CN111061109B - Electrochromic device with asymmetric electrode structure, preparation method and application - Google Patents
Electrochromic device with asymmetric electrode structure, preparation method and application Download PDFInfo
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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
- G02F1/155—Electrodes
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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
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
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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
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
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- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
本发明属于电致变色器件技术领域，公开了一种具有不对称电极结构的电致变色器件、制备方法及应用，采用丙烯酰胺作为单体，N,N‑二甲基双丙烯酰亚胺作为交联剂，过硫酸铵作为热引发剂，四甲基乙二胺作为催化剂，氯化钠作为电解质制备离子导电型聚丙烯酰胺水凝胶作为离子导电层；在透明的ITO电极上沉积均匀的阴极变色薄膜作为电致变色功能层，将导电型水凝胶均匀放置在电致变色层上；再将易于氧化的电化学物质或者易于氧化的金属离子，放置在导电层的边缘，用保鲜膜封装，得到了基于不对称电极结构的电致变色器件。本发明制备了性质优良的器件。器件结构简单，且省去了复杂的封装过程；具有很优异的电致变色性质。
The invention belongs to the technical field of electrochromic devices, and discloses an electrochromic device with an asymmetric electrode structure, a preparation method and an application thereof. Acrylamide is used as a monomer, and N,N-dimethylbisacrylimide is used as a Cross-linking agent, ammonium persulfate as thermal initiator, tetramethylethylenediamine as catalyst, sodium chloride as electrolyte to prepare ion-conducting polyacrylamide hydrogel as ion-conducting layer; uniformly deposited on transparent ITO electrode. The cathodic discoloration film is used as the electrochromic functional layer, and the conductive hydrogel is evenly placed on the electrochromic layer; and then the easily oxidized electrochemical substances or the easily oxidized metal ions are placed on the edge of the conductive layer. After encapsulation, an electrochromic device based on an asymmetric electrode structure was obtained. The present invention produces devices with excellent properties. The structure of the device is simple, and the complicated packaging process is omitted; it has excellent electrochromic properties.
Description
Technical Field
The invention belongs to the technical field of electrochromic devices, and particularly relates to an electrochromic device with an asymmetric electrode structure, a preparation method and application.
Background
At present, the existing electrochromic intelligent windows, such as the intelligent dimming windows on commercial boeing airplanes, are generally inorganic metal oxide materials, have the disadvantages of nonuniform color change and slow color change, and the preparation and packaging of devices are complicated, which is caused by the limitation of the materials; the anti-glare rearview mirror of an automobile is generally prepared and packaged by a liquid organic electrochromic material, and has safety problems, such as easy liquid leakage and the like. Currently, the closest prior art: with the improvement of the technological level and the development of the society, the intelligent color-changing field is more and more concerned by people as a new field due to the wide potential application of the intelligent color-changing field in intelligent windows, automatic control type anti-dazzling rearview mirrors, reflection type display and the like. By electrochromic device is meant a device that reversibly changes color or transparency upon application of a suitable voltage stimulus.
To date, some electrochromic products have been developed and put into use, including some anti-glare rear view mirrors for automobiles, smart color windows for airplanes, and the like, but there are still some problems that exist and restrict the development of electrochromic devices. At present, the mature electrochromic materials are few in application, mainly tungsten trioxide, the material color is difficult to realize multicolor, a magnetron sputtering method is required to be a large-scale instrument, the cost is high, the preparation requirement is high, and the response speed of a device is low due to the limitation of the properties of the material; another material, namely an ultraviolet fine micromolecule electrochromic material, is a highly toxic and harmful material, is difficult to prepare into a solid film, is generally applied in a liquid device form), has single color, is complex in device preparation process, slow in response speed and poor in reversibility, and most devices are in liquid state and the like. Compared with a liquid device, the solid device is safer and has better color change property, but the solid device has a complicated structure and packaging problems, the solid device is generally composed of an electrochromic layer, an ion conducting layer and an ion storage layer, each layer part needs to be constructed into a thin film to be assembled together, and the current laminating packaging process is not mature; but greatly influences the industrialization process and limits the development of the method in practical application.
In summary, the problems of the prior art are as follows: the existing electrochromic products have the defects of single color, complex device preparation process, slow response speed and poor reversibility, and the devices are mostly in liquid state; the complex structure of solid state devices and packaging problems.
