CN111596496A - Visible-infrared independently-controlled electrochromic device - Google Patents

Visible-infrared independently-controlled electrochromic device Download PDF

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CN111596496A
CN111596496A CN202010466939.2A CN202010466939A CN111596496A CN 111596496 A CN111596496 A CN 111596496A CN 202010466939 A CN202010466939 A CN 202010466939A CN 111596496 A CN111596496 A CN 111596496A
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electrochromic
layer
infrared
visible
electrochromic layer
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CN111596496B (en
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曹逊
黄爱彬
邵泽伟
金平实
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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    • 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
    • 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
    • G02F1/1523—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
    • G02F1/153—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
    • G02F1/153—Constructional details
    • G02F1/1533—Constructional details structural features not otherwise provided for
    • 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
    • G02F1/1533—Constructional details structural features not otherwise provided for
    • G02F2001/1536—Constructional details structural features not otherwise provided for additional, e.g. protective, layer inside the cell

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  • Crystallography & Structural Chemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

The invention discloses a visible-infrared independently-controlled electrochromic device. The visible-infrared independent control electrochromic device structurally comprises a first transparent electrode, a first electrochromic layer, a second electrochromic layer, an ion conducting layer and a second transparent electrode, wherein the first transparent electrode, the first electrochromic layer only controls visible light under a high-voltage condition, the second electrochromic layer only controls infrared light transmittance under a low-voltage condition; wherein the high voltage is-5 to 5V, and the low voltage is-2.5 to 2.5V. The invention designs the first electrochromic layer capable of adjusting visible light and the second electrochromic layer only adjusting infrared light, thereby realizing independent adjustment of the transmittance of infrared light and visible light under different voltages and meeting the requirements of actual life.

Description

Visible-infrared independently-controlled electrochromic device
Technical Field
The invention relates to the technical field of chemical material synthesis and functional materials, in particular to a visible-infrared independently-controlled electrochromic device.
Background
The energy is an important foundation for maintaining the sustainable development of national economy and guaranteeing the living standard of people's materials. Nowadays, the problems of energy shortage, environmental pollution and the like are becoming more severe, and scientists are also striving to find methods for energy conservation and consumption reduction while developing new energy. The building is one of the main places where people carry out production and living activities, the building energy consumption accounts for a large proportion in the total energy consumption of the production and living of people, and the energy consumption of the lighting and air conditioning system for improving the building comfort level accounts for more than 75 percent in the total energy consumption of the building. The energy consumption of the two parts is related to the door glass, so that the development of the architectural glass with the energy-saving effect is an important way for realizing the energy saving of buildings. Current architectural glass control energy loss is static, such as Low-E glass with high reflectivity in the infrared band, which prevents infrared from passing through the window; the hollow glass reduces the heat conduction and radiation between the indoor and the outdoor by utilizing the low air heat conduction coefficient. In the 80 s of the last century, scientists put forward the concept of an intelligent window based on electrochromic materials, namely a building window structure material for actively regulating and controlling the intensity of visible and near-infrared transmission light, can dynamically regulate the intensity of the incident light according to the difference of indoor and outdoor environments, reduces the use of air conditioners and lighting systems, and can achieve better energy-saving effect by combining with Low-E and hollow glass. The performance of the electrochromic material determines the strength of the light regulation capability of the intelligent window, and the electrochromic material draws wide attention. The electrochromic is a reversible color change phenomenon of the optical properties of the material, such as transmittance and reflectivity, under the drive of low voltage, and the appearance of the material is represented by reversible change between a blue state and a transparent state. Electrochromism is a hotspot of research nowadays and has a wide application range. The electrochromic device and the technology are mainly applied to the fields of energy-saving building glass, windows of other moving bodies, automobile anti-dazzle rearview mirrors, display screens, electronic paper, camouflage and the like.
Conventional electrochromic devices are composed primarily of five thin films, including two transparent conductive layers, an ion storage layer, an electrochromic layer, and an ion conductive layer. Wherein, the ion storage layer assists the electrochromic layer to apply low voltage on the transparent conducting layer to realize electrochromic reaction. The ion conducting layer provides a lithium ion transmission channel, improves the migration capacity and migration efficiency of lithium ions between the ion storage layer and the electrochromic layer, and the structure and the preparation process of the ion conducting layer are one of the most important technologies for ensuring the electrochromic performance of the device. Electrochromic devices can be classified into three types according to the state of the ion conducting layer, which are respectively: the liquid electrochromic device, the gel state electrochromic device and the all-solid state electrochromic device, wherein the gel state electrochromic device is also a quasi-solid state electrochromic device. Compared with the problems of packaging, liquid leakage and the like of a liquid electrochromic device, the problems of slow response time, poor ionic conductivity and the like of an all-solid electrochromic device, the quasi-solid electrochromic device has good stability and simple preparation process, and the response time of the quasi-solid electrochromic device is longer than that of the all-solid electrochromic device.
