • the electrochromic device adopts a structure in which two electrochromic layers are both anode electrochromic materials or both cathode electrochromic materials. Combined with a specific color change method, the switch between different colors is realized and the electrochromic layer is expanded.
  • the selection range of color-changing materials can easily be extended to more color switching, which can meet the needs of multi-color display and personalized customization.
  • the present application provides an electrochromic device, the electrochromic device comprising a first substrate, a first transparent conductive layer, a first electrochromic layer, an electrolyte layer, and a second electrochromic layer stacked in sequence , The second transparent conductive layer and the second substrate;
  • the materials of the first electrochromic layer and the second electrochromic layer are both cathode electrochromic materials or both anode electrochromic materials.
  • the two electrochromic layers of the electrochromic device provided in this application both use cathode electrochromic material or anode electrochromic material, combined with a specific color change method, can switch between different colors, so that the two electrochromic layers
  • the material does not need to be limited to the combination of cathode electrochromic material and anode electrochromic material, which expands the selection range of electrochromic material.
  • the first transparent conductive layer and the second transparent conductive layer are each independently made of indium-tin oxide (ITO), aluminum zinc oxide (AZO), At least one of fluorine doped tin oxide (FTO), silver nanowires, graphene, carbon nanotubes, metal grids, and silver nanoparticles is formed.
  • ITO indium-tin oxide
  • AZO aluminum zinc oxide
  • FTO fluorine doped tin oxide
  • the thickness of the first transparent conductive layer and the second transparent conductive layer are each independently 1-1000 nm, for example, 1 nm, 2 nm, 5 nm, 8 nm, 10 nm, 15 nm, 20 nm, 25nm, 50nm, 70nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm or 1000nm etc.
  • cathodic electrochromic materials include cathodic electrochromic reduction state coloring materials, cathodic electrochromic oxidation state coloring materials and cathodic electrochromic multicolor materials.
  • Anode electrochromic materials include anode electrochromic reduction state coloring materials, anode electrochromic oxidation state coloring materials and anode electrochromic multicolor materials.
  • the initial state of the cathode electrochromic reduction state coloring material is colorless, and the electron reduction state becomes colored; such materials include TiO 2 , WO 3 , Nb 2 O 5 , MoO 3 , Ta 2 O 5 , Violet essence and its derivatives, etc.
  • the initial state of the cathode electrochromic oxidation state coloring material is colored, and the electron reduction state becomes colorless; such materials include Prussian blue and its derivatives, Ruthenium purple and its derivatives, etc. .
  • the color change of the cathode electrochromic multicolor material can be a variety of color changes, for example, the initial state is color a, the intermediate state of the electron is color b, and the electron reduction state is changed to color c; or it is a two-color change, for example, the initial state is For color a', the reduced electron state becomes color c'; such materials include CoO x , Rh 2 O 3 , ferrocene and its derivatives, etc.
  • the initial state of the anode electrochromic reduction state coloring material is colored, and the electron-losing oxidation state becomes colorless; such materials include polythiophene and its derivatives.
  • the initial state of the anode electrochromic oxidation state coloring material is colorless, and the electron-loss oxidation state becomes colored; such materials include NiO, IrO 2 , polytriphenylamines and their derivatives, etc.
  • the color change of the anode electrochromic multicolor material can be a variety of color changes, for example, the initial state is color d, the electron-losing intermediate state is color e, and the electron-losing oxidation state becomes color f; or it is a two-color change, for example, the initial state is The color d', the electron-losing oxidation state changes to the color f'; such materials include V 2 O 5 , MnO 2 , polyaniline and its derivatives, polypyrrole and its derivatives, etc.
  • the materials of the first electrochromic layer and the second electrochromic layer of the electrochromic device provided in the present application can be respectively selected from the cathode electrochromic reduction state coloring material, the cathode electrochromic oxidation state coloring material and the cathode electrochromic multiple Choose one of the color materials, or the materials of the first electrochromic layer and the second electrochromic layer can also be respectively selected from the anodic electrochromic reduction state coloring material, the anodic electrochromic oxidation state coloring material and the anodic electrochromic layer Choose one of multi-color materials. Combined with a specific color change method, you can switch between different colors. Different types of materials can be matched according to the color requirements of the end product.
  • the materials of the first electrochromic layer and the second electrochromic layer are not at the same time cathodic electrochromic polychromatic materials, and are not at the same time anodic electrochromic polychromic materials.
  • the materials of the first electrochromic layer and the second electrochromic layer are neither cathodic electrochromic polychromatic materials, and neither are anode electrochromic polychromic materials.
  • the preferred choice is Cathodic electrochromic reduction state coloring material, cathode electrochromic oxidation state coloring material, anode electrochromic reduction state coloring material and anode electrochromic oxidation state coloring material. It is understandable that in this case, it does not mean to exclude the use of cathode electrochromic polychromic materials and anode electrochromic polychromic materials.
  • the materials of the first electrochromic layer and the second electrochromic layer are both cathode electrochromic reduction state coloring materials, both are cathode electrochromic oxidation state coloring materials, and It is an anode electrochromic reduction state coloring material or both are anode electrochromic oxidation state coloring materials.
  • the electrochromic device obtained in this way after pretreatment, after applying a forward voltage, one of the two electrochromic layers (layer A) is colored, and the other layer (layer B) is colorless; After the voltage is applied, one layer (layer A) is colorless, and the other layer (layer B) is colored; the color can be switched between the two colors.
  • the material of the two electrochromic layers can also be one of the cathode electrochromic reduction state coloring material, the other the cathode electrochromic oxidation state coloring material; or one of the anode electrochromic reduction state coloring materials
  • the other is an anode electrochromic oxidation state coloring material.
  • the materials of the first electrochromic layer and the second electrochromic layer are not the same material.
  • the materials of the two electrochromic layers are both cathode electrochromic layers.
  • the coloring material in the reduced state of discoloration it is preferable that the materials of the first electrochromic layer and the second electrochromic layer are two materials selected from the coloring materials in the reduced state of electrochromic cathode. If the first electrochromic layer and the second electrochromic layer are made of the same material, the electrochromic device will have no color switching effect after applying forward and reverse voltages. Therefore, the first electrochromic layer and the The material of the second electrochromic layer is preferably different materials.
  • the maximum charge transfer number per unit area of the first electrochromic layer is 0-35C/cm 2 and does not include 0, for example, it can be 0.05C/cm 2 , 0.1C/cm 2 , 0.5C/cm 2 , 1C/cm 2 , 2C/cm 2 , 5C/cm 2 , 8C/cm 2 , 10C/cm 2 , 12C/cm 2 , 15C/cm 2 , 18C/cm 2 , 20C/cm 2 , 22C/cm 2 , 25C/cm 2 , 28C/cm 2 , 30C/cm 2 , 32C/cm 2 or 35C/cm 2, etc.; the maximum charge transfer number per unit area of the second electrochromic layer is 0- 35C/cm 2 and not including 0, for example, it can be 0.05C/cm 2 , 0.1C/cm 2 , 0.5C/cm 2 , 1C/cm
  • the ratio of the maximum charge transfer number per unit area of the first electrochromic layer and the second electrochromic layer is 1:50-50:1, for example, it may be 1:50, 1:45, 1:40, 1:35, 1:30, 1:25, 1:20, 1:15, 1:10, 1:8, 1:6, 1:5, 1:3, 1: 2, 1:1, 2:1, 3:1, 5:1, 6:1, 8:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1 or 50:1; more preferably 1:10-10:1.
  • the maximum number of charge transfer per unit area of the electrochromic layer is related to the type of material and the thickness of the electrochromic layer. For the electrochromic layer of a certain material, the maximum number of charge transfer per unit area increases as the thickness increases. If the thickness of the first electrochromic layer and the second electrochromic layer is too large, and the maximum charge transfer number per unit area is too large, the color change time may become longer when the color is changed, the color change is incomplete, and the color switching effect is not good; if If the thickness of the first electrochromic layer and the second electrochromic layer is too small, and the maximum charge transfer number per unit area is too small, the color may be lighter, the color change effect will be worse, and the device life will be short. If the maximum charge transfer number per unit area of the first electrochromic layer and the second electrochromic layer are too different, the color depth of the two will have a large difference, which will also easily lead to poor color switching effects.
  • the electrolyte layer is a gel electrolyte layer, a liquid electrolyte layer, or a solid electrolyte layer, more preferably a solid electrolyte layer, and even more preferably a solid polymer electrolyte layer.
  • the thickness of the electrolyte layer is 0.1-200 ⁇ m; for example, it can be 0.1 ⁇ m, 0.2 ⁇ m, 0.5 ⁇ m, 0.8 ⁇ m, 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m, 110 ⁇ m, 120 ⁇ m, 130 ⁇ m, 150 ⁇ m, 160 ⁇ m, 180 ⁇ m or 200 ⁇ m etc.
  • a solid electrolyte layer of the following materials can be selected:
  • the solid electrolyte layer contains neutral organic small molecules, and the weight percentage of the neutral organic small molecules is ⁇ 30wt%, such as 25wt%, 20wt%, 15wt%, 10wt%, 5wt%, etc.; the molecular weight of the neutral organic small molecules is less than or equal to 3000, such as 2500, 2000, 1500, 1000, 500, etc.
  • the solid electrolyte layer contains a solid electrolyte polymer, and the solid electrolyte polymer carries a plasticizing group connected by a covalent bond.
  • the solid electrolyte polymer is a copolymer of a monomer or oligomer and an ion conductive polymer, and the side chain of the monomer or oligomer has a plasticizing group, and further, The composition of the solid electrolyte layer further includes a monomer or oligomer segment with a crosslinking group in its side chain.
  • the composition of the solid electrolyte layer includes a copolymer of a monomer or oligomer and an ion conductive polymer, preferably the The copolymer also includes monomers or oligomer fragments with crosslinking groups on the side chains; the same explanation is made for "further” in the following.
  • the plasticizing group and the plasticizing group refer to groups that can weaken the interaction between polymers and reduce the crystallinity of polymers.
  • the solid electrolyte polymer is a plasticized linear polymer and an ion conductive polymer, which are connected by a chemical bond, and the glass transition temperature of the plasticized linear polymer is lower than -20°C, and further
  • the composition of the solid electrolyte layer further includes a monomer or polymer having a crosslinking group on the side chain, and the monomer or polymer having a crosslinking group on the side chain and the plasticized linear polymer And the ion-conducting polymer are connected by chemical bonds.
  • the solid electrolyte polymer is a polymer with a plasticizing group on the side chain and a glass transition temperature lower than -20°C and an ion conductive polymer, and the two are connected by a chemical bond.
  • the composition of the solid electrolyte layer also includes a monomer or polymer with a crosslinking group on the side chain, the monomer or polymer with a crosslinking group on the side chain and the side chain with plasticizing The three groups, the polymer with a glass transition temperature lower than -20°C and the ion conductive polymer, are connected by chemical bonds.
  • the solid electrolyte polymer is a brush polymer, and the brush polymer has a flexible polymer main chain, ion-conducting side chains and immiscible side chains.
  • the solid The composition of the electrolyte layer also includes monomers or oligomers with crosslinking groups on the side chains, and the monomers or oligomers with crosslinking groups on the side chains are copolymerized with the brush in the form of block copolymerization. Shaped polymers are connected by chemical bonds.
  • the immiscible side chain mentioned in this application refers to the side chain that is very different from other side chains or polymers and cannot be effectively blended, while the brush polymer provided in this application refers to the main chain of the polymer that is flexible
  • the introduction of such immiscible side chains in this application can reduce the crystallinity of the polymer, make the polymer in a random state, and thereby improve the overall ion-conducting ability and transparency of the polymer.
  • the ion transport layer is a solid flexible electrolyte layer.
  • the polymer of the solid flexible electrolyte layer can be selected from the following four types of polymers.
  • x, y, and z are each independently selected from an integer greater than zero.
  • the rectangle shown in the formula represents a polymer block with ion-conducting effect (ion conductive polymer block), and the ellipse represents a PR (plasticizing group), or CL (crosslinking group), or NM (Immiscible group), or IC (ion conductive group) these side chain monomers or polymers.
  • Polymer block y with ion-conducting effect such as polyethylene glycol or other materials reported in the literature
  • monomer or polymer block x with plasticizing groups (PR) on the side chain and on the side chain
  • a block copolymer (indicated by PEGPRCL) formed by copolymerization of a monomer or polymer block z with a crosslinking group (CL).
  • polymer block y (such as polyethylene glycol or other materials reported in the literature) with ion-conducting effect and monomer or polymer block x with plasticizing group (PR) on the side chain are copolymerized to form The block copolymer (expressed as PEGPR).
  • the polymer block y with ion-conducting effect such as polyethylene glycol or other materials reported in the literature
  • the linear plasticized polymer (SP) block x such as poly Blocks formed by copolymerization of ethylene, polybutene, polyisobutylene, siloxane, or other materials reported in the literature, etc.
  • monomers or polymer blocks z with crosslinking groups (CL) on the side chains Copolymer expressed as PEGSPCL).
  • polymer block y with ion-conducting effect such as polyethylene glycol or other materials reported in the literature
  • linear plasticized polymer (SP) block x Such as polyethylene, polybutene, polyisobutylene, siloxane, or other materials reported in the literature, etc.
  • block copolymers indicated by PEGSP
  • the ion-conducting polymer block y (such as polyethylene glycol or other materials reported in the literature) and the plasticized polymer (SP-PR) block x with plasticized side chains are formed by chemical reaction.
  • a block copolymer (indicated by PEGSP-PRCL) formed by copolymerization with the monomer or oligomer (CL) block z with a crosslinking group on the side chain.
  • polymer block y with ion-conducting properties such as polyethylene glycol or other materials reported in the literature
  • plasticized polymer (SP-PR) block x with plasticized side chains are connected by chemical reaction
  • the formed block copolymer (indicated by PEGSP-P R).
  • An oligomer or polymer with ion-conducting effect (such as polyethylene glycol or other materials reported in the literature) as a side chain of flexible polymer block x and a side chain that does not blend with the ion-conducting polymer (such as alkyl, aromatic or alkyl, aromatic mixed side chain) flexible polymer block y is connected by chemical reaction, and then with the monomer or oligomer (CL) with crosslinking group on the side chain
  • a comb block copolymer (ICNMCL) formed by copolymerization of block z.
  • oligomers or polymers with ion-conducting effect such as polyethylene glycol or other materials reported in the literature
  • the flexible polymer block x of the side chain and side chains that do not blend with the ion-conducting polymer A comb-shaped block copolymer (ICNM) formed by the flexible polymer block y of chain (alkyl, aromatic or alkyl, aromatic mixed side chain) connected by chemical reaction.
  • ICNM comb-shaped block copolymer
  • the above-mentioned polymer materials used in the ion transport layer also need to be blended with a certain amount of organic salt and/or inorganic salt to form an electrolyte precursor.
  • the inorganic salt includes, but is not limited to, lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, and aluminum salt;
  • the organic salt includes, but is not limited to, ionic liquids, such as EMITFSI and EMIOTF.
  • the electrolyte precursor is cross-linked by heating, photoinitiation and other methods to form the final all-solid electrolyte.
  • plasticizing group (PR) includes but is not limited to the following structures:
  • the crosslinking group (CL) includes but is not limited to the following structures:
  • the main chain of the comb block copolymer includes but is not limited to the following structures:
  • Ion conducting groups include but are not limited to the following structures:
  • the materials of the first substrate and the second substrate are each independently glass or a flexible material, preferably a transparent material.
  • the flexible material includes, but is not limited to, PET (polyethylene terephthalate), cyclic olefin copolymer, cellulose triacetate, and the like.
  • the present application provides a color changing method of the electrochromic device described in the first aspect, and the color changing method includes the following steps:
  • the second electrochromic layer changes from a second color to a fourth color;
  • the pretreatment is: applying a first voltage in a first direction to the electrochromic device to make the first electrochromic layer Changing from the first color to the third color, and the second electrochromic layer keeps the second color unchanged;
  • the function of the pretreatment is to make the first electrochromic layer undergo a reversible oxidation/reduction reaction by gaining and losing electrons, so that its color can be switched; at the same time, the second electrochromic layer undergoes a non-Faraday reaction and partial irreversible electricity.
  • the chemical reaction produces a charge that balances the charges of the electrochromic device.
  • the second electrochromic layer does not undergo a Faraday reaction related to the color change, so the color of the second electrochromic layer remains unchanged.
  • the electrochromic device can be switched between different colors by cyclically applying voltages in opposite directions.
  • the pretreatment step only needs to be performed when the electrochromic device is used for the first time, and no pretreatment is required for subsequent use.
  • the prior art electrochromic device does not have a pretreatment step when it changes color.
  • the two electrochromic layers are both anode electrochromic materials or cathode electrochromic materials, combined with the above-mentioned specific color change method, so that the electrochromic device provided in this application can switch between different colors. , Extending the selection range of electrochromic materials.
  • the pretreatment can be performed by the manufacturer of the electrochromic device, or by the user during the first use, and those skilled in the art can make a selection according to actual needs.
  • the threshold voltage V 1 for changing the first electrochromic layer from the first color to the third color is higher than that in step (2) when the first electrochromic layer is changed from the first color to the third color.
  • the color changes to the threshold voltage V 1 ′ of the third color. Therefore, if the voltage V 1 ′ is applied to the electrochromic device of the present application according to the use method of the existing electrochromic device, it is impossible to preprocess the electrochromic device , And then unable to make it realize color switching.
  • V 1 can be measured by gradually increasing the voltage and observing the reversibility of the color change of the first electrochromic layer; or measured from the cyclic voltammetry curve of the electrochromic device.