The difficulty of solving the technical problems is as follows: 1. for single color, a new material is generally required to be designed, or the existing material is modified to change the spectral absorption change of a substance in oxidation reduction, and long-term exploration and optimization are required; 2. for the problem of complex device process, the structure of the traditional device needs to be improved, all components of the device are organically unified, and a novel design is needed; 3. for the problems of slow response speed and poor reversibility, a proper color-changing material needs to be selected to match with a proper device structure or a novel high-performance material needs to be synthesized by design; 4. most of the current devices are liquid and easy to cause safety problems, and a new device structure needs to be designed to prepare a solid-phase electrochromic material preparation device; 5. for the problems of complex structure and packaging of solid-state devices, efficient and simple device preparation methods need to be designed and appropriate materials are utilized.
The significance of solving the technical problems is as follows: the solution to the above problems is helpful for promoting the progress of electrochromic industrialization, promoting the development of new applications of electrochromic devices, and contributing to the vigorous development of the electrochromic industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an electrochromic device with an asymmetric electrode structure, a preparation method and application.
The invention is realized in such a way that the preparation method of the electrochromic device with the asymmetric electrode structure comprises the following steps:
firstly, preparing ion conductive polyacrylamide hydrogel serving as an ion conductive layer by using acrylamide as a monomer, N, N-dimethyl bisacryloyl imine as a cross-linking agent, ammonium persulfate as a thermal initiator, tetramethylethylenediamine as a catalyst and sodium chloride as an electrolyte;
secondly, depositing a uniform cathode color-changing film on a transparent ITO electrode to serve as an electrochromic functional layer, and uniformly placing conductive hydrogel on the electrochromic layer;
and thirdly, placing the electrochemical substance easy to oxidize or the metal ions easy to oxidize at the edge of the conducting layer, and packaging the conducting layer by using a preservative film to obtain the electrochromic device based on the asymmetric electrode structure.
Further, the synthesizing of the first ion conductive layer material includes: the ionic conducting layer is made of electrolyte-doped hydrogel, 4.773g of acrylamide monomer is dissolved in 30mL of deionized water, and 5mg of N, N-dimethyl bisacryloyl imine, 10mg of ammonium persulfate, 2g of sodium chloride and 20mg of tetramethyl ethylene diamine are added; and sealing the obtained solution, placing the solution in a blast oven, standing at 60 ℃ for 12 hours to obtain colorless and transparent polyacrylamide hydrogel, and washing with deionized water for multiple times to remove residual monomers.
Further, the second step includes: the electrochromic material with the cathode color-changing capability is deposited on the ITO electrode to form a uniform and transparent film.
Further, the electrochromic material with the cathode color-changing capability is WO3，PEDOT:PSS。
Further, the third step includes: and uniformly covering the prepared hydrogel conducting layer on the prepared ITO electrode deposited with the electrochromic layer, placing the substance easy to oxidize at the edge of the ion conducting layer, and packaging the device by using a preservative film to obtain the electrochromic device with the asymmetric electrode structure.
Further, the electrochemical substance easy to oxidize is copper, aluminum, iron and silver; the metal ions easy to oxidize are vanadium ions and chromium ions in low valence state.
Another object of the present invention is to provide an electrochromic device manufactured by the method for manufacturing an electrochromic device having an asymmetric electrode structure. The device has an asymmetric electrode structure and is simple to prepare. Compared with the prior art, the preparation method has the advantages of low cost, easily obtained raw materials, easier preparation into a solid state and contribution to further application of devices.
Another object of the present invention is to provide a use of the electrochromic device in smart windows.
Another object of the present invention is to provide an application of the electrochromic device in an automatic control type anti-glare rearview mirror.
It is another object of the present invention to provide a use of the electrochromic device in a reflective display.
In summary, the advantages and positive effects of the invention are: the electrochromic device adopts cathode color-changing materials deposited on commercial Indium Tin Oxide (ITO) glass as an electrochromic functional layer, polyacrylamide hydrogel doped with electrolyte as an ion conducting layer, electrochemical active materials which are easy to be oxidized as an ion storage layer, and the device is obtained by packaging with a common preservative film. As shown in fig. 6, the device of the present invention has a simple structure and a good color change effect, and omits a complicated packaging process, which is helpful for the development of solid electrochromic devices in practical applications.