However, those conventional electrochromic glasses have only two modulation modes, i.e., light-pass and light-fail. The sunlight mainly comprises near infrared light and visible light containing a large amount of heat, and if the transmission and the non-transmission of the visible light and the near infrared light can be independently regulated and controlled, the transmission of the infrared light and the visible light can be regulated and controlled according to actual needs, so that the diversified requirements of the modern society are met, and the purposes of saving energy and simultaneously meeting lighting are achieved. At present, independent regulation and control of visible-near infrared light electrochromism mainly focuses on designing two layers of tungsten oxide with different microstructures, and not only is the preparation process complicated, but also the independent regulation and control capability is weak, and the regulation and control range is narrow, so that the practical application of an independent adjustable electrochromism device is limited.
Chinese patent CN 109143716A discloses a visible-near infrared light electrochromic composite material, a preparation method and application thereof. The composite material comprises a first structural layer and a second structural layer, wherein the first structural layer can regulate visible light, and the second structural layer regulates infrared light. However, in the invention, an ion diffusion channel must be constructed in the second layer, so that the first layer and the second layer can respectively regulate visible light and infrared light. In the patent, liquid electrolyte is introduced to contact with two layers of electrochromic materials simultaneously, so that the regulation and control of visible light and infrared light are realized. A pore structure must therefore be formed in the second layer, through which pores the electrolyte can contact the first electrochromic layer. Chinese patent CN 105036564 a utilizes conductive oxide nanoparticles to adjust near-infrared transmitted light, and utilizes tungsten oxide to adjust visible light, thereby achieving the purpose of selectively adjusting light (visible light) and heat (near-infrared light). The conductive oxide nanoparticles in this patent then absorb far infrared very strongly, resulting in a weak ability to modulate the mid-and far-infrared light. The conductive oxide nanoparticles can only adjust visible light and near infrared light due to the strong absorption of mid-infrared light by the surface plasmon resonance effect.
Disclosure of Invention
Aiming at the problems that the electrochromic device in the prior art is difficult to independently regulate visible light and infrared light or has weak regulation capability, the invention provides a visible-infrared independently regulated electrochromic device, which adopts a two-layer electrochromic structure and selects a thermochromic material, so that the transmittance of infrared light can be obviously and effectively regulated without influencing the transmittance of visible light, thereby ensuring the independent regulation of visible light and infrared light.
The visible-infrared independent control electrochromic device structurally comprises a first transparent electrode, a first electrochromic layer, a second electrochromic layer, an ion conducting layer and a second transparent electrode, wherein the first transparent electrode, the first electrochromic layer only controls visible light under a high voltage condition, the second electrochromic layer only controls infrared light transmittance under a low voltage condition, and the second transparent electrode are sequentially arranged.
Wherein the high voltage is-5 to 5V, and the low voltage is-2.5 to 2.5V.
Preferably, the material of the first electrochromic layer is WO3-x、TiO2At least one of PEDOT or Prussian blue, with a thickness of 50-500 nm.
Preferably, the material of the second electrochromic layer is monoclinic phase VO2The thickness is 20-200 nm.
The invention introduces the VO which is a thermochromic material2As a second electrochromic layer material. VO (vacuum vapor volume)2The transmittance of the whole infrared band can be regulated and controlled. And research shows that under the drive of an applied voltage, cations enter VO2Can also cause a phase change that results in the film changing from an infrared transmitting state to an infrared blocking state. Therefore, the double-layer film structure can respectively regulate and control infrared light and visible light, and has excellent regulation capacity and wider regulation range.
Preferably, under low voltage conditions, cations can only migrate and intercalate into the second electrochromic layer, such that the second electrochromic layer transitions from an infrared-transparent semiconductor monoclinic structure to an infrared-blocking metal tetragonal structure.
Preferably, the voltage is continuously increased, and under the condition of high voltage, cations migrate into the first electrochromic layer to realize the absorption of visible light.
Preferably, the material of the first transparent electrode and/or the second transparent electrode is at least one of transparent conductive oxide or metal nanowire, the thickness is 100-400nm, and the sheet resistance is 3-100 Ω/cm2The transmittance is more than 75 percent. Preferably, the transparent conductive oxide is at least one of FTO, ITO, ATO, AZO, and the metal nanowire is at least one of Cu, Au, Ag, and Al.
Preferably, the ion conductive layer is a cation conductive layer based on a resin material, wherein the cation is at least one of Li, Na, Al, K, Li, Cs, Rb, Mg and Ca.
Preferably, the visible-infrared independently controllable electrochromic device further comprises an ion storage layer located between the ion conducting layer and the second transparent electrode.
Preferably, the visible-infrared independently controllable electrochromic device further comprises an electron blocking layer and an ion buffer layer between the first electrochromic layer and the second electrochromic layer or between the second electrochromic layer and the ion conducting layer.
Preferably, the second electrochromic layer is prepared on the surface of the first electrochromic layer by a film forming method including magnetron sputtering, laser pulse deposition, molecular beam epitaxy, spin coating, spray coating or pulling. In some embodiments, the second electrochromic layer is prepared on the electron blocking layer or the ion buffer layer between the first electrochromic layer and the second electrochromic layer by the film forming method.