  • the absolute value of the first voltage is greater than or equal to V 1 , where V 1 is the critical voltage for causing the second electrochromic layer to undergo an irreversible electrochemical reaction.
  • the pretreatment step of this application needs to use a higher voltage (greater than or equal to V 1 , less than V 2 ) to cause an irreversible electrochemical reaction of the second electrochromic layer, where V 2 is the voltage at which the electrochromic device is broken down. If the first voltage is greater than V 2 , a part of the electrochromic layer material will be irreversibly changed, the structure will be destroyed, and the quality of the electrochromic device will decrease or even be damaged.
  • the absolute value of the third voltage is less than the absolute value of the first voltage.
  • the third voltage only needs to enable the electrochromic layer material to fully undergo a reversible electrochemical reaction, and no irreversible electrochemical reaction is required. Therefore, the voltage is less than the voltage required for the pretreatment step.
  • the present application provides an electronic terminal containing the electrochromic device as described in the first aspect.
  • the electronic terminal may be consumer electronic products, doors and windows, cabinets, electronic tags, wearable equipment, smart glasses, phototherapy equipment, etc., for example, when the electrochromic device is applied to the above-mentioned electronic terminal, it may be set on the surface or inside of the terminal According to specific application scenarios, it can provide various effects such as appearance diversification, privacy shielding, status display, information differentiation, adjustment of ambient light, and filtering/transmitting light of different preset wavelengths.
  • the two electrochromic layers of the electrochromic device provided in this application both use cathode electrochromic material or anode electrochromic material, combined with a specific color change method, can switch between different colors, so that the two electrochromic layers
  • the material does not need to be limited to the combination of cathode electrochromic material and anode electrochromic material, which expands the selection range of electrochromic material.
  • This electrochromic device can be easily promoted to switch between more colors, which can meet the needs of multi-color display and personalized customization.
  • FIG. 1 is a schematic structural diagram of an electrochromic device provided by an embodiment of the application.
  • 1 is the first substrate
  • 2 is the first transparent conductive layer
  • 3 is the first electrochromic layer
  • 4 is the electrolyte layer
  • 5 is the second electrochromic layer
  • 6 is the second transparent conductive layer
  • 7 is the first electrochromic layer.
  • the preparation method of the electrolyte polymer component in the electrolyte layer is as follows:
  • polymer A (a type of solid electrolyte polymer belonging to PEGPRCL) is as follows:
  • polymer B (a type of solid electrolyte polymer belonging to PEGPR) is as follows:
  • polymer C (a type of solid electrolyte polymer belonging to PEGSPCL) is as follows:
  • polymer D (a type of solid electrolyte polymer belonging to PEGSP) is as follows:
  • polymer E (a type of solid electrolyte polymer belonging to PEGSP-PRCL) is as follows:
  • polymer F (a type of solid electrolyte polymer belonging to PEGSP-PR) is as follows:
  • polymer G (a type of solid electrolyte polymer belonging to ICNMCL) is as follows:
  • the mixture can also be used as an electrolyte precursor directly. Used for device preparation). Light reaction to obtain polymer. After water washing and liquid separation, drying, and removing the solvent, polymer G is obtained.
  • polymer H (a type of solid electrolyte polymer belonging to ICNM) is as follows:
  • the testing method for the maximum charge transfer number per unit area of the electrochromic layer is as follows:
  • electrochromic layer to be tested as the working electrode, Ag/AgCl as the reference electrode, and Pt electrode as the counter electrode, connected to a three-electrode system, and the electrolyte solution is a propylene carbonate solution containing 50% lithium perchlorate;
  • V is the scanning speed when scanning the cyclic voltammetry curve
  • A is the area of the electrochromic layer immersed in the electrolyte solution.
  • This embodiment provides an electrochromic device.
  • the schematic diagram of the structure is shown in FIG.
  • the preparation method of the electrochromic device is as follows:
  • the second electrochromic layer 5 (together with the ITO layer and the glass substrate) is dislocated and covered on the electrolyte coating, and ultraviolet curing causes the electrolyte coating to form the electrolyte layer 4 (thickness of 50 ⁇ m) to obtain an electrochromic device.
  • This embodiment also provides a method for changing the color of the electrochromic device described above, which includes the following steps:
  • Reverse voltage (-1.0V) is applied to the electrochromic device, so that the first electrochromic layer 3 is reduced from colorless to blue-violet, and the second electrochromic layer 5 is oxidized from red to colorless;
  • a forward voltage (0V) is applied to the color-changing device, so that the first electrochromic layer 3 is oxidized from blue-violet to colorless, and the second electrochromic layer 5 is reduced from colorless to red;
  • a reverse voltage ( -1.0V) and forward voltage (0V) make the device color switch between blue-violet and red.
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • the phototherapy equipment can be glasses, helmets, display screens, etc., prepared into lenses or display screens, used to filter/transmit light of different preset wavelengths, and incident light of specific wavelengths to the user's eyes , So as to adjust jet lag, improve sleep quality, relieve fatigue, relieve emotions and other effects.
  • This embodiment provides an electrochromic device.
  • the schematic diagram of the structure is shown in FIG.
  • the preparation method of the electrochromic device is as follows:
  • the ruthenium violet thin film is electrochemically deposited on the electrode to form a second electrochromic layer 5 (thickness 250 nm).
  • the maximum charge transfer number per unit area of the second electrochromic layer 5 was tested, and it was 10.2C/cm 2 , and the ratio of the maximum charge transfer number per unit area of the first electrochromic layer 3 to the second electrochromic layer 5 was 0.87: 1.
  • Electrochromic device Mix the precursor of 10wt% lithium perchlorate, 89.9wt% polymer G, 40%, 40mmol/mL KCl solution and 0.1wt% azobisisobutyronitrile, and coat it on the first electrochromic layer 3 On the top, an electrolyte coating is formed; then the second electrochromic layer 5 (together with the ITO layer and the glass substrate) is dislocated and covered on the electrolyte coating, and the electrolyte coating is cured by ultraviolet to form the electrolyte layer 4 (thickness of 10 ⁇ m) to obtain Electrochromic device.
  • This embodiment also provides a method for changing the color of the electrochromic device described above, which includes the following steps:
  • a reverse voltage (-1.2V) is applied to the device, so that the first electrochromic layer 3 is reduced from deep blue to colorless, while the second electrochromic layer 5 remains purple.
  • This application has no special restrictions on the timing of the pretreatment, which can be executed when the electrochromic device switches between different colors for the first time, or it can be executed immediately after the electrode arrangement step of the foregoing preparation method of the electrochromic device .
  • a forward voltage (0.5V) is applied to the electrochromic device, so that the first electrochromic layer 3 is oxidized from colorless to deep blue, and the second electrochromic layer 5 is reduced from purple to colorless;
  • a reverse voltage (-0.5V) is applied to the device to reduce the first electrochromic layer 3 from dark blue to colorless, and the second electrochromic layer 5 is oxidized from colorless to purple;
  • forward voltage is applied to the device cyclically (0.5V) and reverse voltage (-0.5V), make the device color switch between dark blue and purple.
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • the consumer electronic products can be mobile phones, tablets, computers, watches, etc., applied to the product housing or display screen or any other position, so that the consumer electronic products have rich appearance effects, and can also be used To realize the effect of displaying different status information according to different color status.
  • This embodiment provides an electrochromic device.
  • the schematic diagram of the structure is shown in FIG.
  • the preparation method of the electrochromic device is as follows:
  • the chromic layer 5 (together with the ITO layer and the glass substrate) is dislocated and covered on the electrolyte coating, and thermally cured at 90°C to form the electrolyte layer 4 (with a thickness of 80 ⁇ m) from the electrolyte coating to obtain an electrochromic device.
  • This embodiment also provides a method for changing the color of the electrochromic device described above, which includes the following steps:
  • a reverse voltage (-3.0V) is applied to the device, so that the first electrochromic layer 3 is reduced from colorless to blue, while the second electrochromic layer 5 remains colorless.
  • This application has no special restrictions on the timing of the pretreatment, which can be executed when the electrochromic device switches between different colors for the first time, or it can be executed immediately after the electrode arrangement step of the foregoing preparation method of the electrochromic device .
  • a forward voltage (1.5V) is applied to the electrochromic device, so that the first electrochromic layer 3 is oxidized from blue to colorless, and the second electrochromic layer 5 is reduced from colorless to light gray;
  • a reverse voltage (-1.5V) is applied to the color-changing device, so that the first electrochromic layer 3 is reduced from colorless to blue, and the second electrochromic layer 5 is oxidized from light gray to colorless;
  • the forward voltage (1.5V) and the reverse voltage (-1.5V) switch the device color between light gray and blue.
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • it can be used in doors and windows, and can be used in the glass of doors and windows.
  • the color and transmittance of the glass can be adjusted according to user needs, so as to achieve the effects of shielding privacy, adjusting environmental brightness, and temperature adjustment.
  • This embodiment provides an electrochromic device.
  • the materials of the first electrochromic layer 3 and the second electrochromic layer 5 are both anode electrochromic oxidation state coloring materials, and the electrolyte layer 4 Replace the raw material of the composition with polymer F;
  • the material of the first electrochromic layer 3 is NiO, which is formed by reactive sputtering using Ni as a metal target, with a thickness of 90 nm and a maximum charge transfer per unit area of 18C/cm 2 ;
  • the second electrochromic layer The material of layer 5 is IrO 2 , which is formed by reactive sputtering with Ir as a metal target. The thickness is 125 nm, and the maximum number of charge transfer per unit area is 25C/cm 2.
  • the first electrochromic layer 3 and the second electrochromic layer 3 The ratio of the maximum charge transfer number per unit area of the chromic layer 5 is 0.66:1; the electrolyte layer 4 is mixed with 10wt% lithium perchlorate, 89.9wt% polymer F precursor and 0.1wt% carbonyl diimidazole at 100°C It is formed by heat curing and has a thickness of 50 ⁇ m.
  • This embodiment also provides a method for changing the color of the electrochromic device described above, which includes the following steps:
  • a forward voltage (3V) is applied to the device, so that the first electrochromic layer 3 is oxidized from colorless to tan, while the second electrochromic layer 5 remains colorless.
  • This application has no special restrictions on the timing of the pretreatment, which can be executed when the electrochromic device switches between different colors for the first time, or it can be executed immediately after the electrode arrangement step of the foregoing preparation method of the electrochromic device .
  • a reverse voltage (-1.8V) to the electrochromic device, the first electrochromic layer 3 is reduced from brown to colorless, and the second electrochromic layer 5 is oxidized from colorless to blue-black;
  • a forward voltage (1.8V) is applied to the chromic device, so that the first electrochromic layer 3 is oxidized from colorless to tan, and the second electrochromic layer 5 is reduced from blue-black to colorless;
  • the forward voltage (-1.8V) and forward voltage (1.8V) switch the device color between blue-black and tan.
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • it can be applied to cabinets, it can be applied to the surface of cabinets or glass, according to the effect of diversifying appearance, hiding privacy, adjusting the temperature in the cabinets and so on.
  • This embodiment provides an electrochromic device.
  • the difference from embodiment 1 is that the poly-2-[(2-ethylhexyloxy)methyl]3,4 is weighed when preparing the first electrochromic layer 3.
  • -Thieno 1,4 dioxane is 600mg, spin-coated thickness is 800nm, maximum charge transfer number per unit area is 12.2C/cm 2 ;
  • poly(3-hexyl) weighed when preparing the second electrochromic layer 5 Thiophene) (P3HT) is 50mg, the thickness of spin coating is 12nm, the maximum charge transfer per unit area is 0.25C/cm 2 , the maximum charge transfer per unit area of the first electrochromic layer 3 and the second electrochromic layer 5
  • the ratio of the numbers is 48.8:1; the raw material of the electrolyte layer 4 is replaced by polymer B, which is formed by mixing 10wt% lithium perchlorate, 89.9wt% polymer B precursor and 85% potassium hydroxide 0.1
  • the color of the device can be in blue-violet and red Switch between.
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • wearable devices it can be applied to the housing or display area of the wearable device to achieve the effects of diversified appearance and light filtering.
  • This embodiment provides an electrochromic device.
  • the material of the first electrochromic layer 3 is a cathode electrochromic reduction state coloring material
  • the material of the second electrochromic layer 5 is a cathode electrochromic layer.
  • the raw material of the electrolyte layer 4 is replaced with polymer A;
  • the electrolyte layer 4 is made of lithium perchlorate 10wt%, 89.9wt% polymer A precursor, 0.05wt% cuprous chloride and 0.1wt% N,N,N',N",N"-pentamethyl Diethylenetriamine is mixed and thermally cured at 100°C to form a thickness of 150 ⁇ m.
  • the color of the device can be colorless and Switch between superimposed colors (blue and purple).
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • electronic tags For example, it is used in electronic tags to achieve the effect of status display and information differentiation.
  • This embodiment provides an electrochromic device.
  • the material of the first electrochromic layer 3 is an anode electrochromic reduced state coloring material
  • the material of the second electrochromic layer 5 is an anode electrochromic layer.
  • the coloring material in the chromogenic oxidation state, the raw material of the electrolyte layer is replaced with polymer E;
  • the material of the first electrochromic layer 3 is poly-2-[(2-ethylhexyloxy)methyl]3,4-thiophene, the preparation method refers to Example 1, the thickness is 200nm, and the maximum charge transfer number per unit area is 3.3C/cm 2 ; the material of the second electrochromic layer 5 is NiO, the preparation method refers to Example 4, the thickness is 180nm, the maximum number of charge transfer per unit area is 32C/cm 2 , the first electrochromic layer 3 and the second electrochromic layer 3 The ratio of the maximum number of charge transfers per unit area of the second electrochromic layer 5 is 1:10; the electrolyte layer 4 is mixed with 10% by weight of lithium perchlorate, 89.9% by weight of polymer E precursor and 0.1% by weight of carbonyl diimidide, 100 It is formed by heat curing at °C with a thickness of 30 ⁇ m.
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • This embodiment provides an electrochromic device.
  • the potassium ferricyanide weighed when preparing the first electrochromic layer 3 is 160 mg
  • the spin-coated thickness is 400 nm
  • the maximum charge per unit area The transfer number is 16C/cm 2
  • the thickness of the second electrochromic layer 5 is 250nm
  • the maximum charge transfer number per unit area is 10.2C/cm 2
  • the unit of the first electrochromic layer 3 and the second electrochromic layer 5 The ratio of the maximum number of charge transfers by area is 1.57:1.
  • the color of the device can be dark blue Switch between and purple.
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • This embodiment provides an electrochromic device.
  • the difference from embodiment 3 is that the thickness of the first electrochromic layer 3 is 75nm, the maximum charge transfer per unit area is 30C/cm 2 , and the second electrochromic layer 5 The thickness is 20nm, the maximum charge transfer per unit area is 3C/cm 2 , and the ratio of the maximum charge transfer per unit area of the first electrochromic layer 3 to the second electrochromic layer 5 is 10:1.
  • the color of the device can be light gray and Switch between blue.
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • This embodiment provides an electrochromic device.
  • the schematic diagram of the structure is shown in FIG.
  • the preparation method of the electrochromic device is as follows:
  • the constant current method is used to deposit aniline with a concentration of 0.1 mol/L in a 1 mol/L sulfuric acid solution with a current density of 10 ⁇ A/cm 2 for 30 minutes to form the first electrochromic on the ITO layer plated on the glass substrate Layer 3 (polyaniline film, thickness 280nm).
  • the maximum number of charge transfer per unit area of the first electrochromic layer 3 was tested, and it was 20C/cm 2 .
  • the chromic layer 5 (together with the ITO layer and the glass substrate) is dislocated and covered on the electrolyte coating, and thermally cured at 120°C to form the electrolyte layer 4 (with a thickness of 60 ⁇ m) to obtain an electrochromic device.
  • This embodiment also provides a method for changing the color of the electrochromic device described above, which includes the following steps:
  • a forward voltage (2.5V) is applied to the device, so that the first electrochromic layer 3 is oxidized from green to deep blue, while the second electrochromic layer 5 remains yellow.
  • This application has no special restrictions on the timing of the pretreatment, which can be executed when the electrochromic device switches between different colors for the first time, or it can be executed immediately after the electrode arrangement step of the foregoing preparation method of the electrochromic device .
  • Reverse voltage (-1.0V) is applied to the electrochromic device, so that the first electrochromic layer 3 is reduced from dark blue to green, and the second electrochromic layer 5 is oxidized from yellow to gray-black;
  • the device applies a forward voltage (1.2V) to oxidize the first electrochromic layer 3 from green to dark blue, and the second electrochromic layer 5 is reduced from gray-black to yellow;
  • the device is cyclically applied with a forward voltage (1.2 V) and reverse voltage (-1.0V), make the device color realize color switching.
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • This embodiment provides an electrochromic device.
  • the difference from embodiment 7 is that the poly-2-[(2-ethylhexyloxy)methyl]3,4 is weighed when preparing the first electrochromic layer 3.
  • -Thieno 1,4 dioxane is 20mg
  • the thickness of spin coating is 6nm
  • the maximum charge transfer per unit area is 0.1C/cm 2
  • the thickness of the second electrochromic layer 5 is 25nm
  • the maximum charge transfer per unit area The number is 5C/cm 2
  • the ratio of the maximum charge transfer number per unit area of the first electrochromic layer 3 and the second electrochromic layer 5 is 0.02:1.
  • the electrochromic device provided in this embodiment can be used in terminal products such as consumer electronics, electronic tags, doors and windows, cabinets, wearable devices, smart glasses, and phototherapy equipment.
  • the electrochromic device provided in embodiment 1 is used for color switching.
  • the method is different from that in embodiment 1 in that the device is directly cyclically applied with forward voltage (1.2V) and reverse voltage (-1.2V) to change the color;
  • first electrochromic layer 3 and the second electrochromic layer 5 are both anode electrochromic reduced state coloring materials, they are both in the reduced state in the initial state. Due to the low voltage potential, sufficient charge cannot be provided to oxidize the material Fading, so the device cannot perform color switching.

