CN116243528A - Production method of solid electrochromic device with uniform color and solid electrochromic device - Google Patents
Production method of solid electrochromic device with uniform color and solid electrochromic device Download PDFInfo
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- 238000002955 isolation Methods 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 23
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 23
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- 238000001755 magnetron sputter deposition Methods 0.000 claims description 13
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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
- 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
- G02F1/155—Electrodes
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention discloses a production method of a solid electrochromic device with uniform color, which comprises the following steps: step 1: anode gel was prepared: dissolving anhydrous nickel chloride in absolute ethanol, then adding citric acid, then adding water, then adding an alcohol-soluble polymer; preparing a first intermediate piece and a second intermediate piece, wherein the first intermediate piece consists of a first glass substrate (1), a first transparent conductive layer (2) plated on the first glass substrate, a cathode electrochromic layer (3), an electronic isolation layer (4) and an ion storage layer (5), and the second intermediate piece consists of a second glass substrate (8) and a second transparent conductive layer (7) plated on the second glass substrate; step 2: preparing an anode gel layer on the surface of the ion storage layer of the first intermediate prepared in the step 1 by using the anode gel prepared in the step 1; step 3: and (3) carrying out heat treatment after the second intermediate piece obtained in the step (2) is opposite to the first intermediate piece prepared in the step (1) and clamped. The product prepared by the electrochromic method has better modulation amplitude and color uniformity.
Description
Technical Field
The invention relates to the technical field of photoelectricity, in particular to an electrochromic element.
Background
Electrochromic refers to a phenomenon that optical properties (reflectivity, transmittance, absorptivity, etc.) of a material undergo a stable and reversible color change under the action of an applied electric field, and is represented by a reversible change in color and transparency in appearance. Materials having electrochromic properties are referred to as electrochromic materials, and devices made from electrochromic materials are referred to as electrochromic devices.
In industry, intelligent dimming glass, displays and automatic anti-glare rearview mirrors based on electrochromic principle have been applied.
The prior art CN112394580A discloses an all-solid-state quick-response electrochromic device, which relates to the field of electrochromic and comprises a substrate, and a first conductive layer, an electrochromic layer, an ion conductive layer, an ion storage layer and a second conductive layer which are sequentially arranged on the substrate; a transition layer; the transition layer is positioned between the electrochromic layer and the first conductive layer or in at least one of the ion storage layers, and the transition layer is a rugged conductive film layer. The invention is intended to achieve uniform coloring and fading. The prior art CN112198731a discloses an electrochromic film system and an electrochromic device. The electrochromic film system comprises a first transparent protective layer, a first conductive film layer, an ion storage layer, an ion conduction conveying layer, an ion color-changing layer, a second conductive film layer and a second transparent protective layer which are sequentially laminated, wherein the first conductive film layer is made of metal oxide, the ion storage layer is made of lithium alloy or lithium metal oxide, the ion conduction conveying layer is made of lithium-containing polyanion compound, the ion color-changing layer is made of metal oxide, and the second conductive film layer is made of metal oxide. The invention expects short electrochromic response time and uniform color variation.
With the development of electrochromic elements, industry desires electrochromic products and methods of manufacture that can achieve uniform coloration.
Disclosure of Invention
The invention aims to provide a production method of a solid-state electrochromic device with uniform color and the solid-state electrochromic device.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method of producing a uniformly-electrochromic solid state electrochromic device comprising:
step 1: anode gel was prepared: dissolving anhydrous nickel chloride in absolute ethanol, then adding citric acid, then adding water, then adding an alcohol-soluble polymer; preparing a first intermediate piece and a second intermediate piece, wherein the first intermediate piece consists of a first glass substrate (1), a first transparent conductive layer (2) plated on the first glass substrate, a cathode electrochromic layer (3), an electronic isolation layer (4) and an ion storage layer (5), and the second intermediate piece consists of a second glass substrate (8) and a second transparent conductive layer (7) plated on the second glass substrate;
step 2: preparing an anode gel layer on the surface of the ion storage layer of the first intermediate prepared in the step 1 by using the anode gel prepared in the step 1;
step 3: and (3) carrying out heat treatment after the second intermediate piece obtained in the step (2) is opposite to the first intermediate piece prepared in the step (1) and clamped.
In the step 1, the molar ratio of the anhydrous nickel chloride to the anhydrous ethanol is 1:20-40 parts; the molar ratio of the anhydrous nickel chloride to the citric acid is 1:6-8; the molar ratio of water to absolute ethanol is 1:20-40 parts; the molar ratio of the alcohol-soluble polymer to the absolute ethanol is 1:20-40.
In the step 1, the alcohol-soluble high polymer is selected from at least one or two of nonionic polyvinylpyrrolidone and polyethylene glycol.
In the step 2, anode gel is coated firstly, and baked for 10-25 minutes at 90-100 ℃ after coating; the coating and baking are repeated at least twice to obtain a gel layer.
Wherein in the step 3, the heat treatment temperature is 400-450 ℃.