The invention has the following beneficial effects:
1. two types of visible light and infrared light films which are independently regulated and controlled are designed to be used as the first electrochromic layer and the second electrochromic layer respectively, so that the regulation and control capability of independently regulating and controlling infrared light and visible light and the regulation and control range of infrared light are improved.
2. The first and second electrochromic layers may be prepared through a continuous sputtering process, avoiding the use of a special preparation process, thereby reducing a preparation period and production costs.
3. By introducing other auxiliary layer materials, the response speed and the cycling stability of the electrochromic device can be further improved.
Drawings
FIG. 1 is a block diagram of a visible-infrared independently controlled electrochromic device prepared in example 1;
FIG. 2 is a spectrum of different voltages applied to a visible-infrared independently controlled electrochromic device prepared in example 1;
FIG. 3 is a scanning electron microscope photograph of a cross-section of a half device of example 1, i.e., a device obtained by depositing two electrochromic layers on the surface of a transparent substrate;
FIG. 4 is a memory effect diagram of a visible-infrared independently modulated electrochromic device including an electron blocking layer prepared in example 4;
fig. 5 is a schematic diagram of the visible-infrared independently controlled electrochromic device prepared in example 11 changing color at different voltages.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention.
The basic structure of the visible-infrared independent control electrochromic device comprises a first transparent electrode, a first electrochromic layer, a second electrochromic control layer, an ion conducting layer and a second transparent electrode which are orderly arranged. By designing the multiple electrochromic layers, independent regulation and control of infrared light and visible light can be realized when external bias is different.
As an example, the electrochromic device of the present invention is composed of a first transparent electrode, a first electrochromic layer, a second electrochromic layer, an ion conducting layer, and a second transparent electrode in order, wherein an ion storage layer may be selectively inserted. The invention designs the first electrochromic layer capable of adjusting visible light and the electrochromic layer material only adjusting infrared light, thereby realizing independent adjustment of the transmittance of infrared light and visible light under different voltages and meeting the requirements of actual life.
For example, materials for the first electrochromic layer include, but are not limited to, WO3-x、TiO2PEDOT or prussian blue, etc. For example WO which may be conventional3And the like cathode electrochromic material. The material is amorphous and has a loose structure. In some embodiments, the first electrochromic layer has a thickness of 50-500 nm.
For example, the material of the second electrochromic layer may be VO2And the like. The second electrochromic layer is made of monoclinic phase VO2The reason for this is VO of monoclinic phase only2Has infrared adjusting performance. VO (vacuum vapor volume)2The device has larger adjusting capacity in an infrared region, so that the device prepared by the invention has better visible-infrared independent adjusting and controlling performance. The second electrochromic layer may have a thickness of 20-200 nm.
Also, the thickness ratio of the first electrochromic layer and the second electrochromic layer may be 20: 1-2: 1. too high a thickness of the second electrochromic layer may affect the amount of ions entering the first electrochromic layer through the second electrochromic layer, thereby reducing the ability of the first electrochromic layer to adjust the transmission of visible light. In addition, the second electrochromic layer also affects the mobility of ions, and too thick will result in a decrease in cation mobility. However, too thin a thickness of the second electrochromic layer may result in insufficient adjustment capability of the infrared portion.
The cation migration capability is weak at low voltage, and only VO can be inserted2In (1), making VO2The film is converted from a semiconductor monoclinic structure which is penetrated by infrared light into a metal tetragonal structure which is blocked by the infrared light, and the voltage cation is continuously increasedAnd the light migrates into the first electrochromic layer in one step, so that the visible light is absorbed strongly. Compared with the conventional dual-mode independently-controlled electrochromic device, the dual-mode independently-controlled electrochromic device has the advantages of simpler structure, stronger regulation capability and larger infrared regulation range.
According to the invention, by regulating and controlling the contact interface between the two layers of electrochromic materials, the migration efficiency of cations can be improved, the accumulation at the interface is avoided, and the cycle stability of the device is improved.
Specifically, the contact state between interfaces of each layer is adjusted by adjusting the thickness and the preparation process of each functional layer in the device, so that the visible-infrared transmittance electrochromic intelligent window which can be widely popularized and has use value and can be independently regulated and controlled is obtained. The interface between the two layers of electrochromic materials influences the releasing and embedding power of cations driven by an external voltage. By optimizing the bonding between the two layers of material, interface defects are reduced, and cations tend to be easily trapped by the defects when migrating at the interface, thereby resulting in incomplete fading. Specifically, the thickness of the two layers of material is first adjusted, primarily by adjusting the sputtering time of each layer. The intercalation depth is different due to different migration kinetics of cations in different layers. In a specific embodiment, VO2The layer must not be too thick, otherwise it goes into WO3The number of cations in the polymer is insufficient, and the adjusting capability of the device in a visible light range is influenced. Second, VO2And WO3The film has some absorption in the visible range, so reasonable thickness can optimize the performance of the device. As can be seen from comparison of the test results of the examples, the first electrochromic layer (WO)3) Thickness of about 350nm, second electrochromic layer (VO)2) The thickness is about 30nm, and the thickness is preferable. In addition, the surface roughness and the interface bonding force of the film can be controlled by cooperatively adjusting the sputtering pressure and the power. The lower the surface roughness, the better the bond between the two films and the stronger the ion transport capability. By comparison of the examples, it can be found that WO3The deposition process of the layer is that the total pressure is 2.0Pa and the power of a direct current power supply is 70W, and the WO with an amorphous structure is obtained3Film, VO2The deposition conditions of the layers are total pressure of 1Pa and direct current power supply power of 100W, and a monoclinic structure is obtainedVO2。
Moreover, the present invention utilizes WO simultaneously3Iso-cathode electrochromic material and VO2When the thermochromic material is used as the first electrochromic material and the second electrochromic material, the independent regulation of visible light and infrared light is realized by regulating and controlling the embedding and the releasing of cations in the two layers of materials and the interface of the two layers of materials, so that the electrochromic device has innovativeness in structure and function. In addition, the simple superposition of the thermochromism and electrochromism functions of the visible-infrared independent control electrochromic device can realize the infrared light control and the visible-infrared independent control.