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

一种电致变色器件及其变色方法。电致变色器件包括依次层叠的第一基底（1）、第一透明导电层（2）、第一电致变色层（3）、电解质层（4）、第二电致变色层（5）、第二透明导电层（6）和第二基底（7）；其中，第一电致变色层（3）和第二电致变色层（5）的材料均为阴极电致变色材料或均为阳极电致变色材料。电致变色器件的变色方法包括：对预处理后的电致变色器件循环施加与第一电压方向相反和相同的电压，使电致变色器件在不同颜色间切换。由于采用了两层电致变色层均为阳极电致变色材料或均为阴极电致变色材料的结构，结合特定的变色方法，能够在不同颜色间的切换，扩展电致变色材料的选择范围。

Description

一种电致变色器件及其变色方法 技术领域
本申请属于变色器件技术领域，具体涉及一种电致变色器件及其变色方法。
背景技术
电致变色是指材料的光学属性在外加电场的作用下发生稳定、可逆的颜色变化的现象，在外观上表现为颜色和透明度的可逆变化。具有电致变色性能的材料称为电致变色材料，用电致变色材料做成的器件称为电致变色器件。电致变色器件在变色眼镜、电子显示、军事隐藏、建筑节能等领域有非常重要的应用前景。
现有的电致变色器件一般采用导电层-电致变色层-电解质层-离子储存层(电致变色层)-导电层的层叠结构。其中，电致变色层是电致变色器件的核心之一，构成电致变色层的电致变色材料可分成无机电致变色材料与有机电致变色材料。无机电致变色材料具有稳定、响应快的优点，如三氧化钨(WO 3)、五氧化二钒(V 2O 5)、氧化镍(NiO)、二氧化钛(TiO 2)。有机电致变色材料种类多，颜色丰富，便于设计，如紫罗精、聚噻吩类。电致变色材料根据颜色变化还可分成阴极电致变色材料与阳极电致变色材料。阴极电致变色材料可以得电子发生还原反应，在着色和褪色之间切换颜色；阳极电致变色材料可以失电子发生氧化反应，在着色和褪色之间切换颜色。
当前，大多数电致变色器件的制作工艺较复杂，颜色变化单一，难以满足多色显示以及个性化定制的需求。为了实现电致变色器件的颜色切换，现有技术选用在颜色变化上能相互匹配的阴极电致变色材料和阳极电致变色材料来组装电致变色器件。例如选用变色范围在红色至无色的阴极电致变色材料，和变色范围在无色至蓝色的阳极电致变色材料组装器件，实现电致变色器件在红色至蓝色之间的切换。
CN 105278198A公开了一种互补型无机全固态电致变色器件及其制备方法，该器件包括由下至上依次设置的衬底、透明导电层、阳极电致变色层、离子存储层、快离子传输层、阴极电致变色层和透明导电层。CN 105607375A公开了一种高通量筛选固态无机电致变色材料的电致变色器件及其制备方法，其中每一个电致变色器件单元自下透明导电层起从内至外依次镀制有阴极电致变色层、固态电解质层、阳极电致变色层及上透明层。CN 110109311A公开了一种全固态电致变色器件及其制备方法，该器件由依次设置的衬底A、透明导电 层A、阳极电致变色层、固体电解质层、阴极电致变色层、透明导电层B和衬底B组合而成，阴极电致变色层为掺杂金属原子的氧化钨薄膜，阳极电致变色层为掺杂金属原子的氧化镍薄膜。这些电致变色器件均采用了阴极电致变色层和阳极电致变色层配合的结构。
但是，由于目前电致变色材料的种类较少，对于阳极电致变色材料(或阴极电致变色材料)可能难以找到与其颜色相匹配的阴极电致变色材料(或阳极电致变色材料)，需要自主设计研发；而颜色相匹配的又可能都属于阳极电致变色材料或阴极电致变色材料。这就导致上述结构的电致变色器件在实际应用中容易受到颜色、材料或工艺的限制，难以推广到更多颜色的相互切换。
发明内容
本申请提供一种电致变色器件及其变色方法。该电致变色器件采用了两层电致变色层均为阳极电致变色材料或均为阴极电致变色材料的结构，结合特定的变色方法，实现了在不同颜色间的切换，扩展了电致变色材料的选择范围，易于推广到更多颜色的相互切换，可以满足多色显示以及个性化定制的需求。
第一方面，本申请提供一种电致变色器件，所述电致变色器件包括依次层叠的第一基底、第一透明导电层、第一电致变色层、电解质层、第二电致变色层、第二透明导电层和第二基底；
其中，所述第一电致变色层和所述第二电致变色层的材料均为阴极电致变色材料或均为阳极电致变色材料。
本申请提供的电致变色器件的两层电致变色层均采用阴极电致变色材料或阳极电致变色材料，结合特定的变色方法，可以在不同颜色间切换，从而使得两层电致变色层的材料无需局限于阴极电致变色材料与阳极电致变色材料的组合，扩展了电致变色材料的选择范围。
在本申请一实施方式中，所述第一透明导电层和所述第二透明导电层各自独立地由氧化铟锡(indium-tin oxide，ITO)、氧化锌铝(aluminum zinc oxide，AZO)、氟掺杂氧化锡(fluorine doped tin oxide，FTO)、银纳米线、石墨烯、碳纳米管、金属网格和银纳米颗粒中的至少一种形成。
在本申请一实施方式中，所述第一透明导电层和所述第二透明导电层的厚度各自独立地为1-1000nm，例如可以是1nm、2nm、5nm、8nm、10nm、15nm、20nm、25nm、50nm、70nm、100nm、150nm、200nm、250nm、300nm、350nm、400nm、450nm、500nm、550nm、600nm、650nm、700nm、750nm、800nm、850nm、900nm、950nm或1000nm等。
本领域中，阴极电致变色材料包括阴极电致变色还原态着色材料、阴极电致变色氧化态着色材料和阴极电致变色多色材料。
阳极电致变色材料包括阳极电致变色还原态着色材料、阳极电致变色氧化态着色材料和阳极电致变色多色材料。
如本文所使用，阴极电致变色还原态着色材料初始态为无色，得电子还原态变为有色；此类材料包括TiO 2，WO 3，Nb 2O 5，MoO 3，Ta 2O 5，紫精及其衍生物等。
阴极电致变色氧化态着色材料初始态为有色，得电子还原态变为无色；此类材料包括普鲁士蓝(Prussian blue)类及其衍生物，钌紫(Ruthenium purple)类及其衍生物等。
阴极电致变色多色材料的颜色变化可以是多种颜色变化，例如初始态为颜色a，得电子中间态为颜色b，得电子还原态变为颜色c；或者是双色变化，例如初始态为颜色a’，得电子还原态变为颜色c’；此类材料包括CoO x，Rh 2O 3，二茂铁及其衍生物等。
阳极电致变色还原态着色材料初始态为着色，失电子氧化态变为无色；此类材料包括聚噻吩及其衍生物等。
阳极电致变色氧化态着色材料初始态为无色，失电子氧化态变为有色；此类材料包括NiO，IrO 2，聚三苯胺类及其衍生物等。
阳极电致变色多色材料的颜色变化可以是多种颜色变化，例如初始态为颜色d，失电子中间态为颜色e，失电子氧化态变为颜色f；或者是双色变化，例如初始态为颜色d’，失电子氧化态变为颜色f’；此类材料包括V 2O 5，MnO 2，聚苯胺及其衍生物，聚吡咯及其衍生物等。
本申请提供的电致变色器件的第一电致变色层和第二电致变色层的材料可以分别从阴极电致变色还原态着色材料、阴极电致变色氧化态着色材料和阴极电致变色多色材料中任选一种，或者第一电致变色层和第二电致变色层的材料也可以分别从阳极电致变色还原态着色材料、阳极电致变色氧化态着色材料和阳极电致变色多色材料中任选一种。结合特定的变色方法，可以在不同颜色间切换。可以根据终端产品对颜色的需求，进行不同类型材料之间的匹配。
在本申请一实施方式中，所述第一电致变色层和所述第二电致变色层的材料不同时为阴极电致变色多色材料，且不同时为阳极电致变色多色材料。
在本申请一实施方式中，所述第一电致变色层和所述第二电致变色层的材料均不为阴极电致变色多色材料，且均不为阳极电致变色多色材料。
由于阴极电致变色多色材料和阳极电致变色多色材料的材料选择、颜色匹配较为复杂，当终端产品对电致变色器件的产品需求为在两种颜色状态之间进行切换时，优先选用阴极电致变色还原态着色材料、阴极电致变色氧化态着色材料、阳极电致变色还原态着色材料和阳极电致变色氧化态着色材料。可以理解的是，在此情况下，并不表示排除阴极电致变色多色材料和阳极电致变色多色材料的使用。
在本申请一实施方式中，所述第一电致变色层和所述第二电致变色层的材料均为阴极电致变色还原态着色材料、均为阴极电致变色氧化态着色材料、均为阳极电致变色还原态着色材料或均为阳极电致变色氧化态着色材料。这样得到的电致变色器件，经过预处理后，在施加正向电压后，两层电致变色层中一层(A层)为着色，另一层(B层)为无色；在施加反向电压后，则切换为一层(A层)为无色，另一层(B层)为着色；颜色可以在两种颜色之间切换。
本申请中，两层电致变色层的材料也可以一者为阴极电致变色还原态着色材料，另一者为阴极电致变色氧化态着色材料；或一者为阳极电致变色还原态着色材料，另一者为阳极电致变色氧化态着色材料。这样得到的电致变色器件的颜色可以在无色和两层电致变色层的叠加色之间切换。
在本申请一实施方式中，所述第一电致变色层和所述第二电致变色层的材料不为相同材料，具体而言，以两层电致变色层的材料均为阴极电致变色还原态着色材料为例，则优选第一电致变色层和第二电致变色层的材料为从阴极电致变色还原态着色材料中选出的两种材料。若第一电致变色层和第二电致变色层采用相同的材料，则在施加正反向电压后，电致变色器件无颜色切换效果，因此本申请中所述第一电致变色层和所述第二电致变色层的材料优选为不相同材料。
在本申请一实施方式中，所述第一电致变色层的单位面积最大电荷转移数为0-35C/cm 2且不包括0，例如可以是0.05C/cm 2、0.1C/cm 2、0.5C/cm 2、1C/cm 2、2C/cm 2、5C/cm 2、8C/cm 2、10C/cm 2、12C/cm 2、15C/cm 2、18C/cm 2、20C/cm 2、22C/cm 2、25C/cm 2、28C/cm 2、30C/cm 2、32C/cm 2或35C/cm 2等；所述第二电致变色层的单位面积最大电荷转移数为0-35C/cm 2且不包括0，例如可以是0.05C/cm 2、0.1C/cm 2、0.5C/cm 2、1C/cm 2、2C/cm 2、5C/cm 2、8C/cm 2、10C/cm 2、12C/cm 2、15C/cm 2、18C/cm 2、20C/cm 2、22C/cm 2、25C/cm 2、28C/cm 2、30C/cm 2、32C/cm 2或35C/cm 2等。
在本申请一实施方式中，所述第一电致变色层与所述第二电致变色层的单 位面积最大电荷转移数之比为1:50-50:1，例如可以是1:50、1:45、1:40、1:35、1:30、1:25、1:20、1:15、1:10、1:8、1:6、1:5、1:3、1:2、1:1、2:1、3:1、5:1、6:1、8:1、10:1、15:1、20:1、25:1、30:1、35:1、40:1、45:1或50:1；进一步优选为1:10-10:1。
电致变色层的单位面积最大电荷转移数与材料种类和电致变色层厚度有关。对于确定材质的电致变色层，单位面积最大电荷转移数随着厚度增大而增大。若第一电致变色层和第二电致变色层的厚度过大，单位面积最大电荷转移数过大，则在变色时可能导致变色时间变长，变色不完全，颜色切换效果不好；若第一电致变色层和第二电致变色层的厚度过小，单位面积最大电荷转移数过小，则可能导致颜色较浅，变色效果变差，且器件寿命短。若第一电致变色层和第二电致变色层的单位面积最大电荷转移数差别过大，二者颜色深度差别较大，同样容易导致颜色切换效果不好。
在本申请一实施方式中，所述电解质层为凝胶态电解质层、液态电解质层或固态电解质层，进一步优选为固态电解质层，更进一步优选为固态聚合物电解质层。
在本申请一实施方式中，所述电解质层的厚度为0.1-200μm；例如可以是0.1μm、0.2μm、0.5μm、0.8μm、1μm、2μm、5μm、8μm、10μm、20μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm、100μm、110μm、120μm、130μm、150μm、160μm、180μm或200μm等。
本申请对所述电解质层的种类没有特殊限制，示例性的，可以选择如下材质的固态电解质层：
在本申请一实施方式中，所述固态电解质层中包含中性有机小分子，所述中性有机小分子的重量百分含量≤30wt％，例如25wt％、20wt％、15wt％、10wt％、5wt％等；所述中性有机小分子的分子量≤3000，例如2500、2000、1500、1000、500等。