The hydroxyl value of the polyethylene glycol is 13-30mgKOH/g, and the number average molecular weight is 3000-10000.
The molar ratio of the nonionic polyvinylpyrrolidone to the polyethylene glycol is 2:1-2.
An electrochromic device prepared by a method for producing a solid electrochromic device having uniform color,
the solar cell comprises a first glass substrate (1), a first transparent conductive layer (2) plated on the first glass substrate, a cathode electrochromic layer (3), an electronic isolation layer (4), an ion storage layer (5), an anode electrochromic layer (6) prepared by gel treatment, a second glass substrate (8) and a second transparent conductive layer (7) plated on the second glass substrate.
Wherein the first transparent oxide conductive layer (2) is prepared by a magnetron sputtering method; the cathode electrochromic layer (3) is prepared by a magnetron sputtering method; the electronic isolation layer (4) is Ta prepared by a magnetron sputtering method 2 O 5 A layer; the ion storage layer (5) is vacuum evaporation LiTaO 3 A layer;
wherein the second transparent oxide conductive layer (7) is prepared by a magnetron sputtering method.
Wherein the thickness of the first transparent oxide conductive layer (2) is 30-100nm; the thickness of the cathode electrochromic layer (3) is 150-350nm; the thickness of the electronic isolation layer (4) is 10-50nm; the thickness of the ion storage layer (5) is 300-500nm; wherein the second transparent oxide conductive layer (7) has a thickness of 30-100nm.
In summary, the beneficial effects of the invention are as follows: the electrochromic element has higher coloring efficiency, longer cycle life and uniform coloring effect.
Description of the drawings:
FIG. 1 is a schematic illustration of the present invention prior to coating;
FIG. 2 is a schematic illustration of the present invention after coating;
FIG. 3 is a schematic illustration of a product of the present invention after heat treatment;
FIG. 4 is a schematic diagram of a test for color uniformity.
The specific embodiment is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-3, fig. 3 shows a schematic structural diagram of an electrochromic element having a high transition rate according to the present invention. In fig. 3, a first glass substrate (1) is sequentially included; a first transparent oxide conductive layer (2); a cathode electrochromic layer (3); an electronic isolation layer (4); an ion storage layer (5); an anodic electrochromic layer (6); a second transparent oxide conductive layer (7); a second glass substrate (8). The electrochromic element of fig. 1 has a high transition rate and a longer cycle time. Fig. 1 shows an assembly comprising a first glass substrate (1), a first transparent oxide conductive layer (2), a cathode electrochromic layer (3), an electronic isolation layer (4), an ion storage layer (5), and an assembly comprising a second transparent oxide conductive layer (7), a second glass substrate (8); a schematic illustration of the fabrication of an anodic electrochromic layer (6) on an ion storage layer 5 is shown in fig. 2.
Integral process steps
Anode gel was prepared: dissolving anhydrous nickel chloride in absolute ethanol, then adding citric acid, then adding water, then adding an alcohol-soluble polymer;
129g of anhydrous nickel chloride is taken and dissolved in 20-40mol of absolute ethyl alcohol under the vibration stirring state; then adding 6-10mol of citric acid, heating and stirring uniformly in a vibration state; subsequently, 1mol of deionized water was added and stirred uniformly in a shaking state to obtain a first solution. Dissolving an alcohol-soluble polymer in a first solution under vibration and heating states, wherein the ratio of the alcohol-soluble polymer to absolute ethyl alcohol in the first solution is 1:20-40, the alcohol-soluble polymer is a mixture of nonionic polyvinylpyrrolidone and polyethylene glycol, the molar ratio of the nonionic polyvinylpyrrolidone to the polyethylene glycol is 2:1-2, and standing for a period of time to obtain anode gel.
The anode gel prepared above can be subsequently coated.
Preparing a first intermediate piece and a second intermediate piece:
the first glass substrate and the second glass substrate are commercially available glasses according to the need.
A first transparent oxide conductive layer and a second transparent oxide conductive layer.
Wherein the first transparent oxide conductive layer and the second transparent oxide conductive layer may employ a transparent oxide conductive layer of ITO, AZO, GZO or the like having similar properties. In the invention, the thickness of the transparent oxide conductive layer is 30-100nm; the light transmittance is more than 84%; the refractive index is 1.8-2.2.
The preparation method of the first transparent oxide conductive layer and the second transparent oxide conductive layer comprises the following steps: vacuumizing the magnetron sputtering plating equipment to 0.5X10 -5 -1.0×10 -5 mmHg; ar gas is then introduced, and the pressure of the working cavity is controlled to be 4 multiplied by 10 through a valve -3 -6×10 -3 mmHg and ITO, AZO, GZO targets are used for sputtering a 30-100nm thick transparent oxide conductive layer on a substrate.
A cathode electrochromic layer.
The cathode electrochromic layer is a tungsten oxide layer. The tungsten oxide layer has a thickness of 150-300nm and a refractive index of 1.9-2.3.