The following exemplifies a specific technical scheme for preparing the visible-infrared independently-controlled electrochromic device.
An inorganic electrochromic layer (namely a first electrochromic layer) and an electron blocking layer are prepared on the surface of a transparent conductive glass substrate through continuous deposition. By magnetron sputtering method, metal tungsten, molybdenum or titanium is used as a target material, sputtering gas is argon and oxygen, total pressure is 0.5-2.0Pa, oxygen partial pressure is 0-50%, the distance between the target material and a substrate is 10-20cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied on the target material is 30-150W or the power density is 0.6-3.0W/cm2The surface of the first electrochromic layer film is deposited by a direct current power supply to 50 nm-500 nm.
Continue with V2O3The total pressure is 0.5-2.0Pa, the oxygen partial pressure is 0-50%, the distance between the target and the substrate is 10-20cm, the initial substrate temperature is room temperature, the power of the direct current power supply applied on the target is 100-400W or the power density is 2-8.0W/cm2And depositing a second electrochromic layer film with the surface of 20 nm-200 nm by using a direct current power supply. In the above process, the target material is V2O3The sputtering process is reactive sputtering, and the obtained film is VO2A film.
And then preparing an ion conducting layer by a magnetron sputtering technology or an ultraviolet radiation curing technology by preparing a resin precursor according to the prior art, and finally preparing a second transparent conductive electrode on the upper surface of the sample by the magnetron sputtering technology or directly covering transparent conductive glass as an electrode.
The direct current magnetron sputtering system equipment used for magnetron sputtering deposition in the invention can comprise a deposition chamber, a sample chamber, a plurality of target heads, a substrate plate, a direct current, and a series of mechanical pumps and vacuum pumps, wherein the target heads and the substrate plate form a certain angle and are separated by a certain distance, and a direct current power supply is connected on the target heads. Ultrasonically cleaning the substrate, ultrasonically cleaning the substrate with acetone, absolute ethyl alcohol and deionized water for 20min respectively, and blow-drying with compressed air. Covering a certain part of conductive substrate with high-temperature adhesive tape as electrode, fixing on substrate tray, placing into sample introduction chamber, pumping to below 5Pa, opening baffle valve, and feeding into vacuum degree (background vacuum degree) of 10-4Pa or less.
The transmittance of the prepared visible-infrared independently-controlled electrochromic device in an infrared wavelength range is 10-80% under the voltage of 0V-1V.
The prepared visible-infrared independently-controlled electrochromic device has the highest light modulation range of 60-72% in the visible light wavelength range under the voltage of 1V-1.5V.
After the prepared visible-infrared independently-controlled electrochromic device is subjected to an external electric field circulation test action of 0V-1.5V voltage for 1000 times, the adjustment amplitude of the material in the visible light and infrared wavelength ranges can reach 95% of that of the initial test.
The visible light modulation amplitude of the visible-infrared independent control electrochromic device is 60-72%, the infrared light modulation amplitude is 60-70%, the complete coloring time is 3-5 s, the fading time is 1-3 s, and the coloring efficiency is 30-100 cm2/C。
The present invention will be described in detail by way of examples. It is to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art in light of the foregoing description are intended to be included within the scope of the invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Firstly, an ITO transparent conductive glass substrate is used, a substrate is respectively cleaned by acetone, ethanol and deionized water for 20min in an ultrasonic mode, then the substrate is fixed on a substrate tray by a high-temperature adhesive tape, the substrate tray is placed into a sample chamber, a mechanical pump is started to pump to be below 5Pa, a baffle valve is opened, and the substrate tray is sent to a vacuum degree (background vacuum degree) to reach 10-4Pa or less. And continuously depositing and preparing the first electrochromic layer and the second electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2And the deposition time is 30min, and the inorganic electrochromic layer film (namely the first electrochromic layer) with the thickness of about 350nm is obtained. With V2O3The target material is a target material, the total pressure is 1Pa, the oxygen partial pressure is 30 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 2W/cm2And depositing the surface for 20min by using a direct current power supply to obtain a second electrochromic layer with the thickness of 30 nm. According to the prior art, resin slurry prepared by an organic solvent, a stabilizer, a curing resin, a precursor and an ion source according to a certain proportion is coated on the surface of the thin film through vacuum drip irrigation or screen printing to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the photocuring is to uniformly irradiate the device for 50min under a 100W ultraviolet lamp. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. The visible-infrared independently controlled electrochromic device provided by the invention can be obtained, and the structural schematic diagram is shown in figure 1. The visible-infrared visible light independent control spectrum is shown in FIG. 2, and the infrared transmittance is gradually reduced with the gradual increase of voltageThen, the visible light transmittance rapidly decreases. Fig. 3 is a cross-sectional scanning electron microscope picture of a half-device, i.e. a schematic representation of two electrochromic layers deposited on the surface of a transparent substrate. It can be seen from fig. 3 that the first and second dots are tightly coupled to each other to facilitate ion intercalation and deintercalation.