在本申请一实施方式中，所述固态电解质层中包含固体电解质聚合物，所述固体电解质聚合物带有以共价键连接的塑化基团。
在本申请一实施方式中，所述固体电解质聚合物为单体或低聚物与离子导电聚合物的共聚物，所述单体或低聚物的侧链具有可塑化基团，进一步地，所述固态电解质层的组成成分还包括侧链带有交联基团的单体或低聚物片段。
本申请所述的“进一步地”指的是，在上述的限定中，所述固态电解质层的组成成分在包括单体或低聚物与离子导电聚合物的共聚物的前提下，优选所 述共聚物中还包括侧链带有交联基团的单体或低聚物片段；对于下述中的“进一步地”做同样解释。
所述塑化基团以及可塑化基团指的是能减弱高分子间的相互作用，降低高分子结晶性的基团。
在本申请一实施方式中，所述固体电解质聚合物为塑化线性聚合物和离子导电聚合物，二者以化学键连接，所述塑化线性聚合物玻璃化温度低于-20℃，进一步地，所述固态电解质层的组成成分还包括侧链上具有交联基团的单体或聚合物，所述侧链上具有交联基团的单体或聚合物与所述塑化线性聚合物和离子导电聚合物三者以化学键连接。
在本申请一实施方式中，所述固体电解质聚合物为侧链带有塑化基团且玻璃化温度低于-20℃的聚合物和离子导电聚合物，二者以化学键连接，进一步地，所述固态电解质层的组成成分还包括侧链上具有交联基团的单体或聚合物，所述侧链上具有交联基团的单体或聚合物与所述侧链带有塑化基团且玻璃化温度低于-20℃的聚合物和离子导电聚合物三者以化学键连接。
在本申请一实施方式中，所述固体电解质聚合物为刷状聚合物，所述刷状聚合物具有柔性聚合物主链、离子导电型侧链和非混相侧链，进一步地，所述固态电解质层的组成成分还包括侧链上具有交联基团的单体或低聚物，所述侧链上具有交联基团的单体或低聚物以嵌段共聚的形式与所述刷状聚合物以化学键相连。
本申请所述的非混相侧链指的是和其他侧链或高分子性质差别大，不可有效共混的侧链，而本申请提供的刷状聚合物指的是高分子的主链是柔性聚合物，侧链有两种，一种侧链是用于导离子的，另一种侧链是和导离子侧链性能差别较大，不可有效共混的其它类型侧链。本申请引入这种不可混的侧链可以降低高分子的结晶度，使高分子处于无规状态，进而提高高分子整体导离子能力和透明度。
在本申请一实施方式中，所述离子转移层是固态柔性电解质层。所述固态柔性电解质层的聚合物可以选自于以下四大类聚合物。
在以下四类聚合物的结构式中，x、y、和z各自独立地选自大于0的整数。式中所示的长方形代表具有导离子作用的聚合物嵌段(离子导电聚合物嵌段)，椭圆形代表了带有PR(塑化基团)、或CL(交联基团)、或NM(非混相基团)、或IC(离子导电基团)这些侧链的单体或聚合物。
(1)
Figure PCTCN2021083600-appb-000001
具有导离子作用的聚合物嵌段y(如聚乙二醇或其他文献报道过的材料)与侧链上具有塑化基团(PR)的单体或聚合物嵌段x，以及侧链上具有交联基团(CL)的单体或聚合物嵌段z进行共聚形成的嵌段共聚物(以PEGPRCL表示)。或是具有导离子作用的聚合物嵌段y(如聚乙二醇或其他文献报道过的材料)与侧链上具有塑化基团(PR)的单体或聚合物嵌段x进行共聚形成的嵌段共聚物(以PEGPR表示)。
(2)
Figure PCTCN2021083600-appb-000002
具有导离子作用的聚合物嵌段y(如聚乙二醇或其他文献报道过的材料)与具有玻璃化转变温度低于-20℃的线性塑化聚合物(SP)嵌段x(如聚乙烯、聚丁烯、聚异丁烯、硅氧烷、或其他文献报道过的材料等)，以及侧链上具有交联基团(CL)的单体或聚合物嵌段z进行共聚形成的嵌段共聚物(以PEGSPCL表示)。或是具有导离子作用的聚合物嵌段y(如聚乙二醇或其他文献报道过的材料)与具有玻璃化转变温度低于-20℃的线性塑化聚合物(SP)嵌段x(如聚乙烯、聚丁烯、聚异丁烯、硅氧烷、或其他文献报道过的材料等)通过化学反应连接起来形成的嵌段共聚物(以PEGSP表示)。
(3)
Figure PCTCN2021083600-appb-000003
具有导离子性的高分子嵌段y(如聚乙二醇或其他文献报道过的材料)与具 有塑化侧链的塑化高分子(SP-PR)嵌段x通过化学反应连接起来形成，再与侧链上具有交联基团的单体或低聚物(CL)嵌段z进行共聚形成的嵌段共聚物(以PEGSP-PRCL表示)。或是具有导离子性的高分子嵌段y(如聚乙二醇或其他文献报道过的材料)与具有塑化侧链的塑化高分子(SP-PR)嵌段x通过化学反应连接起来形成的嵌段共聚物(以PEGSP-P R表示)。
(4)
Figure PCTCN2021083600-appb-000004
具有导离子作用的寡聚物或高分子(如聚乙二醇或其他在文献中报道的材料)作为侧链的柔性高分子嵌段x和具有与导离子高分子不共混的侧链(如烷基类、芳香类或烷基、芳香混合类侧链)的柔性高分子嵌段y通过化学反应连接起来，再与侧链上具有交联基团的单体或低聚物(CL)嵌段z进行共聚形成的梳状嵌段共聚物(ICNMCL)。或是具有导离子作用的寡聚物或高分子(如聚乙二醇或其他在文献中报道的材料)作为侧链的柔性高分子嵌段x和具有与导离子高分子不共混的侧链如(烷基类、芳香类或烷基、芳香混合类侧链)的柔性高分子嵌段y通过化学反应连接起来形成的梳状嵌段共聚物(ICNM)。
上述用于离子转移层的高分子材料还需要与一定量的有机盐和/或无机盐共混形成电解质前体。所述无机盐包括但不限于锂盐、钠盐、钾盐、镁盐、钙盐、铝盐；所述有机盐包括但不限于离子液体，例如EMITFSI、EMIOTF。有时候，还需要引入引发剂来共混形成电解质前体，电解质前体通过加热，光引发等方法交联形成最终的全固态电解质。
在本申请中，塑化基团(PR)包括但不限于以下结构：
Figure PCTCN2021083600-appb-000005
交联基团(CL)包括但不限于以下结构：
Figure PCTCN2021083600-appb-000006
梳状嵌段共聚物的主链包括但不限于以下结构：
Figure PCTCN2021083600-appb-000007
离子导电基团(IC)包括但不限于以下结构：
Figure PCTCN2021083600-appb-000008
在本申请一实施方式中，所述第一基底和所述第二基底的材料各自独立地为玻璃或柔性材料，优选为透明材料。所述柔性材料包括但不限于PET(聚对苯二甲酸乙二醇酯)、环烯烃共聚物、三醋酸纤维素等。
第二方面，本申请提供一种第一方面所述的电致变色器件的变色方法，所述变色方法包括如下步骤：
(1)对预处理后的电致变色器件施加第二方向的第二电压，所述第二方向与第一方向相反，使所述第一电致变色层从第三颜色变为第一颜色，所述第二电致变色层从第二颜色变为第四颜色；所述预处理为：对所述电致变色器件施加第一方向的第一电压，使所述第一电致变色层从第一颜色变为第三颜色，所述第二电致变色层保持第二颜色不变；
(2)对预处理后的电致变色器件施加第一方向的第三电压，使所述第一电致变色层从第一颜色变为第三颜色，所述第二电致变色层从第四颜色变为第二颜色。
本申请中，所述预处理的作用是通过得失电子使第一电致变色层发生可逆氧化/还原反应，使其颜色产生切换；同时，第二电致变色层发生非法拉第反应和部分不可逆电化学反应，产生的电荷使电致变色器件的电荷平衡，此时第二电致变色层不发生与变色相关的法拉第反应，因此第二电致变色层颜色保持不变。经过预处理后，即可通过循环施加方向相反的电压使电致变色器件在不同颜色间切换。且所述预处理步骤只需要在电致变色器件第一次使用时进行，后 续使用时无需再进行预处理。而现有技术的电致变色器件在变色时，无预处理步骤。本申请通过设置两层电致变色层均为阳极电致变色材料或阴极电致变色材料的结构，结合上述特定的变色方法，使本申请提供的电致变色器件实现了在不同颜色间的切换，扩展了电致变色材料的选择范围。
在实际应用中，所述预处理既可以由电致变色器件的生产者执行，也可以由用户在第一次使用时执行，本领域技术人员可以根据实际需要进行选择。
需要说明的是，本申请的预处理步骤中使第一电致变色层从第一颜色变为第三颜色的临界电压V 1高于步骤(2)中使第一电致变色层从第一颜色变为第三颜色的临界电压V 1'，因此若按照现有电致变色器件的使用方法，对本申请的电致变色器件施加电压V 1'，是无法对电致变色器件进行预处理的，进而无法使其实现颜色切换。其中，V 1可以通过逐步增大电压，观察第一电致变色层的颜色变化的可逆性测得；或者从电致变色器件的循环伏安曲线测得。
在本申请一实施方式中，所述第一电压的绝对值为大于等于V 1，其中V 1为使所述第二电致变色层发生不可逆电化学反应的临界电压。
本申请的预处理步骤需要使用较高的电压(大于等于V 1，小于V 2)来使得第二电致变色层发生不可逆电化学反应，其中V 2为电致变色器件被击穿的电压。若第一电压大于V 2，则会使一部分电致变色层材料发生不可逆变化，结构被破坏，导致电致变色器件质量下降，甚至损坏。
在本申请一实施方式中，所述第三电压的绝对值小于所述第一电压的绝对值。在颜色切换过程中，第三电压只要能使电致变色层材料充分发生可逆电化学反应即可，无需再进行不可逆电化学反应，因此该电压小于预处理步骤所需的电压。
第三方面，本申请提供一种电子终端，所述电子终端中含有如第一方面所述的电致变色器件。
所述电子终端可以是消费电子产品，门窗，橱柜，电子标签，穿戴设备，智能眼镜，光疗设备等，例如，当所述电致变色器件应用于上述电子终端时，可以设置于终端表面或内部等任意需要的位置，根据具体应用场景起到外观多样化、遮挡隐私、状态显示、信息区分、调节环境光亮、过滤/透过不同预设波长的光线等效果。
与现有技术相比，本申请具有以下有益效果：
本申请提供的电致变色器件的两层电致变色层均采用阴极电致变色材料或阳极电致变色材料，结合特定的变色方法，可以在不同颜色间切换，从而使得 两层电致变色层的材料无需局限于阴极电致变色材料与阳极电致变色材料的组合，扩展了电致变色材料的选择范围。此电致变色器件易于推广到更多颜色的相互切换，可以满足多色显示以及个性化定制的需求。
附图说明
图1为本申请实施例提供的电致变色器件的结构示意图；
其中，1为第一基底，2为第一透明导电层，3为第一电致变色层，4为电解质层，5为第二电致变色层，6为第二透明导电层，7为第二基底。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述具体实施方式仅仅是帮助理解本申请，不应视为对本申请的具体限制。
本申请实施例中，电解质层中电解质聚合物成分的制备方法如下：
高分子A(属于PEGPRCL的一类固态电解质聚合物)的制备方法如下：
Figure PCTCN2021083600-appb-000009
在合适的有机溶剂中加入溴代异丁酸封端的PEG(聚乙二醇)，带有塑化基 团的丙烯酸酯，带有两个丙烯酸的交联基团，一价铜催化剂，PMDETA(N,N,N',N",N"-五甲基二亚乙基三胺)配体。该混合溶液(不加溶剂的该混合物也可用作电解质前体直接用于器件制备)在100℃条件下反应12小时，通过硅藻土过滤和减压除去溶剂得到高分子A。
高分子B(属于PEGPR的一类固态电解质聚合物)的制备方法如下：
Figure PCTCN2021083600-appb-000010
在合适的有机溶剂中加入PEG二胺(聚乙二醇二胺)，以及邻苯二甲酰氯，在碱性条件下直接聚合得到高分子电解质(不加溶剂的该混合物也可用作电解质前体直接用于器件制备)。经过水洗分液，干燥，除去溶剂，得到高分子B。
高分子C(属于PEGSPCL的一类固态电解质聚合物)的制备方法如下：
Figure PCTCN2021083600-appb-000011
在合适的有机溶剂中加入PEG(聚乙二醇)，聚硅氧烷二胺，交联剂四胺，缩合剂CDI(羰基二咪唑)(不加溶剂的该混合物也可用作电解质前体直接用于器件制备)。90℃反应得到聚合物。经过水洗分液，干燥，除去溶剂，得到高分子C。
高分子D(属于PEGSP的一类固态电解质聚合物)的制备方法如下：
Figure PCTCN2021083600-appb-000012
在合适的有机溶剂中加入PEG(聚乙二醇)，聚硅氧烷二胺，缩合剂CDI(羰基二咪唑)(不加溶剂的该混合物也可用作电解质前体直接用于器件制备)。120℃反应得到聚合物经过水洗分液，干燥，除去溶剂，得到高分子D。