The preparation method of the cathode electrochromic layer comprises the following steps: vacuumizing the magnetron sputtering plating equipment to 0.5X10 -5 -1.0×10 -5 mmHg; ar gas is then introduced, and the pressure of the working cavity is controlled to be 2 multiplied by 10 through a valve -3 -5×10 -3 mmHg, and a tungsten target is utilized to manufacture a tungsten oxide cathode electrochromic layer with the thickness of 150-350nm in the presence of oxygen. In general, in addition to magnetron sputtering plating, the cathode electrochromic layer can also be prepared by tungsten oxide evaporation.
Electronic isolation layer
The electronic isolation layer is Ta 2 O 5 A layer. Ta 2 O 5 The thickness is 10-50nm, and the refractive index is 2.0-2.1.
The preparation method of the electronic isolation layer comprises the following steps: vacuumizing the magnetron sputtering plating equipment to 0.5X10 -5 -1.0×10 - 5 mmHg; ar gas is then introduced, and the pressure of the working cavity is controlled to be 2 multiplied by 10 through a valve -3 -5×10 -3 mmHg and Ta target in the presence of oxygen to produce Ta having a thickness of 10-50nm 2 O 5 A layer.
In order to improve the color retention performance, the invention provides an electronic isolation layer which does not influence the effective transmission of ions. The thickness of the electron isolation layer has an influence on the dielectric properties of the electrolyte layer, said electron isolation layer having a thickness of 10-50nm.
Ion storage layer
The ion storage layer is used for providing Li ions, and can be a Li metal layer or a Li-containing compound such as Li 2 CO 3 A LiF layer, etc. The invention selects the Li-containing compound lithium carbonate layer with the thickness of 150-600nm and LiF layer with the thickness of 150-600nm. The ion storage layer is manufactured by adopting a vacuum evaporation mode.
The above is the layers prepared by vapor deposition. For the anodic electrochromic layer, the preparation method adopts a tungsten oxide gel coating mode.
Coating of anodic electrochromic layers
The nickel oxide gel is coated on the surface of an ion storage layer (5) of a combined body formed by combining a first glass substrate (1), a first transparent oxide conductive layer (2), a cathode electrochromic layer (3), an electronic isolation layer (4) and an ion storage layer (5).
The coating method comprises the following steps: taking outThe gel of nickel oxide is prepared by the steps of,coating the nickel oxide gel layer in multiple passes, for example at least 3 passes; for example by spin coating or spraying. After each application, the coating is heated at 120-140 ℃ for 5-10 minutes. Spraying on 10-20cm of nickel oxide gel at a time in an amount of 3-10ml 2 On the surface of (2)
After cooling, the coating is appliedAnode electrochromic layer withThe components of the first glass substrate (1), the first transparent oxide conductive layer (2), the cathode electrochromic layer (3), the electronic isolation layer (4) and the ion storage layer (5) are placed at the temperature of 160-200 ℃ and heated for 10-15 minutes.
Heat treatment of anodic electrochromic layers
The component coated with the anode electrochromic layer and provided with the first glass substrate, the first transparent oxide conductive layer, the cathode electrochromic layer, the electronic isolation layer and the ion storage layer is buckled with the second glass substrate provided with the second transparent oxide conductive layer, so that the second transparent oxide conductive layer is opposite to the anode electrochromic layer.
Subsequently, the heat treatment furnace was clamped by a clamping device. Heating the heat treatment furnace to 90-100 ℃ and keeping the temperature for 1-2 hours, then heating to 400-450 ℃ at a heating rate of 10 ℃/min, and naturally cooling the inside of the furnace after the heat treatment is finished. The clamping force at this step refers to the force required for intimate bonding.
Packaging
After the heat treatment is completed, the product of the present invention is protected from damage by encapsulation, although the product does not have a liquid component. The encapsulation material may be selected from glues with high water-oxygen barrier properties, such as epoxy or acrylic. The package should fill the seal completely without holes.
Testing
The test method and conditions were as follows:
the test conditions are used for fading and coloring within +/-2V voltage, and the conversion time and the light modulation amplitude of each device are recorded in situ by adopting an electrochemical workstation and an ultraviolet spectrophotometer.
Color uniformity test: and dividing the area to be tested into grids, and respectively testing each grid in the fading and coloring states by using a colorimeter.
The embodiment of the invention comprises the following steps:
example 1
Taking 1mol of anhydrous nickel chloride, and dissolving the 1mol of anhydrous nickel chloride in 20mol of absolute ethyl alcohol under the vibration stirring state; then adding 8mol of citric acid, heating and stirring uniformly in a vibration state; subsequently, 1mol of deionized water was added and stirred uniformly in a shaking state to obtain a first solution. Dissolving 1mol of alcohol-soluble polymer in 20mol of absolute ethyl alcohol under a heating state, wherein the alcohol-soluble polymer is a mixture of nonionic polyvinylpyrrolidone and polyethylene glycol, the molar ratio of the nonionic polyvinylpyrrolidone to the polyethylene glycol is 2:1, adding an ethanol solution of the alcohol-soluble polymer into the first solution, stirring uniformly under a vibration heating state, and standing for a period of time to obtain anode gel.