The invention combines the conductive hydrogel with the cathode and anode functional materials with good electrochemical activity to prepare the device with excellent properties. The device has a simple structure, and a complex packaging process is omitted, so that the device is more suitable for actual production. As shown in fig. 6, compared with the prior art, the device of the present invention has excellent electrochromic properties, and has good application prospects in the field of intelligent color-changing windows, such as electrochromic dimming intelligent windows (fig. 4 shows good uniformity and electrochromic performance by a large-area device), reflective energy-saving billboards, and the like. The raw materials used in the invention are all common commercialized mature substances, the complex synthesis is removed, the preparation process is simple, no organic solvent is used in the whole process, the common organic electrochromic material using water as a solvent generally uses toxic and harmful organic solvents to dissolve organic functional materials, a large amount of organic solvents can be used in the preparation process, the environment and human body are damaged, and the preparation method conforms to the current environment-friendly theme. Reduces the damage to the environment and the human body, has good repeatability and is very suitable for industrialized application.
Drawings
FIG. 1 shows an electrochromic device with an asymmetric electrode structure, a method for manufacturing the electrochromic device, and an application of the electrochromic device
FIG. 2 is a photograph (4 cm area) of an electrochromic device based on an asymmetric electrode structure in a colorless and blue reversible manner according to an embodiment of the present invention2) (ii) a Area 2 cm.
Fig. 3 is a schematic diagram of the corresponding spectrum change of the electrochromic device based on the asymmetric electrode structure in the colorless and blue reversible conversion provided by the embodiment of the invention.
FIG. 4 is a photograph showing the reversible conversion between colorless and blue colors of a large-area electrochromic device based on an asymmetric electrode structure provided by an embodiment of the invention (the area is 50 cm)2)。
Fig. 5 shows transmittance change of colorless and blue reversibly switchable 3000 seconds for a large area electrochromic device based on an asymmetric electrode structure provided by an embodiment of the invention.
Fig. 6 is a comparison of a large-area electrochromic device based on an asymmetric electrode structure provided by an embodiment of the present invention with the prior art.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In view of the problems in the prior art, the present invention provides an electrochromic device with an asymmetric electrode structure, a method for manufacturing the electrochromic device, and an application of the electrochromic device, and the present invention is described in detail below with reference to the accompanying drawings.
As shown in fig. 1, a method for manufacturing an electrochromic device having an asymmetric electrode structure according to an embodiment of the present invention includes the following steps:
s101: preparing ion-conductive polyacrylamide hydrogel serving as an ion-conductive layer by using acrylamide as a monomer, N, N-dimethyl bisacryloyl imine as a cross-linking agent, ammonium persulfate as a thermal initiator, tetramethylethylenediamine as a catalyst and sodium chloride as an electrolyte;
s102: depositing uniform cathodic discolouration films on transparent ITO electrodes (e.g. WO)3PEDOT: PSS, etc.) as an electrochromic functional layer, a conductive hydrogel was uniformly placed on the electrochromic layer;
s103: and then placing easily-oxidized electrochemical substances such as some common metal wires (copper, aluminum, iron, silver and the like) or easily-oxidized metal ions (low-valence vanadium ions, chromium ions and the like) at the edge of the conducting layer, and packaging with a preservative film to obtain the electrochromic device based on the asymmetric electrode structure.
The preparation method of the electrochromic device with the asymmetric electrode structure provided by the embodiment of the invention specifically comprises the following steps: (1) synthesizing an ion conductive layer material; (2) preparing an electrode with an electrochromic functional layer; (3) and (5) constructing an electrochromic device.
(1) Synthesis of ion conductive layer material: the ion conducting layer material is electrolyte-doped hydrogel, 4.773g of acrylamide monomer is dissolved in 30mL of deionized water, and 5mg of N, N-dimethyl bisacryloyl imine, 10mg of ammonium persulfate, 2g of sodium chloride and 20mg of tetramethyl ethylene diamine are added. And sealing the obtained solution, placing the solution in a blast oven, standing at 60 ℃ for 12 hours to obtain colorless and transparent polyacrylamide hydrogel, and washing with deionized water for multiple times to remove residual monomers.
(2) Preparation of an electrode with an electrochromic functional layer: electrochromic materials to be provided with cathodically coloring capability (e.g. WO)3PEDOT: PSS, etc.) was deposited on the ITO electrode to form a uniform transparent film.