高分子E(属于PEGSP-PRCL的一类固态电解质聚合物)的制备方法如下：
Figure PCTCN2021083600-appb-000013
在合适的有机溶剂中加入PEG(聚乙二醇)，聚硅氧烷二醇，交联剂四醇，缩合剂CDI(羰基二咪唑)(不加溶剂的该混合物也可用作电解质前体直接用于器件制备)100℃反应得到聚合物。经过水洗分液，干燥，除去溶剂，得到高分子E。
高分子F(属于PEGSP-PR的一类固态电解质聚合物)的制备方法如下：
Figure PCTCN2021083600-appb-000014
在合适的有机溶剂中加入PEG(聚乙二醇)，聚硅氧烷二醇，缩合剂CDI(羰基二咪唑)(不加溶剂的该混合物也可用作电解质前体直接用于器件制备)。100℃反应得到聚合物。经过水洗分液，干燥，除去溶剂，得到高分子F。
高分子G(属于ICNMCL的一类固态电解质聚合物)的制备方法如下：
Figure PCTCN2021083600-appb-000015
在合适的有机溶剂中加入丙烯酸烷基酯，丙烯酸聚乙二醇酯，二丙烯酸乙二醇酯，AIBN(偶氮二异丁氰)(不加溶剂的该混合物也可用作电解质前体直接用于器件制备)。光照反应得到聚合物。经过水洗分液，干燥，除去溶剂，得到高分子G。
高分子H(属于ICNM的一类固态电解质聚合物)的制备方法如下：
Figure PCTCN2021083600-appb-000016
在合适的有机溶剂中加入丙烯酸烷基酯，丙烯酸聚乙二醇酯，AIBN(偶氮二异丁氰)(不加溶剂的该混合物也可用作电解质前体直接用于器件制备)。光照反应得到聚合物。经过水洗分液，干燥，除去溶剂，得到高分子H。
需要说明的是，本申请实施例中，当第一电致变色层3的电势高于第二电 致变色层5的电势时，电压方向称为正向；当第一电致变色层3的电势低于第二电致变色层5的电势时，电压方向称为反向。
本申请实施例中，电致变色层的单位面积最大电荷转移数的测试方法如下：
1.将待测试的电致变色层作为工作电极，Ag/AgCl作为参比电极，Pt电极作为对电极，接入三电极体系，电解质溶液为含50％高氯酸锂的碳酸丙二醇酯溶液；
2.采用电化学工作站对上述三电极体系进行循环伏安测试，设置起始电压和终止电压为0V，扫描速率0.05V/s，扫描圈数6圈，灵敏度e^(-2)，扫描的最高电压和最低电压根据电致变色层的材料进行适当调整，当所测试的电致变色层在扫描时出现完整的对称氧化还原峰即可；
3.对循环伏安曲线的面积进行积分，面积积分结果记为S；
4.计算单位面积最大电荷转移数Q＝S/(2×V×A)；
其中，V为扫描循环伏安曲线时的扫速，A为浸入电解质溶液中的电致变色层的面积。
实施例1
本实施例提供一种电致变色器件，其结构示意图如图1所示，包括依次层叠的第一基底1、第一透明导电层2、第一电致变色层3、电解质层4、第二电致变色层5、第二透明导电层6和第二基底7；其中，第一电致变色层3和第二电致变色层5的材料均为阳极电致变色还原态着色材料。
该电致变色器件的制备方法如下：
1)制备第一电致变色层3：
将300mg聚2-[(2-乙基己氧基)甲基]3,4-噻吩并1,4二氧烷溶于10mL邻二甲苯中，磁力搅拌10h，之后将得到的溶液滴到镀在玻璃基板(第一基底1)上的ITO层(第一透明导电层2)上，旋涂，干燥后形成第一电致变色层3(厚度200nm)。测试第一电致变色层3的单位面积最大电荷转移数，为3.3C/cm 2。
2)制备第二电致变色层5：
将400mg聚(3-己基噻吩)(P3HT)溶于10mL氯仿中，磁力搅拌10h，之后将得到的溶液滴到镀在玻璃基板(第二基底7)上的ITO层(第二透明导电层6)上，旋涂，干燥后形成第二电致变色层5(厚度300nm)。测试第二电致变色层5的单位面积最大电荷转移数，为4.2C/cm 2，第一电致变色层3与第二电致变色层5的单位面积最大电荷转移数之比为0.79:1。
3)组装电致变色器件：
将高氯酸锂10wt％、89.9wt％高分子H的前体和偶氮二异丁腈0.1wt％混合，涂布在上述第一电致变色层3上，形成电解质涂层；然后将上述第二电致变色层5(连同ITO层和玻璃基板)错位覆盖在电解质涂层上，紫外固化使电解质涂层形成电解质层4(厚度为50μm)，得到电致变色器件。
4)布置电极：
使用丙酮清洗错位露出的第一电致变色层3和第二电致变色层5材料，使第一透明导电层2和第二透明导电层6暴露，将铜胶贴附到导电层上分别作为正负电极。
本实施例还提供一种上述电致变色器件的变色方法，包括如下步骤：
(1)进行施加正向电压的预处理：
将第一电致变色层3与电源正极相连，将第二电致变色层5与电源负极相连，对器件施加正向电压(1.8V)，使得第一电致变色层3从蓝紫色被氧化至无色，而第二电致变色层5仍然保留红色。本申请对预处理的时机没有特殊限制，其可以在该电致变色器件第一次进行不同颜色间的切换之前，和前述制备方法的布置电极步骤之后的任意时间点执行。
(2)不同颜色间的切换：
对电致变色器件施加反向电压(-1.0V)，使第一电致变色层3从无色被还原至蓝紫色，第二电致变色层5从红色被氧化至无色；对电致变色器件施加正向电压(0V)，使第一电致变色层3从蓝紫色被氧化至无色，第二电致变色层5从无色被还原至红色；对器件循环施加反向电压(-1.0V)和正向电压(0V)，使器件颜色在蓝紫色和红色之间切换。
本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗，橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。例如应用于光疗设备中，该光疗设备可以是眼镜，头盔，显示屏等，制备成镜片或显示屏幕，用于过滤/透过不同预设波长的光线，将特定波长的光线入射至用户眼部，从而起到调节时差、提高睡眠质量、解除疲乏、舒缓情绪等效果。
实施例2
本实施例提供一种电致变色器件，其结构示意图如图1所示，包括依次层叠的第一基底1、第一透明导电层2、第一电致变色层3、电解质层4、第二电致变色层5、第二透明导电层6和第二基底7；其中，第一电致变色层3和第二电致变色层5的材料均为阴极电致变色氧化态着色材料。
该电致变色器件的制备方法如下：
1)制备第一电致变色层3：
称取80mg铁氰化钾溶于25mL去离子水，称取60mg乙酸镍溶于25mL去离子水，搅拌均匀。将铁氰化钾溶液加入到乙酸镍溶液中形成沉淀，分别用水和乙醇洗3次沉淀。将沉淀烘干，称取50mg重新分散于10mL去离子水中形成溶液。之后将得到的溶液滴到镀在玻璃基板(第一基底1)上的ITO层(第一透明导电层2)上，旋涂，干燥后形成第一电致变色层3(普鲁士蓝类，厚度200nm)。测试第一电致变色层3的单位面积最大电荷转移数，为8.9C/cm 2。
2)制备第二电致变色层5：
先配置50mL浓度为35mmol/mL的氯化钾溶液，鼓氮气除氧。然后取25mL，将六氰基钌酸四钾盐水合物溶解于此溶液中。将剩下的25mL氯化钾除氧溶液再配制1mmol/mL的氯化铁溶液。将获得两个溶液快速磁子搅拌共混得到亮紫色的钌紫的胶体悬浮溶液。再用盐酸将获得的胶体溶液调节至PH＝2。最后在通氮气的下，加入1mL,1mmol/mL的氯化钌溶液。之后将得到的溶液转移到电化学池中，使用玻璃基底(第二基底7)的ITO(第二透明导电层6)为电极，采用循环伏安法，在-0.2V和0.6V间循环，将钌紫薄膜电化学沉积到电极上形成第二电致变色层5(厚度250nm)。测试第二电致变色层5的单位面积最大电荷转移数，为10.2C/cm 2，第一电致变色层3与第二电致变色层5的单位面积最大电荷转移数之比为0.87:1。
3)组装电致变色器件：
将高氯酸锂10wt％、89.9wt％高分子G的前体，40％,40mmol/mL的KCl溶液和偶氮二异丁腈0.1wt％混合，涂布在上述第一电致变色层3上，形成电解质涂层；然后将上述第二电致变色层5(连同ITO层和玻璃基板)错位覆盖在电解质涂层上，紫外固化使电解质涂层形成电解质层4(厚度为10μm)，得到电致变色器件。
4)布置电极：
使用丙酮清洗错位露出的第一电致变色层3和第二电致变色层5材料，使第一透明导电层2和第二透明导电层6暴露，将铜胶贴附到导电层上分别作为正负电极。
本实施例还提供一种上述电致变色器件的变色方法，包括如下步骤：
(1)进行施加反向电压的预处理：
对器件施加反向电压(-1.2V)，使得第一电致变色层3从深蓝色被还原至无色，而第二电致变色层5仍然保持紫色。本申请对预处理的时机没有特殊限 制，其可以在该电致变色器件第一次进行不同颜色间的切换时执行，也可以在该电致变色器件的前述制备方法的布置电极步骤之后立即执行。
(2)不同颜色间的切换：
对电致变色器件施加正向电压(0.5V)，使第一电致变色层3从无色被氧化至深蓝色，第二电致变色层5从紫色被还原至无色；对电致变色器件施加反向电压(-0.5V)，使第一电致变色层3从深蓝色被还原至无色，第二电致变色层5从无色被氧化至紫色；对器件循环施加正向电压(0.5V)和反向电压(-0.5V)，使器件颜色在深蓝色和紫色之间切换。
本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗，橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。例如应用于消费电子产品中，该消费电子产品可以是手机、平板、电脑、手表等，应用于产品壳体或者显示屏或其它任意位置，从而使得消费电子产品具有丰富的外观效果，也可以用于实现根据不同颜色状态显示不同状态信息等效果。
实施例3
本实施例提供一种电致变色器件，其结构示意图如图1所示，包括依次层叠的第一基底1、第一透明导电层2、第一电致变色层3、电解质层4、第二电致变色层5、第二透明导电层6和第二基底7；其中，第一电致变色层3和第二电致变色层5的材料均为阴极电致变色还原态着色材料。
该电致变色器件的制备方法如下：
1)制备第一电致变色层3：
将100mg,99.9％纯度的钨粉溶于10mL,30wt％的过氧化氢溶液中，室温下搅拌4h，搅拌后过滤掉下层沉淀物，加入无水乙醇和冰乙酸，继续搅拌4h。之后将得到的溶液滴到镀在玻璃基板(第一基底1)上的ITO层(第一透明导电层2)上，旋涂，450℃高温干燥后形成第一电致变色层3(WO 3，厚度10nm)。测试第一电致变色层3的单位面积最大电荷转移数，为7C/cm 2。
2)制备第二电致变色层5：
将130mg Nb 2O 5粉末溶于2.5mL冰醋酸和12.5mL丁醇的混合溶液，磁力搅拌10h，之后将得到的溶液滴到镀在玻璃基板(第二基底7)上的ITO层(第二透明导电层6)上，旋涂，700℃高温干燥后形成第二电致变色层5(厚度50nm)。测试第二电致变色层5的单位面积最大电荷转移数，为13C/cm 2，第一电致变色层3与第二电致变色层5的单位面积最大电荷转移数之比为0.54:1。
3)组装电致变色器件：
将高氯酸锂10wt％、89.9wt％高分子C的前体和羰基二咪唑0.1wt％混合，涂布在上述第一电致变色层3上，形成电解质涂层；然后将上述第二电致变色层5(连同ITO层和玻璃基板)错位覆盖在电解质涂层上，90℃热固化使电解质涂层形成电解质层4(厚度为80μm)，得到电致变色器件。
4)布置电极：
使用丙酮清洗错位露出的第一电致变色层3和第二电致变色层5材料，使第一透明导电层2和第二透明导电层6暴露，将铜胶贴附到导电层上分别作为正负电极。
本实施例还提供一种上述电致变色器件的变色方法，包括如下步骤：
(1)进行施加反向电压的预处理：
对器件施加反向电压(-3.0V)，使得第一电致变色层3从无色被还原至蓝色，而第二电致变色层5仍然保持无色。本申请对预处理的时机没有特殊限制，其可以在该电致变色器件第一次进行不同颜色间的切换时执行，也可以在该电致变色器件的前述制备方法的布置电极步骤之后立即执行。
(2)不同颜色间的切换：
对电致变色器件施加正向电压(1.5V)，使第一电致变色层3从蓝色被氧化至无色，第二电致变色层5从无色被还原至浅灰色；对电致变色器件施加反向电压(-1.5V)，使第一电致变色层3从无色被还原至蓝色，第二电致变色层5从浅灰色被氧化至无色；对器件循环施加正向电压(1.5V)和反向电压(-1.5V)，使器件颜色在浅灰色和蓝色之间切换。
本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗，橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。例如应用于门窗中，可以应用于门窗的玻璃中，根据用户需求对玻璃的颜色、透过率等进行调节，从而起到遮挡隐私、调节环境光亮、温度调节等效果。