The first glass substrate and the second glass substrate are commercially available glasses according to the need. And manufacturing a first transparent oxide conductive layer on the first glass substrate, and manufacturing a second transparent oxide conductive layer on the second glass substrate. ITO is selected as the transparent oxide conductive layer, and the thickness is 50nm.
The thickness of the cathode electrochromic layer tungsten oxide is 200nm.
Electronic isolation layer Ta 2 O 5 The thickness was 35nm.
The thickness of the ion storage layer LiF is 300nm. The ion storage layer is manufactured by adopting a vacuum evaporation mode.
Coating of the anodic electrochromic layer: and coating gel on the surface of the ion storage layer (5) for 2 times. After each application, baking is carried out at 120-140 ℃ for 5-10 minutes. After coating, the coating is placed at the temperature of 150-180 ℃ and heated for 10-15 minutes. The thickness of the coating is 600nm after heating and drying.
Heat treatment of the anodic electrochromic layer: the functional layers of the first glass substrate (1) and the second glass substrate are aligned, and the second transparent oxide conductive layer is opposite to the cathode electrochromic layer. The furnace is clamped by a clamping device. The heat treatment furnace is heated to 90-100 ℃ and kept for 1-2 hours, then heated to 420 ℃, the heating rate is 10 ℃/min, and the furnace is naturally cooled after the heat treatment is completed.
And packaging after the heat treatment is finished.
Example 2
Taking 1mol of anhydrous nickel chloride, and dissolving the 1mol of anhydrous nickel chloride in 30mol of absolute ethyl alcohol under the vibration stirring state; then adding 8mol of citric acid, heating and stirring uniformly in a vibration state; subsequently, 1mol of deionized water was added and stirred uniformly in a shaking state to obtain a first solution. Dissolving 1mol of alcohol-soluble polymer in 30mol of absolute ethyl alcohol under a heating state, wherein the alcohol-soluble polymer is a mixture of nonionic polyvinylpyrrolidone and polyethylene glycol, the molar ratio of the nonionic polyvinylpyrrolidone to the polyethylene glycol is 2:2, adding an ethanol solution of the alcohol-soluble polymer into the first solution, stirring uniformly under a vibration heating state, and standing for a period of time to obtain anode gel.
The first glass substrate and the second glass substrate are commercially available glasses according to the need. And manufacturing a first transparent oxide conductive layer on the first glass substrate, and manufacturing a second transparent oxide conductive layer on the second glass substrate. ITO is selected as the transparent oxide conductive layer, and the thickness is 40nm.
The thickness of the cathode electrochromic layer tungsten oxide is 230nm.
Electronic isolation layer Ta 2 O 5 The thickness was 40nm.
The thickness of the ion storage layer LiF is 350nm. The ion storage layer is manufactured by adopting a vacuum evaporation mode.
Coating of the anodic electrochromic layer: and coating gel on the surface of the ion storage layer (5) for 2 times. After each application, baking is carried out at 120-140 ℃ for 5-10 minutes. After coating, the coating is placed at the temperature of 150-180 ℃ and heated for 10-15 minutes. The thickness of the coating is 650nm after heating and drying.
Heat treatment of the anodic electrochromic layer: the functional layers of the first glass substrate (1) and the second glass substrate are aligned, and the second transparent oxide conductive layer is opposite to the cathode electrochromic layer. The furnace is clamped by a clamping device. Heating the heat treatment furnace to 90-100 ℃ and keeping the temperature for 1-2 hours, then heating to 450 ℃, wherein the heating rate is 10 ℃/min, and naturally cooling the inside of the furnace after the heat treatment is finished.
And packaging after the heat treatment is finished.
Example 3
Taking 1mol of anhydrous nickel chloride, and dissolving the 1mol of anhydrous nickel chloride in 40mol of absolute ethyl alcohol under the vibration stirring state; then adding 8mol of citric acid, heating and stirring uniformly in a vibration state; subsequently, 1mol of deionized water was added and stirred uniformly in a shaking state to obtain a first solution.
Adding 1mol of an alcohol-soluble polymer into the first solution, wherein the alcohol-soluble polymer is a mixture of nonionic polyvinylpyrrolidone and polyethylene glycol, the molar ratio of the nonionic polyvinylpyrrolidone to the polyethylene glycol is 2:2, stirring uniformly in a vibration heating state, and standing for a period of time to obtain the anode gel.
The first glass substrate and the second glass substrate are commercially available glasses according to the need. And manufacturing a first transparent oxide conductive layer on the first glass substrate, and manufacturing a second transparent oxide conductive layer on the second glass substrate. ITO is selected as the transparent oxide conductive layer, and the thickness is 35nm.
The thickness of the cathode electrochromic layer tungsten oxide is 250nm.
Electronic isolation layer Ta 2 O 5 The thickness was 30nm.
The thickness of the ion storage layer LiF is 320nm. The ion storage layer is manufactured by adopting a vacuum evaporation mode.