Example 2
Firstly, an ITO transparent conductive glass substrate is used, a substrate is respectively cleaned by acetone, ethanol and deionized water for 20min in an ultrasonic mode, then the substrate is fixed on a substrate tray by a high-temperature adhesive tape, the substrate tray is placed into a sample chamber, a mechanical pump is started to pump to be below 5Pa, a baffle valve is opened, and the substrate tray is sent to a vacuum degree (background vacuum degree) to reach 10-4Pa or less. And continuously depositing and preparing the first electrochromic layer and the second electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2And the deposition time is 15min, and the inorganic electrochromic layer film (namely the first electrochromic layer) with the thickness of about 100nm is obtained. With V2O3The target material is a target material, the total pressure is 1Pa, the oxygen partial pressure is 30 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 2W/cm2And depositing the surface for 20min by using a direct current power supply to obtain a second electrochromic layer with the thickness of 30 nm. According to the prior art, resin slurry prepared by an organic solvent, a stabilizer, a curing resin, a precursor and an ion source according to a certain proportion is coated on the surface of the thin film through vacuum drip irrigation or screen printing to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the photocuring is to uniformly irradiate the device for 50min under a 100W ultraviolet lamp. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. Is ready to obtainThe visible-infrared independently-controlled electrochromic device provided by the invention.
Example 3
Firstly, an ITO transparent conductive glass substrate is used, a substrate is respectively cleaned by acetone, ethanol and deionized water for 20min in an ultrasonic mode, then the substrate is fixed on a substrate tray by a high-temperature adhesive tape, the substrate tray is placed into a sample chamber, a mechanical pump is started to pump to be below 5Pa, a baffle valve is opened, and the substrate tray is sent to a vacuum degree (background vacuum degree) to reach 10-4Pa or less. And continuously depositing and preparing the first electrochromic layer and the second electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2And the deposition time is 30min, and the inorganic electrochromic layer film (namely the first electrochromic layer) with the thickness of about 350nm is obtained. With V2O3The target material is a target material, the total pressure is 1Pa, the oxygen partial pressure is 30 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 200W or the power density is 4W/cm2And depositing the surface for 20min by using a direct current power supply to obtain a second electrochromic layer with the thickness of 100 nm. According to the prior art, resin slurry prepared by an organic solvent, a stabilizer, a curing resin, a precursor and an ion source according to a certain proportion is coated on the surface of the thin film through vacuum drip irrigation or screen printing to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the photocuring is to uniformly irradiate the device for 50min under a 100W ultraviolet lamp. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. The visible-infrared independently controlled electrochromic device provided by the invention can be obtained.
Example 4
Firstly, an ITO transparent conductive glass substrate is used for dividing the substrate into two partsUltrasonic cleaning with acetone, ethanol and deionized water for 20min, fixing on a substrate tray with high temperature adhesive tape, placing into a sample chamber, pumping to below 5Pa, opening a baffle valve, and sending into vacuum degree (background vacuum degree) of 10-4Pa or less. And continuously depositing and preparing the first electrochromic layer and the second electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2And the deposition time is 30min, and the inorganic electrochromic layer film (namely the first electrochromic layer) with the thickness of about 350nm is obtained. With V2O3The target material is a target material, the total pressure is 1Pa, the oxygen partial pressure is 30 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 2W/cm2And depositing the surface for 20min by using a direct current power supply to obtain a second electrochromic layer with the thickness of 30 nm. At VO2Silicon is used as a target material on the film, sputtering gases are argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 10 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 110W or the power density is 2.2W/cm2Depositing SiO about 5nm on the surface by using a direct current power supply2A film. According to the prior art, resin slurry prepared by an organic solvent, a stabilizer, a curing resin, a precursor and an ion source according to a certain proportion is coated on the surface of the thin film through vacuum drip irrigation or screen printing to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the photocuring is to uniformly irradiate the device for 50min under a 100W ultraviolet lamp. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. The visible-infrared independent control electrochromic device provided by the invention can be obtainedAnd (3) a component. The insertion of the electron blocking layer significantly improves the memory effect, as shown in fig. 4.