实施例4
本实施例提供一种电致变色器件，与实施例1的区别在于，第一电致变色层3和第二电致变色层5的材料均为阳极电致变色氧化态着色材料，电解质层4的组成原料替换为高分子F；
其中，第一电致变色层3的材料为NiO，由Ni作为金属靶材通过反应溅射的方式成膜，厚度为90nm，单位面积最大电荷转移数为18C/cm 2；第二电致变色层5的材料为IrO 2，由Ir作为金属靶材通过反应溅射的方式成膜，厚度为125nm，单位面积最大电荷转移数为25C/cm 2，第一电致变色层3与第二电致变色 层5的单位面积最大电荷转移数之比为0.66:1；电解质层4通过高氯酸锂10wt％、89.9wt％高分子F的前体和羰基二咪唑0.1wt％混合，100℃下热固化形成，厚度为50μm。
本实施例还提供一种上述电致变色器件的变色方法，包括如下步骤：
(1)进行施加正向电压的预处理：
对器件施加正向电压(3V)，使得第一电致变色层3从无色被氧化至棕褐色，而第二电致变色层5仍然保持无色。本申请对预处理的时机没有特殊限制，其可以在该电致变色器件第一次进行不同颜色间的切换时执行，也可以在该电致变色器件的前述制备方法的布置电极步骤之后立即执行。
(2)不同颜色间的切换：
对电致变色器件施加反向电压(-1.8V)，使第一电致变色层3从棕褐色被还原至无色，第二电致变色层5从无色被氧化至蓝黑色；对电致变色器件施加正向电压(1.8V)，使第一电致变色层3从无色被氧化至棕褐色，第二电致变色层5从蓝黑色被还原至无色；对器件循环施加反向电压(-1.8V)和正向电压(1.8V)，使器件颜色在蓝黑色和棕褐色之间切换。
本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗，橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。例如应用于橱柜中，可以应用于橱柜的表面或者玻璃中，根据外观多样化、遮挡隐私、调节橱柜内温度等效果。
实施例5
本实施例提供一种电致变色器件，与实施例1的区别在于，制备第一电致变色层3时称取的聚2-[(2-乙基己氧基)甲基]3,4-噻吩并1,4二氧烷为600mg，旋涂出的厚度为800nm，单位面积最大电荷转移数为12.2C/cm 2；制备第二电致变色层5时称取的聚(3-己基噻吩)(P3HT)为50mg，旋涂出的厚度为12nm，单位面积最大电荷转移数为0.25C/cm 2，第一电致变色层3与第二电致变色层5的单位面积最大电荷转移数之比为48.8:1；电解质层4的组成原料替换为高分子B，通过高氯酸锂10wt％、89.9wt％高分子B的前体和85％氢氧化钾0.1wt％混合12h后形成，厚度为50μm。
通过对本实施例提供的电致变色器件施加正向电压(1.8V)进行预处理，然后循环施加反向电压(-1.0V)和正向电压(0.4V)，可以使器件颜色在蓝紫色和红色之间切换。
本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗， 橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。例如应用于穿戴设备中，可以应用于穿戴设备的壳体或者显示区域，起到外观多样化、滤光等效果。
实施例6
本实施例提供一种电致变色器件，与实施例1的区别在于，第一电致变色层3的材料为阴极电致变色还原态着色材料，第二电致变色层5的材料为阴极电致变色氧化态着色材料，电解质层4的组成原料替换为高分子A；
第一电致变色层3的材料为WO 3，制备方法参考实施例3，厚度为50nm，单位面积最大电荷转移数为20C/cm 2；第二电致变色层5的材料为钌紫，制备方法参考实施例2，厚度为250nm，单位面积最大电荷转移数为10.2C/cm 2，第一电致变色层3与第二电致变色层5的单位面积最大电荷转移数之比为1.96:1；电解质层4通过高氯酸锂10wt％、89.9wt％高分子A的前体、0.05wt％氯化亚铜和0.1wt％N,N,N',N",N"-五甲基二亚乙基三胺混合，100℃下热固化形成，厚度为150μm。
通过对本实施例提供的电致变色器件施加反向电压(-3V)进行预处理，然后循环施加正向电压(1.2V)和反向电压(-1.5V)，可以使器件颜色在无色和叠加色(蓝色与紫色)之间切换。
本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗，橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。例如应用于电子标签中，起到状态显示和信息区分的效果。
实施例7
本实施例提供一种电致变色器件，与实施例1的区别在于，第一电致变色层3的材料为阳极电致变色还原态着色材料，第二电致变色层5的材料为阳极电致变色氧化态着色材料，电解质层的组成原料替换为高分子E；
第一电致变色层3的材料为聚2-[(2-乙基己氧基)甲基]3,4-噻吩，制备方法参考实施例1，厚度为200nm，单位面积最大电荷转移数为3.3C/cm 2；第二电致变色层5的材料为NiO，制备方法参考实施例4，厚度为180nm，单位面积最大电荷转移数为32C/cm 2，第一电致变色层3与第二电致变色层5的单位面积最大电荷转移数之比为1:10；电解质层4通过高氯酸锂10wt％、89.9wt％高分子E的前体和羰基二咪0.1wt％混合，100℃下热固化形成，厚度为30μm。
通过对本实施例提供的电致变色器件施加正向电压(1.8V)进行预处理，然后循环施加反向电压(-1.0V)和正向电压(1V)，可以使器件颜色在无色和叠加色(棕黑色与蓝紫色)之间切换。
本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗，橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。
实施例8
本实施例提供一种电致变色器件，与实施例2的区别在于，制备第一电致变色层3时称取的铁氰化钾为160mg，旋涂出的厚度为400nm，单位面积最大电荷转移数为16C/cm 2，第二电致变色层5的厚度为250nm，单位面积最大电荷转移数为10.2C/cm 2，第一电致变色层3与第二电致变色层5的单位面积最大电荷转移数之比为1.57:1。
通过对本实施例提供的电致变色器件施加反向电压(-1.2V)进行预处理，然后循环施加正向电压(0.5V)和反向电压(-0.5V)，可以使器件颜色在深蓝色和紫色之间切换。本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗，橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。
实施例9
本实施例提供一种电致变色器件，与实施例3的区别在于，第一电致变色层3的厚度为75nm，单位面积最大电荷转移数为30C/cm 2，第二电致变色层5的厚度为20nm，单位面积最大电荷转移数为3C/cm 2，第一电致变色层3与第二电致变色层5的单位面积最大电荷转移数之比为10:1。
通过对本实施例提供的电致变色器件施加反向电压(-3V)进行预处理，然后循环施加正向电压(1.5V)和反向电压(-1.5V)，可以使器件颜色在浅灰色和蓝色之间切换。本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗，橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。
实施例10
本实施例提供一种电致变色器件，其结构示意图如图1所示，包括依次层叠的第一基底1、第一透明导电层2、第一电致变色层3、电解质层4、第二电致变色层5、第二透明导电层6和第二基底7；其中，第一电致变色层3和第二电致变色层5的材料均为阳极电致变色多色材料。
该电致变色器件的制备方法如下：
1)制备第一电致变色层3：
采用恒电流法，将浓度为0.1mol/L的苯胺在1mol/L的硫酸溶液中，用10μA/cm 2的电流密度沉积30min，在镀在玻璃基板上的ITO层上形成第一电致变色层3(聚苯胺薄膜，厚度280nm)。测试第一电致变色层3的单位面积最大电荷转移数，为20C/cm 2。
2)制备第二电致变色层5：
将300mg V 2O 5片状晶体捣碎后放入坩埚，在马弗炉中用800℃加热使其完全熔化成流动性的胶体状，保温5min后倒入盛胶桶，并加入20mL去离子水，搅拌均匀得到V 2O 5胶体溶液。之后将得到的溶液滴到镀在玻璃基板上的ITO层上，旋涂，形成第二电致变色层5(厚度350nm)。测试第二电致变色层5的单位面积最大电荷转移数，为35C/cm 2，第一电致变色层3与第二电致变色层5的单位面积最大电荷转移数之比为0.57:1。
3)组装电致变色器件：
将高氯酸锂10wt％、89.9wt％高分子D的前体和羰基二咪唑0.1wt％混合，涂布在上述第一电致变色层3上，形成电解质涂层；然后将上述第二电致变色层5(连同ITO层和玻璃基板)错位覆盖在电解质涂层上，120℃热固化使电解质涂层形成电解质层4(厚度为60μm)，得到电致变色器件。
4)布置电极：
使用丙酮清洗错位露出的第一电致变色层3和第二电致变色层5材料，使第一透明导电层2和第二透明导电层6暴露，将铜胶贴附到导电层上分别作为正负电极。
本实施例还提供一种上述电致变色器件的变色方法，包括如下步骤：
(1)进行施加正向电压的预处理：
对器件施加正向电压(2.5V)，使得第一电致变色层3从绿色被氧化至深蓝色，而第二电致变色层5仍然保持黄色。本申请对预处理的时机没有特殊限制，其可以在该电致变色器件第一次进行不同颜色间的切换时执行，也可以在该电致变色器件的前述制备方法的布置电极步骤之后立即执行。
(2)不同颜色间的切换：
对电致变色器件施加反向电压(-1.0V)，使第一电致变色层3从深蓝色被还原至绿色，第二电致变色层5从黄色被氧化至灰黑色；对电致变色器件施加正向电压(1.2V)，使第一电致变色层3从绿色被氧化至深蓝色，第二电致变色层5从灰黑色被还原至黄色；对器件循环施加正向电压(1.2V)和反向电压(-1.0V)，使器件颜色实现颜色切换。
本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗，橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。
实施例11
本实施例提供一种电致变色器件，与实施例7的区别在于，制备第一电致 变色层3时称取的聚2-[(2-乙基己氧基)甲基]3,4-噻吩并1,4二氧烷为20mg，旋涂出的厚度为6nm，单位面积最大电荷转移数为0.1C/cm 2，第二电致变色层5的厚度为25nm，单位面积最大电荷转移数为5C/cm 2，第一电致变色层3与第二电致变色层5的单位面积最大电荷转移数之比为0.02:1。
通过对本实施例提供的电致变色器件施加正向电压(1.8V)进行预处理，然后循环施加反向电压(-1.0V)和正向电压(1V)，可以使器件颜色在无色和叠加色(棕黑色与蓝紫色)之间切换。
本实施例提供的电致变色器件可以用于消费电子产品，电子标签，门窗，橱柜，穿戴设备，智能眼镜，光疗设备等终端产品中。
对比例1
使用实施例1提供的电致变色器件进行颜色切换，方法与实施例1的区别在于，直接对器件循环施加正向电压(1.2V)和反向电压(-1.2V)进行变色；
(1)对器件施加正向电压(1.2V)，第一电致变色层3无法失电子发生氧化反应，第二电致变色层5无法得电子发生还原反应，第一电致变色层3和第二电致变色层5都不变色；
(2)对器件施加反向电压(-1.2V)，第一电致变色层3无法得电子发生还原反应，第二电致变色层5无法失电子发生氧化反应，第一电致变色层3和第二电致变色层5都不变色；
(3)循环施加正向电压(1.2V)和反向电压(-1.2V)，器件颜色不能切换。
由于第一电致变色层3和第二电致变色层5均为阳极电致变色还原态着色材料，初始态时均处在还原态，由于加压电位低，无法提供足够的电荷使材料氧化褪色，故器件不能够进行颜色切换。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，均落在本申请的保护范围和公开范围之内。