Coating of the anodic electrochromic layer: and coating gel on the surface of the ion storage layer (5) for 2 times. After each application, baking is carried out at 120-140 ℃ for 5-10 minutes. After coating, the coating is placed at the temperature of 150-180 ℃ and heated for 10-15 minutes. The thickness of the coating is 600nm after heating and drying.
Heat treatment of the anodic electrochromic layer: the functional layers of the first glass substrate (1) and the second glass substrate are aligned, and the second transparent oxide conductive layer is opposite to the cathode electrochromic layer. The furnace is clamped by a clamping device. The heat treatment furnace is heated to 90-100 ℃ and kept for 1-2 hours, then heated to 420 ℃, the heating rate is 10 ℃/min, and the furnace is naturally cooled after the heat treatment is completed.
And packaging after the heat treatment is finished.
Example 4
Taking 1mol of anhydrous nickel chloride, and dissolving the 1mol of anhydrous nickel chloride in 35mol of absolute ethyl alcohol under the vibration stirring state; then adding 8mol of citric acid, heating and stirring uniformly in a vibration state; subsequently, 1mol of deionized water was added and stirred uniformly in a shaking state to obtain a first solution.
Adding 1mol of an alcohol-soluble polymer into the first solution, wherein the alcohol-soluble polymer is a mixture of nonionic polyvinylpyrrolidone and polyethylene glycol, the molar ratio of the nonionic polyvinylpyrrolidone to the polyethylene glycol is 2:1.5, stirring uniformly in a vibration heating state, and standing for a period of time to obtain the anode gel.
The first glass substrate and the second glass substrate are commercially available glasses according to the need. And manufacturing a first transparent oxide conductive layer on the first glass substrate, and manufacturing a second transparent oxide conductive layer on the second glass substrate. ITO is selected as the transparent oxide conductive layer, and the thickness is 35nm.
The thickness of the cathode electrochromic layer tungsten oxide is 280nm.
Electronic isolation layer Ta 2 O 5 The thickness was 35nm.
The thickness of the ion storage layer LiF is 300nm. The ion storage layer is manufactured by adopting a vacuum evaporation mode.
Coating of the anodic electrochromic layer: and coating gel on the surface of the ion storage layer (5) for 2 times. After each application, baking is carried out at 120-140 ℃ for 5-10 minutes. After coating, the coating is placed at the temperature of 150-180 ℃ and heated for 10-15 minutes. The thickness of the coating is 500nm after heating and drying.
Heat treatment of the anodic electrochromic layer: the functional layers of the first glass substrate (1) and the second glass substrate are aligned, and the second transparent oxide conductive layer is opposite to the cathode electrochromic layer. The furnace is clamped by a clamping device. The heat treatment furnace is heated to 90-100 ℃ and kept for 1-2 hours, then the temperature is raised to 440 ℃, the heating rate is 10 ℃/min, and the furnace is naturally cooled after the heat treatment is completed.
And packaging after the heat treatment is finished.
Comparative example 1
Taking 1mol of anhydrous nickel chloride, and dissolving the 1mol of anhydrous nickel chloride in 40mol of absolute ethyl alcohol under the vibration stirring state; then adding 8mol of citric acid, heating and stirring uniformly in a vibration state; subsequently, 1mol of deionized water was added and stirred uniformly in a shaking state to obtain a first solution. After standing for a period of time, an anode gel was obtained.
The first glass substrate and the second glass substrate are commercially available glasses according to the need. And manufacturing a first transparent oxide conductive layer on the first glass substrate, and manufacturing a second transparent oxide conductive layer on the second glass substrate. ITO is selected as the transparent oxide conductive layer, and the thickness is 30nm.
The thickness of the anode electrochromic layer tungsten oxide is 280nm.
Electronic isolation layer Ta 2 O 5 The thickness was 35nm.
The thickness of the ion storage layer LiF is 300nm. The ion storage layer is manufactured by adopting a vacuum evaporation mode.
Coating of the anodic electrochromic layer: and coating gel on the surface of the ion storage layer (5) for 2 times. After each application, baking is carried out at 120-140 ℃ for 5-10 minutes. After coating, the coating is placed at the temperature of 150-180 ℃ and heated for 10-15 minutes. The thickness of the coating is 500nm after heating and drying.
Heat treatment of the anodic electrochromic layer: the functional layers of the first glass substrate (1) and the second glass substrate are aligned, and the second transparent oxide conductive layer is opposite to the cathode electrochromic layer. The furnace is clamped by a clamping device. The heat treatment furnace is heated to 90-100 ℃ and kept for 1-2 hours, then the temperature is raised to 460 ℃, the heating rate is 10 ℃/min, and the furnace is naturally cooled after the heat treatment is completed.
And packaging after the heat treatment is finished.
Comparative example 2
Taking 1mol of anhydrous nickel chloride, and dissolving the 1mol of anhydrous nickel chloride in 35mol of absolute ethyl alcohol under the vibration stirring state; then adding 8mol of citric acid, heating and stirring uniformly in a vibration state; subsequently, 1mol of deionized water was added and stirred uniformly in a shaking state to obtain a first solution.