Example 5
Firstly, an ITO transparent conductive glass substrate is used, a substrate is respectively cleaned by acetone, ethanol and deionized water for 20min in an ultrasonic mode, then the substrate is fixed on a substrate tray by a high-temperature adhesive tape, the substrate tray is placed into a sample chamber, a mechanical pump is started to pump to be below 5Pa, a baffle valve is opened, and the substrate tray is sent to a vacuum degree (background vacuum degree) to reach 10-4Pa or less. And continuously depositing and preparing the first electrochromic layer and the second electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2And the deposition time is 30min, and the inorganic electrochromic layer film (namely the first electrochromic layer) with the thickness of about 350nm is obtained. With V2O3The target material is a target material, the total pressure is 1Pa, the oxygen partial pressure is 30 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 2W/cm2And depositing the surface for 20min by using a direct current power supply to obtain a second electrochromic layer with the thickness of 30 nm. At VO2Lithium fluoride is used as a target material on the film, the sputtering gas is argon, the total pressure is 1.0Pa, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, and the power of a direct current power supply applied to the target material is 50W or the power density is 1W/cm2And depositing a lithium fluoride film with the thickness of about 10nm on the surface by using a direct current power supply. According to the prior art, resin slurry prepared by an organic solvent, a stabilizer, a curing resin, a precursor and an ion source according to a certain proportion is coated on the surface of the thin film through vacuum drip irrigation or screen printing to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the light curing is to place the device in 100W ultravioletThe lamp was turned off and irradiated uniformly for 50 min. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. The visible-infrared independently controlled electrochromic device provided by the invention can be obtained, and the visible-infrared independently controlled spectrum is shown in figure 3.
Example 6
Firstly, an ITO transparent conductive glass substrate is used, a substrate is respectively cleaned by acetone, ethanol and deionized water for 20min in an ultrasonic mode, then the substrate is fixed on a substrate tray by a high-temperature adhesive tape, the substrate tray is placed into a sample chamber, a mechanical pump is started to pump to be below 5Pa, a baffle valve is opened, and the substrate tray is sent to a vacuum degree (background vacuum degree) to reach 10-4Pa or less. And continuously depositing and preparing the first electrochromic layer and the second electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2Depositing for 30min to obtain an inorganic electrochromic layer WO with the thickness of about 350nm3A thin film (i.e., a first electrochromic layer). In WO3Silicon is used as a target material on the film, sputtering gases are argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 10 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 110W or the power density is 2.2W/cm2SiO with surface deposited by about 5nm using DC power supply2A film. With V2O3The target material is a target material, the total pressure is 1Pa, the oxygen partial pressure is 30 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 2W/cm2And depositing the surface for 20min by using a direct current power supply to obtain a second electrochromic layer with the thickness of 30 nm. At VO2Lithium fluoride is used as a target material on the film, the sputtering gas is argon, the total pressure is 1.0Pa, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, and the power of a direct current power supply applied to the target material is 50W or the power density is 1W/cm2The surface is deposited by using a direct current power supply to be about 10nmAnd a lithium fluoride thin film on the right side. According to the prior art, resin slurry prepared by an organic solvent, a stabilizer, a curing resin, a precursor and an ion source according to a certain proportion is coated on the surface of the thin film through vacuum drip irrigation or screen printing to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the photocuring is to uniformly irradiate the device for 50min under a 100W ultraviolet lamp. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. The visible-infrared independently controlled electrochromic device provided by the invention can be obtained.
Example 7
Firstly, an ITO transparent conductive glass substrate is used, a substrate is respectively cleaned by acetone, ethanol and deionized water for 20min in an ultrasonic mode, then the substrate is fixed on a substrate tray by a high-temperature adhesive tape, the substrate tray is placed into a sample chamber, a mechanical pump is started to pump to be below 5Pa, a baffle valve is opened, and the substrate tray is sent to a vacuum degree (background vacuum degree) to reach 10-4Pa or less. And continuously depositing and preparing the first electrochromic layer and the second electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2Depositing for 30min to obtain an inorganic electrochromic layer WO with the thickness of about 350nm3A thin film (i.e., a first electrochromic layer). In WO3Lithium fluoride is used as a target material on the film, the sputtering gas is argon, the total pressure is 1.0Pa, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, and the power of a direct current power supply applied to the target material is 50W or the power density is 1W/cm2And depositing a lithium fluoride film with the thickness of about 10nm on the surface by using a direct current power supply. With V2O3Is a target material, the total pressure is 1Pa, the oxygen partial pressure is 30 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, and the target material is appliedThe power of the direct current power supply is 100W or the power density is 2W/cm2And depositing the surface for 20min by using a direct current power supply to obtain a second electrochromic layer with the thickness of 30 nm. At VO2Silicon is used as a target material on the film, sputtering gases are argon and oxygen, the total pressure is 1.0Pa, the oxygen partial pressure is 10 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 110W or the power density is 2.2W/cm2Depositing SiO about 5nm on the surface by using a direct current power supply2A film. According to the prior art, resin slurry prepared by an organic solvent, a stabilizer, a curing resin, a precursor and an ion source according to a certain proportion is coated on the surface of the thin film through vacuum drip irrigation or screen printing to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the photocuring is to uniformly irradiate the device for 50min under a 100W ultraviolet lamp. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. The visible-infrared independently controlled electrochromic device provided by the invention can be obtained.