Claims (13)

  1. 一种电致变色器件，其包括依次层叠的第一基底、第一透明导电层、第一电致变色层、电解质层、第二电致变色层、第二透明导电层和第二基底；
    其中，所述第一电致变色层和所述第二电致变色层的材料均为阴极电致变色材料或均为阳极电致变色材料。
  2. 根据权利要求1所述的电致变色器件，其中，所述第一透明导电层和所述第二透明导电层各自独立地由氧化铟锡、氧化锌铝、氟掺杂氧化锡、银纳米线、石墨烯、碳纳米管、金属网格和银纳米颗粒中的至少一种形成。
  3. 根据权利要求1或2所述的电致变色器件，其中，所述第一透明导电层和所述第二透明导电层的厚度各自独立地为1-1000nm。
  4. 根据权利要求1-3任一项所述的电致变色器件，其中，所述第一电致变色层和所述第二电致变色层的材料不同时为阴极电致变色多色材料，且不同时为阳极电致变色多色材料。
  5. 根据权利要求1-4任一项所述的电致变色器件，其中，所述第一电致变色层和所述第二电致变色层的材料均不为阴极电致变色多色材料，且均不为阳极电致变色多色材料。
  6. 根据权利要求1-5任一项所述的电致变色器件，其中，所述第一电致变色层和所述第二电致变色层的材料均为阴极电致变色还原态着色材料、均为阴极电致变色氧化态着色材料、均为阳极电致变色还原态着色材料或均为阳极电致变色氧化态着色材料。
  7. 根据权利要求1-6任一项所述的电致变色器件，其中，所述第一电致变色层的单位面积最大电荷转移数为0-35C/cm 2且不包括0，所述第二电致变色层的单位面积最大电荷转移数为0-35C/cm 2且不包括0。
  8. 根据权利要求1-7任一项所述的电致变色器件，其中，所述第一电致变色层与所述第二电致变色层的单位面积最大电荷转移数之比为1:50-50:1，优选为1:10-10:1。
  9. 根据权利要求1-8任一项所述的电致变色器件，其中，所述电解质层为凝胶态电解质层、液态电解质层或固态电解质层，进一步优选为固态电解质层，更进一步优选为固态聚合物电解质层；
    任选地，所述电解质层的厚度为0.1-200μm。
  10. 根据权利要求1-9任一项所述的电致变色器件，其中，所述第一基底和所述第二基底的材料各自独立地为玻璃或柔性材料；
    任选地，所述柔性材料为PET、环烯烃共聚物或三醋酸纤维素。
  11. 一种如权利要求1-10任一项所述的电致变色器件的变色方法，其包括如下步骤：
    (1)对预处理后的电致变色器件施加第二方向的第二电压，所述第二方向与第一方向相反，使所述第一电致变色层从第三颜色变为第一颜色，所述第二电致变色层从第二颜色变为第四颜色；所述预处理为：对所述电致变色器件施加第一方向的第一电压，使所述第一电致变色层从第一颜色变为第三颜色，所述第二电致变色层保持第二颜色不变；
    (2)对预处理后的电致变色器件施加第一方向的第三电压，使所述第一电致变色层从第一颜色变为第三颜色，所述第二电致变色层从第四颜色变为第二颜色。
  12. 根据权利要求11所述的变色方法，其中，所述第一电压的绝对值为大于等于V 1，其中V 1为使所述第二电致变色层发生不可逆电化学反应的临界电压；
    任选地，所述第三电压的绝对值小于所述第一电压的绝对值。
  13. 一种电子终端，其含有如权利要求1-10任一项所述的电致变色器件。
PCT/CN2021/083600 2020-04-01 2021-03-29 一种电致变色器件及其变色方法 WO2021197268A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2022544672A JP2023512976A (ja) 2020-04-01 2021-03-29 エレクトロクロミックデバイス、およびその変色方法
EP21780291.7A EP4083699A4 (en) 2020-04-01 2021-03-29 ELECTROCHROMIC DEVICE AND ITS ELECTROCHROMIC METHOD
KR1020227028551A KR20220129053A (ko) 2020-04-01 2021-03-29 전기 변색 소자 및 이의 변색 방법
US17/798,516 US20230063383A1 (en) 2020-04-01 2021-03-29 Electrochromic device and electrochromic method therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010249974.9A CN113495392B (zh) 2020-04-01 2020-04-01 一种电致变色器件及其变色方法
CN202010249974.9 2020-04-01