Adding an alcohol-soluble polymer into the first solution, wherein the alcohol-soluble polymer is nonionic polyvinylpyrrolidone, the nonionic polyvinylpyrrolidone is 1.5mol, stirring uniformly in a vibration heating state, and standing for a period of time to obtain anode gel.
The first glass substrate and the second glass substrate are commercially available glasses according to the need. And manufacturing a first transparent oxide conductive layer on the first glass substrate, and manufacturing a second transparent oxide conductive layer on the second glass substrate. ITO is selected as the transparent oxide conductive layer, and the thickness is 30nm.
The thickness of the cathode electrochromic layer tungsten oxide is 290nm.
Electronic isolation layer Ta 2 O 5 The thickness was 40nm.
The thickness of the ion storage layer LiF is 300nm. The ion storage layer is manufactured by adopting a vacuum evaporation mode.
Coating of the anodic electrochromic layer: and coating gel on the surface of the ion storage layer (5). After coating, the coating is placed at the temperature of 150-180 ℃ and heated for 10-15 minutes. The thickness of the coating is 500nm after heating and drying.
Heat treatment of the anodic electrochromic layer: the functional layers of the first glass substrate (1) and the second glass substrate are aligned, and the second transparent oxide conductive layer is opposite to the cathode electrochromic layer. The furnace is clamped by a clamping device. The heat treatment furnace is heated to 90-100 ℃ and kept for 1-2 hours, then the temperature is raised to 460 ℃, the heating rate is 10 ℃/min, and the furnace is naturally cooled after the heat treatment is completed.
And packaging after the heat treatment is finished.
Comparative example 3
Taking 1mol of anhydrous nickel chloride, and dissolving the 1mol of anhydrous nickel chloride in 30mol of absolute ethyl alcohol under the vibration stirring state; then adding 8mol of citric acid, heating and stirring uniformly in a vibration state; subsequently, 1mol of deionized water was added and stirred uniformly in a shaking state to obtain a first solution.
Adding polyethylene glycol into the first solution, stirring uniformly in a vibration heating state, and standing for a period of time to obtain anode gel, wherein the amount of the polyethylene glycol is 1.5 mol.
The first glass substrate and the second glass substrate are commercially available glasses according to the need. And manufacturing a first transparent oxide conductive layer on the first glass substrate, and manufacturing a second transparent oxide conductive layer on the second glass substrate. ITO is selected as the transparent oxide conductive layer, and the thickness is 25nm.
The thickness of the cathode electrochromic layer tungsten oxide is 200nm.
Electronic isolation layer Ta 2 O 5 The thickness was 50nm.
The thickness of the ion storage layer LiF is 250nm. The ion storage layer is manufactured by adopting a vacuum evaporation mode.
Coating of the anodic electrochromic layer: and coating gel on the surface of the ion storage layer (5) for 2 times. After each application, baking is carried out at 120-140 ℃ for 5-10 minutes. After coating, the coating is placed at the temperature of 150-180 ℃ and heated for 10-15 minutes. The thickness of the coating is 650nm after heating and drying.
Heat treatment of the anodic electrochromic layer: the functional layers of the first glass substrate (1) and the second glass substrate are aligned, and the second transparent oxide conductive layer is opposite to the cathode electrochromic layer. The furnace is clamped by a clamping device. The heat treatment furnace is heated to 90-100 ℃ and kept for 1-2 hours, then the temperature is raised to 460 ℃, the heating rate is 10 ℃/min, and the furnace is naturally cooled after the heat treatment is completed.
And packaging after the heat treatment is finished.
Comparative example 4
The first glass substrate and the second glass substrate are commercially available glasses according to the need. And manufacturing a first transparent oxide conductive layer on the first glass substrate, and manufacturing a second transparent oxide conductive layer on the second glass substrate. ITO is selected as the transparent oxide conductive layer, and the thickness is 30nm.
The thickness of the cathode electrochromic layer tungsten oxide is 220nm.
Electronic isolation layer Ta 2 O 5 The thickness was 40nm.
The thickness of the ion storage layer LiF is 300nm. The ion storage layer is manufactured by adopting a vacuum evaporation mode.
The anode electrochromic layer is prepared on the surface of the second transparent oxide conductive layer by adopting a magnetron sputtering method, wherein the thickness is 230nm.
And (3) heat treatment: the functional layers of the first glass substrate (1) and the second glass substrate are aligned. The furnace is clamped by a clamping device. The temperature of the heat treatment furnace is raised to 400 ℃, the temperature raising rate is 10 ℃/min, and the furnace is naturally cooled after the heat treatment is completed.
And packaging after the heat treatment is finished.
Comparative example 5
Taking 1mol of nickel acetate tetrahydrate, and dissolving the nickel acetate tetrahydrate in 30mol of ethylene glycol methyl ether under the vibration stirring state; then adding ammonia water, heating and stirring uniformly in a vibration state. After standing for a period of time, an anode gel was obtained.