Example 8
Firstly, an ITO transparent conductive glass substrate is used, a substrate is respectively cleaned by acetone, ethanol and deionized water for 20min in an ultrasonic mode, then the substrate is fixed on a substrate tray by a high-temperature adhesive tape, the substrate tray is placed into a sample chamber, a mechanical pump is started to pump to be below 5Pa, a baffle valve is opened, and the substrate tray is sent to a vacuum degree (background vacuum degree) to reach 10-4Pa or less. And continuously depositing and preparing the first electrochromic layer and the second electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2And the deposition time is 30min, and the inorganic electrochromic layer film (namely the first electrochromic layer) with the thickness of about 350nm is obtained. With V2O3The target material is a target material, the total pressure is 1Pa, the oxygen partial pressure is 30 percent, the distance between the target material and the substrate is 15cm, the initial substrate temperature is room temperature, the power of a direct current power supply applied to the target material is 100W or the power density is 2W/cm2And depositing the surface for 20min by using a direct current power supply to obtain a second electrochromic layer with the thickness of 30 nm. Preparing an organic electrochromic material on the surface of the film by vacuum evaporation, and preparing a 300 nm-thick PEDOT/PSS film according to the prior art. According to the prior art, resin slurry prepared by an organic solvent, a stabilizer, a curing resin, a precursor and an ion source according to a certain proportion is coated on the surface of the thin film through vacuum drip irrigation or screen printing to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the photocuring is to uniformly irradiate the device for 50min under a 100W ultraviolet lamp. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. The visible-infrared independently controlled electrochromic device provided by the invention can be obtained.
Example 9
Firstly, an ITO transparent conductive glass substrate is used, a substrate is respectively cleaned by acetone, ethanol and deionized water for 20min in an ultrasonic mode, then the substrate is fixed on a substrate tray by a high-temperature adhesive tape, the substrate tray is placed into a sample chamber, a mechanical pump is started to pump to be below 5Pa, a baffle valve is opened, and the substrate tray is sent to a vacuum degree (background vacuum degree) to reach 10-4Pa or less. And continuously depositing and preparing the first electrochromic layer and the second electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2And the deposition time is 30min, and the inorganic electrochromic layer film (namely the first electrochromic layer) with the thickness of about 350nm is obtained. With V2O3The total pressure is 1Pa, the oxygen partial pressure is 30 percent, and the distance between the target material and the substrate is15cm, the initial substrate temperature is room temperature, and the power of the direct current power supply applied to the target is 100W or the power density is 2W/cm2And depositing the surface for 20min by using a direct current power supply to obtain a second electrochromic layer with the thickness of 30 nm. Preparing dilute nitric acid with concentration of 35%, soaking the film for 90s, cleaning with deionized water and anhydrous ethanol, and using dry N2The residual solvent is purged. Preparing an organic electrochromic material on the surface of the film by vacuum evaporation, and preparing a 300 nm-thick PEDOT/PSS film according to the prior art. According to the prior art, resin slurry prepared by an organic solvent, a stabilizer, a curing resin, a precursor and an ion source according to a certain proportion is coated on the surface of the thin film through vacuum drip irrigation or screen printing to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the photocuring is to uniformly irradiate the device for 50min under a 100W ultraviolet lamp. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. The visible-infrared independently controlled electrochromic device provided by the invention can be obtained.
Example 10
Firstly, an ITO transparent conductive glass substrate is used, a substrate is respectively cleaned by acetone, ethanol and deionized water for 20min in an ultrasonic mode, then the substrate is fixed on a substrate tray by a high-temperature adhesive tape, the substrate tray is placed into a sample chamber, a mechanical pump is started to pump to be below 5Pa, a baffle valve is opened, and the substrate tray is sent to a vacuum degree (background vacuum degree) to reach 10-4Pa or less. And depositing and preparing a first electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2And the deposition time is 30min, and the inorganic electrochromic layer film (namely the first electrochromic layer) with the thickness of about 350nm is obtained. VO configuration according to the prior art2Solid content of 5%Preparing VO on the surface of the thin film by spin coating in a dispersion liquid and PMA as a solvent2The film (i.e. the second electrochromic layer) was rotated at 3000rpm and had a thickness of about 50 nm. After completion of the spin coating, it was dried on a hot plate at 70 ℃. And then coating resin slurry prepared by organic solvent, stabilizer, curing resin, precursor and ion source according to a certain proportion on the surface of the film by vacuum drip irrigation or screen printing according to the prior art to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the photocuring is to uniformly irradiate the device for 50min under a 100W ultraviolet lamp. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. The visible-infrared independently controlled electrochromic device provided by the invention can be obtained.