Publications (1)

Publication Number Publication Date
WO2021197268A1 true WO2021197268A1 (zh) 2021-10-07

Family

ID=77927724

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/083600 WO2021197268A1 (zh) 2020-04-01 2021-03-29 一种电致变色器件及其变色方法

Country Status (6)

Country Link
US (1) US20230063383A1 (zh)
EP (1) EP4083699A4 (zh)
JP (1) JP2023512976A (zh)
KR (1) KR20220129053A (zh)
CN (2) CN113495392B (zh)
WO (1) WO2021197268A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116203771A (zh) * 2023-03-17 2023-06-02 浙江景昇薄膜科技有限公司 一种电致变色组件及其制备方法与应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114126302B (zh) * 2021-12-07 2024-01-23 维沃移动通信有限公司 壳体及电子设备

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6211995B1 (en) * 1998-09-22 2001-04-03 Forkarpatent 1 Uppsala Ab Electrochromic device comprising tandem layers of cathodic/anodic materials
US20140205746A1 (en) * 2013-01-21 2014-07-24 Kinestral Technologies, Inc. Process for preparing a multi-layer electrochromic structure
CN105229526A (zh) * 2013-01-21 2016-01-06 基内斯恰技术股份有限公司 电致变色锂镍第四族混合金属氧化物
CN105278198A (zh) 2015-11-17 2016-01-27 崔玉柱 互补型无机全固态电致变色器件及其制备方法
CN105607375A (zh) 2016-02-29 2016-05-25 中国建筑材料科学研究总院 高通量筛选固态无机电致变色材料的电致变色器件及其制备方法
CN107922829A (zh) * 2015-03-24 2018-04-17 弗劳恩霍夫应用研究促进协会 具有改善的电解质层的电致变色元件
CN208488635U (zh) * 2018-04-11 2019-02-12 赵林 一种多色电致变色玻璃
CN110109311A (zh) 2019-04-19 2019-08-09 东北大学秦皇岛分校 一种全固态电致变色器件及其制备方法
CN110658660A (zh) * 2019-10-16 2020-01-07 暨南大学 基于多层功能薄膜的电致变色器件及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6087316A (ja) * 1983-10-20 1985-05-17 Nissan Motor Co Ltd エレクトロクロミツク素子
US5086351A (en) * 1989-07-13 1992-02-04 M&T Chemicals, Inc. Electrochromic elements, materials for use in such element, processes for making such elements and such materials and use of such element in an electrochromic glass device
US7342708B2 (en) * 2004-04-26 2008-03-11 Tropics Enterprise Co. Ltd. Electrochromic device using poly(3,4-ethylenedioxythiophene) and derivatives thereof
BR102013007194B1 (pt) * 2013-03-27 2021-12-21 Universidade De São Paulo-Usp Dispositivo eletrocrômico aplicado como janela eletrocrômica ou pixel e uso do referido dispositivo
CN110262152A (zh) * 2019-06-17 2019-09-20 浙江工业大学 一种高颜色对比度的电致变色器件及其组装方法
CN110928095A (zh) * 2019-11-14 2020-03-27 浙江工业大学 一种能够实现在任意颜色之间转变的双电致变色层器件及组装方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6211995B1 (en) * 1998-09-22 2001-04-03 Forkarpatent 1 Uppsala Ab Electrochromic device comprising tandem layers of cathodic/anodic materials
US20140205746A1 (en) * 2013-01-21 2014-07-24 Kinestral Technologies, Inc. Process for preparing a multi-layer electrochromic structure
CN105229526A (zh) * 2013-01-21 2016-01-06 基内斯恰技术股份有限公司 电致变色锂镍第四族混合金属氧化物
CN107922829A (zh) * 2015-03-24 2018-04-17 弗劳恩霍夫应用研究促进协会 具有改善的电解质层的电致变色元件
CN105278198A (zh) 2015-11-17 2016-01-27 崔玉柱 互补型无机全固态电致变色器件及其制备方法
CN105607375A (zh) 2016-02-29 2016-05-25 中国建筑材料科学研究总院 高通量筛选固态无机电致变色材料的电致变色器件及其制备方法
CN208488635U (zh) * 2018-04-11 2019-02-12 赵林 一种多色电致变色玻璃
CN110109311A (zh) 2019-04-19 2019-08-09 东北大学秦皇岛分校 一种全固态电致变色器件及其制备方法
CN110658660A (zh) * 2019-10-16 2020-01-07 暨南大学 基于多层功能薄膜的电致变色器件及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4083699A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116203771A (zh) * 2023-03-17 2023-06-02 浙江景昇薄膜科技有限公司 一种电致变色组件及其制备方法与应用

Also Published As

Publication number Publication date
JP2023512976A (ja) 2023-03-30
US20230063383A1 (en) 2023-03-02
EP4083699A1 (en) 2022-11-02
EP4083699A4 (en) 2024-02-14
CN113495392A (zh) 2021-10-12
CN116560148A (zh) 2023-08-08
CN113495392B (zh) 2023-06-16
KR20220129053A (ko) 2022-09-22

Similar Documents

Publication Publication Date Title
Rai et al. A review on recent advances in electrochromic devices: a material approach
Madasamy et al. Viologen-based electrochromic materials and devices
CN103582844B (zh) 稳定的电致变色模块
Heuer et al. Electrochromic window based on conducting poly (3, 4‐ethylenedioxythiophene)–poly (styrene sulfonate)
Mortimer Electrochromic materials
EP2196847B1 (en) Electrochromic display device and method for manufacturing the same
Thakur et al. Hybrid materials and polymer electrolytes for electrochromic device applications
Abaci et al. Morphological and electrochemical properties of PPy, PAni bilayer films and enhanced stability of their electrochromic devices (PPy/PAni–PEDOT, PAni/PPy–PEDOT)
Xu et al. Switchable window based on electrochromic polymers
WO2021197268A1 (zh) 一种电致变色器件及其变色方法
CN1938395A (zh) 新的电致变色材料和器件
Wang et al. Electropolymerized polyaniline/manganese iron oxide hybrids with an enhanced color switching response and electrochemical energy storage
Pathak et al. Recent progress in electrochromic energy storage materials and devices: a minireview
Ma et al. Using room temperature ionic liquid to fabricate PEDOT/TiO2 nanocomposite electrode-based electrochromic devices with enhanced long-term stability
WO2007008978A2 (en) Electrochromic devices utilizing very low band gap conjugated polymers: preparation and use
US20120127554A1 (en) Display device and color electronic paper using the same
CN208270897U (zh) 柔性电致变色器件
Ahmadian-Alam et al. Fabrication and assessment of an electrochromic and radar-absorbent dual device based on the new smart polythiophene-based/RGO/Fe3O4 ternary nanocomposite
Rozman et al. Flexible electrochromic tape using steel foil with WO3 thin film
Kao et al. High contrast and low-driving voltage electrochromic device containing triphenylamine dendritic polymer and zinc hexacyanoferrate
JPWO2009031422A1 (ja) エレクトロクロミック表示素子の製造方法
Meng Organic Electronics for Electrochromic Materials and Devices
Neo et al. Fundamentals of electrochromic materials and devices
Kuo et al. Electrosynthesis of electrochromic polymers based on bis-(4-(N-carbazolyl) phenyl)-phenylphosphine oxide and 3, 4-propylenedioxythiophene derivatives and studies of their applications in high contrast dual type electrochromic devices
JP2011085622A (ja) 電解液および電気化学デバイス

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21780291

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022544672

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2021780291

Country of ref document: EP

Effective date: 20220726

NENP Non-entry into the national phase

Ref country code: DE