The first glass substrate and the second glass substrate are commercially available glasses according to the need. And manufacturing a first transparent oxide conductive layer on the first glass substrate, and manufacturing a second transparent oxide conductive layer on the second glass substrate. ITO is selected as the transparent oxide conductive layer, and the thickness is 30nm.
The thickness of the anode electrochromic layer tungsten oxide is 280nm.
Electronic isolation layer Ta 2 O 5 The thickness was 35nm.
The thickness of the ion storage layer LiF is 300nm. The ion storage layer is manufactured by adopting a vacuum evaporation mode.
Coating of the anodic electrochromic layer: and coating gel on the surface of the ion storage layer (5) for 2 times. After each application, baking is carried out at 120-140 ℃ for 5-10 minutes. After coating, the coating is placed at the temperature of 150-180 ℃ and heated for 10-15 minutes. The thickness of the coating is 500nm after heating and drying.
Heat treatment of the anodic electrochromic layer: the functional layers of the first glass substrate (1) and the second glass substrate are aligned, and the second transparent oxide conductive layer is opposite to the cathode electrochromic layer. The furnace is clamped by a clamping device. The heat treatment furnace is heated to 90-100 ℃ and kept for 1-2 hours, then the temperature is raised to 460 ℃, the heating rate is 10 ℃/min, and the furnace is naturally cooled after the heat treatment is completed.
And packaging after the heat treatment is finished.
Testing
The test method and conditions were as follows:
and (3) carrying out fading and coloring under the test condition within +/-2V voltage, adopting an electrochemical workstation and an ultraviolet spectrophotometer for in-situ recording, and finally obtaining the conversion time and the light modulation amplitude of each device.
See in particular Table 1
In the present invention, a plurality of (at least two) functional layers are formed by the baking treatment and the heat treatment. In the preparation process, after the gel coating material is dispersed or dissolved under anhydrous condition, water is added to carry out hydrolysis reaction after reaction, and a Ni-O polymer is generated to form colloid.
After the alcohol-soluble polymer is dissolved, a new three-dimensional structure is formed in the heating and stirring process, and the new three-dimensional structure is combined with the Ni-O polymer to form a space complex three-dimensional structure.
Then in the coating process, the alcohol solution is gradually volatilized through multiple coating and relatively low-temperature heating, and a multi-layer coating is formed after multiple coating. In the heat treatment process, absolute ethyl alcohol is used for coating to form a coating layer, and finally, a crystalline state is formed.
In the invention, after gel drying, the gel and the transparent oxide conductive layer are subjected to heat treatment under the action of pressure, on one hand, a multi-layer microscopic amorphous structure is formed, and on the other hand, the gel and the transparent oxide conductive layer have good contact property. The three-dimensional structure formed by the coating and drying under the alcohol solution is then in close contact during the heat treatment, so that the surface conductivity is improved and the color uniformity is improved.
The effective light emitting surface of the products prepared in examples and comparative examples of the present invention was classified into, for example, 4, 9, 16, 20, 25 or more blocks, which can be determined according to the size of the surface of the product, and each of the grids in the discolored and colored states was separately tested using a colorimeter.
Test results
The following table shows the results of the fade and stain tests of example 1.
As can be seen from the above table, the devices have color differences among 9 zones, lab value differences are small, and the macroscopic light differences are basically colorless difference differences.
Similar measurements were made for other embodiments of the present invention, and it was found that Lab values vary greatly depending on the particular film thickness, and that Lab differences for each zone are relatively small, essentially without color difference differences when observed visually.
Comparative example 1 was tested in the same manner.
| Block block | Fade Lab | Coloring Lab |
| 1 | (77.4,-14.4,-12.1) | (72.7,-9.1,62.5) |
| 2 | (75.2,-15.1,-12.3) | (71.4,-9.5,61.9) |
| 3 | (79.4,-16.5,-12.9) | (75.5,-9.2,62.7) |
| 4 | (75.5,-17.2,-13.4) | (71.6,-9.5,59.4) |
| 5 | (76.7,-18.9,-13.1) | (72.9,-9.3,62.7) |
| 6 | (78.9,-13.7,-12.5) | (75.3,-9.8,61.9) |
| 7 | (76.0,-14.5,-12.7) | (71.2,-8.7,61.4) |
| 8 | (75.7,-14.1,-12.4) | (71.2,-8.1,61.4) |
| 9 | (79.8,-15.3,-12.2) | (76.1,-9.9,62.2) |
Comparative example 2 was tested in the same manner.
Comparative examples 3-5 were tested by the same method, and the average value of 9 zone sampling points Lab was measured by using a color difference meter average measurement mode and compared with the value of the 5 th zone sampling point Lab to obtain the Delat value as follows:
| Delat L | Delat a | Delat b | |
| comparative example 3 | 1.9 | 2.1 | 2.1 |
| Comparative example 4 | 2.4 | 3.3 | 2.5 |
| Comparative example 5 | 2.5 | 3.1 | 2.2 |
The electrochromic component with uniform color can be manufactured by the technical scheme of the invention. The gel of the invention produces a three-dimensional nanometer microcosmic amorphous structure, and the nickel oxide is in a uniform amorphous structure state, and has longer cycle life,
The wettability of the gel coating is improved, so that the gel coating has good adhesive property; on one hand, the long chain forms a three-dimensional structure, and the short chain polymer forms a more complex three-dimensional structure on the long chain through acting force of a bond. Such a three-dimensional structure serves to support the colloid formed by hydrolysis of the nickel-containing compound during film formation, providing structure for amorphous formation.