Example 11
Firstly, an ITO transparent conductive glass substrate is used, a substrate is respectively cleaned by acetone, ethanol and deionized water for 20min in an ultrasonic mode, then the substrate is fixed on a substrate tray by a high-temperature adhesive tape, the substrate tray is placed into a sample chamber, a mechanical pump is started to pump to be below 5Pa, a baffle valve is opened, and the substrate tray is sent to a vacuum degree (background vacuum degree) to reach 10-4Pa or less. And depositing and preparing a first electrochromic layer on the surface of the substrate by a magnetron sputtering method. Taking metal tungsten as a target material, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6 percent, setting the distance between the target material and a substrate to be 15cm, setting the initial substrate temperature to be room temperature, and setting the power of a direct current power supply applied to the target material to be 70W or setting the power density to be 1.54W/cm2And the deposition time is 30min, and the inorganic electrochromic layer film (namely the first electrochromic layer) with the thickness of about 350nm is obtained. VO configuration according to the prior art2Preparing VO on the surface of the thin film by spin coating, wherein the solid content of the dispersion is 5 percent and the solvent is PMA2The film (i.e. the second electrochromic layer) was rotated at 3000 rpm. After completion of the spin coating, it was dried on a hot plate at 70 ℃. Preparing organic electrochromic material on the surface of the film by vacuum evaporation, and preparing a 300 nm-thick PEDOT (PSS) film according to the prior artAnd (3) a membrane. And then coating resin slurry prepared by organic solvent, stabilizer, curing resin, precursor and ion source according to a certain proportion on the surface of the film by vacuum drip irrigation or screen printing according to the prior art to form a resin layer (namely an ion conduction layer). The complete device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. And covering the ITO transparent conductive electrode which is the same as the first transparent electrode on the hard template. Wherein the photocuring is to uniformly irradiate the device for 50min under a 100W ultraviolet lamp. And after the device is solidified, removing organic matters on the surface of the redundant device by using an organic solvent. The visible-infrared independently controlled electrochromic device provided by the invention can be obtained. VO prepared by spin coating2Compared with a film prepared by sputtering, the film is more loose, so that the transmission of cations is more facilitated, and the visible-infrared independent regulation and control capability can be realized at lower voltage. As shown in fig. 5, the transmittance of the visible-infrared independently controlled electrochromic device prepared in example 11 was varied at different voltages. When the voltage is from 0V to 1V, the visible light transmittance does not change much, and the infrared transmittance is significantly reduced as shown in fig. 3. When the voltage is further increased to 1.5V, the visible light transmittance is obviously reduced. Open circuit voltage tests show that the device has a good memory effect, and 0V means that the cathode and the anode of the device are connected to represent the charge storage capacity. Fig. 5 shows that the device has excellent visible-infrared independent regulation and control capability, and better memory effect and charge storage capability, and can further expand other applications.

Claims (10)

1. The visible-infrared independently-controlled electrochromic device is characterized by comprising a first transparent electrode, a first electrochromic layer, a second electrochromic layer, an ion conducting layer and a second transparent electrode, wherein the first transparent electrode, the first electrochromic layer only controls visible light under a high voltage condition, the second electrochromic layer only controls infrared light transmittance under a low voltage condition; wherein the high voltage is-5 to 5V, and the low voltage is-2.5 to 2.5V.
2. The visible-infrared independently controllable electrochromic device according to claim 1, wherein the material of said first electrochromic layer is WO3-x、TiO2At least one of PEDOT or Prussian blue, with a thickness of 50-500 nm.
3. The visible-infrared independently controllable electrochromic device according to claim 1 or 2, wherein the material of the second electrochromic layer is monoclinic phase VO2The thickness is 20-200 nm.
4. The visible-infrared independent modulation electrochromic device according to any one of claims 1 to 3, wherein under low voltage conditions, cations can only migrate and intercalate into the second electrochromic layer, such that the second electrochromic layer changes from an infrared-transparent semiconductor monoclinic structure to an infrared-blocking metal tetragonal structure.
5. The visible-infrared independently controllable electrochromic device according to any one of claims 1 to 4, wherein the voltage is continuously increased, and under a high voltage condition, cations migrate into the first electrochromic layer, so that absorption of visible light is realized.
6. The visible-infrared independent control electrochromic device according to any one of claims 1 to 5, wherein the material of the first transparent electrode and/or the second transparent electrode is at least one of transparent conductive oxide or metal nanowire, the thickness is 100-400nm, and the sheet resistance is 3-100 Ω/cm2The transmittance is more than 75 percent.
7. Visible-infrared independently modulatable electrochromic device according to any one of claims 1 to 6, characterized in that said ion-conducting layer is a cation-conducting layer based on a resinous material, wherein the cation is at least one of Li, Na, Al, K, Li, Cs, Rb, Mg and Ca.
8. The visible-infrared independently modulated electrochromic device according to any one of claims 1 to 7, further comprising an ion storage layer located between the ion conducting layer and the second transparent electrode.
9. The visible-infrared independently modulated electrochromic device according to any one of claims 1 to 8, further comprising an electron blocking layer and an ion buffer layer between the first electrochromic layer and the second electrochromic layer or between the second electrochromic layer and the ion conducting layer.
10. The visible-infrared independently controllable electrochromic device according to any one of claims 1 to 9, wherein the second electrochromic layer is prepared on the surface of the first electrochromic layer by a film forming method comprising magnetron sputtering, laser pulse deposition, molecular beam epitaxy, spin coating, spray coating or pulling.
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