After the formation of the coating, the nickel oxide coating is finally formed by heat treatment. The nickel oxide coating has better bonding effect with other coatings in the heat treatment process, so that the nickel oxide coating has excellent bonding effect.
According to the technical scheme, the electrochromic product with high uniform color is finally obtained.
The foregoing is merely a specific implementation of the present application and other modifications and variations can be made by those skilled in the art based on the above-described examples in light of the above teachings. It is to be understood by persons skilled in the art that the foregoing detailed description is provided for the purpose of illustrating the present application and that the scope of the present application is to be controlled by the scope of the appended claims.
Furthermore, those skilled in the art will appreciate that while some embodiments described herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the following claims, any of the claimed embodiments can be used in any combination.
Claims (10)
1. A method of producing a uniformly-electrochromic solid state electrochromic device comprising:
step 1: anode gel was prepared: dissolving anhydrous nickel chloride in absolute ethanol, then adding citric acid, then adding water, then adding an alcohol-soluble polymer; preparing a first intermediate piece and a second intermediate piece, wherein the first intermediate piece consists of a first glass substrate (1), a first transparent conductive layer (2) plated on the first glass substrate, a cathode electrochromic layer (3), an electronic isolation layer (4) and an ion storage layer (5), and the second intermediate piece consists of a second glass substrate (8) and a second transparent conductive layer (7) plated on the second glass substrate;
step 2: preparing an anode gel layer on the surface of the ion storage layer of the first intermediate prepared in the step 1 by using the anode gel prepared in the step 1;
step 3: and (3) carrying out heat treatment after the second intermediate piece obtained in the step (2) is opposite to the first intermediate piece prepared in the step (1) and clamped.
2. The method of producing a uniformly-colored solid state electrochromic device according to claim 1, wherein: in the step 1, the molar ratio of the anhydrous nickel chloride to the anhydrous ethanol is 1:20-40 parts; the molar ratio of the anhydrous nickel chloride to the citric acid is 1:6-8; the molar ratio of water to absolute ethanol is 1:20-40 parts; the molar ratio of the alcohol-soluble polymer to the absolute ethanol is 1:20-40.
3. The method of producing a uniformly-colored solid state electrochromic device according to claim 1, wherein: in the step 1, the alcohol-soluble high polymer is selected from at least one or two of nonionic polyvinylpyrrolidone and polyethylene glycol.
4. The method of producing a uniformly-colored solid state electrochromic device according to claim 1, wherein: in the step 2, anode gel is coated firstly, and baked for 10-25 minutes at 90-100 ℃ after coating; the coating and baking are repeated at least twice to obtain a gel layer.
5. The method of producing a uniformly-colored solid state electrochromic device according to claim 1, wherein: wherein in the step 3, the heat treatment temperature is 400-450 ℃.
6. A method of producing a uniformly-colored solid state electrochromic device according to claim 3, wherein:
the hydroxyl value of the polyethylene glycol is 13-30mgKOH/g, and the number average molecular weight is 3000-10000.
7. A method of producing a uniformly-colored solid state electrochromic device according to claim 3, wherein:
the molar ratio of the nonionic polyvinylpyrrolidone to the polyethylene glycol is 2:1-2.
8. An electrochromic device prepared using the method of producing a uniformly-colored solid state electrochromic device according to claims 1-7, characterized in that:
the solar cell comprises a first glass substrate (1), a first transparent conductive layer (2) plated on the first glass substrate, a cathode electrochromic layer (3), an electronic isolation layer (4), an ion storage layer (5), an anode electrochromic layer (6) prepared by gel treatment, a second glass substrate (8) and a second transparent conductive layer (7) plated on the second glass substrate.
9. The electrochromic device according to claim 8, wherein:
wherein the first transparent oxide conductive layer (2) is prepared by a magnetron sputtering method; the cathode electrochromic layer (3) is prepared by a magnetron sputtering method; the electronic isolation layer (4) is Ta prepared by a magnetron sputtering method 2 O 5 A layer; the ion storage layer (5) is vacuum evaporation LiTaO 3 A layer;
wherein the second transparent oxide conductive layer (7) is prepared by a magnetron sputtering method.
10. The electrochromic device according to claim 8, wherein:
wherein the thickness of the first transparent oxide conductive layer (2) is 30-100nm; the thickness of the cathode electrochromic layer (3) is 150-350nm; the thickness of the electronic isolation layer (4) is 10-50nm; the thickness of the ion storage layer (5) is 300-500nm; wherein the second transparent oxide conductive layer (7) has a thickness of 30-100nm.
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