(3) Construction of electrochromic devices: uniformly covering the hydrogel conducting layer prepared in the step (1) on the ITO electrode deposited with the electrochromic layer prepared in the step (2), placing substances easy to oxidize (such as metals like iron, copper, aluminum, silver and the like or metal ions easy to oxidize, such as low-valence vanadium ions, chromium ions and the like) at the edge of the ion conducting layer, and packaging the device by using a preservative film. Thus obtaining the electrochromic device with the asymmetric electrode structure.
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1
The preparation method of the electrochromic device with the asymmetric electrode structure provided by the embodiment of the invention specifically comprises the following steps:
(1) synthesis of ion conductive layer material: the ion conducting layer material is electrolyte-doped hydrogel, 4.773g of acrylamide monomer is dissolved in 30mL of deionized water, and 5mg of N, N-dimethyl bisacryloyl imine, 10mg of ammonium persulfate, 2g of sodium chloride and 20mg of tetramethyl ethylene diamine are added. And sealing the obtained solution, placing the solution in a blast oven, standing at 60 ℃ for 12 hours to obtain colorless and transparent polyacrylamide hydrogel, and washing with deionized water for multiple times to remove residual monomers.
(2) Preparation of an electrode with an electrochromic functional layer: an electrochromic material with cathodic discoloration capability (commercial PEDOT: PSS dispersion) was deposited on the ITO electrode by spin coating to form a uniform transparent film.
(3) Construction of electrochromic devices: and (3) uniformly covering the hydrogel conducting layer prepared in the step (1) on the ITO electrode deposited with the electrochromic layer prepared in the step (2), placing an easily-oxidized substance (silver colloid here) on the edge of the ion conducting layer, and packaging the device by using a preservative film. The electrochromic device with the asymmetric electrode structure of the invention can be obtained.
As shown in figure 3, the working voltage of the electrochromic glass prepared by the invention is about-1.5V, the device can be converted from a colorless transparent state into a blue opaque state when the voltage of-1.5V is applied, and can be changed back to the original colorless transparent state when the opposite voltage of + 0.4V is applied, and the color change intensity of the device is almost not changed after the device is cycled for many times.
To demonstrate its application in the field of smart windows, large area devices were prepared and tested for uniformity, and found to be uniformly discolored with high contrast, as shown in fig. 4. And figure 5 shows that there is no decay in the discoloration strength of the device above the discoloration-fade cycle of 3000 seconds.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A preparation method of an electrochromic device with an asymmetric electrode structure is characterized by comprising the following steps:
firstly, preparing ion conductive polyacrylamide hydrogel serving as an ion conductive layer by using acrylamide as a monomer, N, N-dimethyl bisacryloyl imine as a cross-linking agent, ammonium persulfate as a thermal initiator, tetramethylethylenediamine as a catalyst and sodium chloride as an electrolyte;
secondly, depositing a uniform cathode color-changing film on a transparent ITO electrode to serve as an electrochromic functional layer, and uniformly placing conductive hydrogel on the electrochromic layer;
thirdly, placing the electrochemical substance easy to oxidize or the metal ions easy to oxidize at the edge of the conducting layer, and packaging the conducting layer by using a preservative film to obtain the electrochromic device based on the asymmetric electrode structure;
the first step of synthesizing the ion conducting layer material comprises the following steps: the ionic conducting layer is made of electrolyte-doped hydrogel, 4.773g of acrylamide monomer is dissolved in 30mL of deionized water, and 5mg of N, N-dimethyl bisacryloyl imine, 10mg of ammonium persulfate, 2g of sodium chloride and 20mg of tetramethyl ethylene diamine are added; and sealing the obtained solution, placing the solution in a blast oven, standing at 60 ℃ for 12 hours to obtain colorless and transparent polyacrylamide hydrogel, and washing with deionized water for multiple times to remove residual monomers.
2. The method of preparing an electrochromic device having an asymmetric electrode structure according to claim 1, wherein the second step includes: the electrochromic material with the cathode color-changing capability is deposited on the ITO electrode to form a uniform and transparent film.
3. The method of claim 2, wherein the electrochromic material with cathodically coloring capability is WO3，PEDOT:PSS。
4. The method of preparing an electrochromic device having an asymmetric electrode structure according to claim 1, wherein the third step includes: and uniformly covering the prepared hydrogel conducting layer on the prepared ITO electrode deposited with the electrochromic layer, placing the substance easy to oxidize at the edge of the ion conducting layer, and packaging the device by using a preservative film to obtain the electrochromic device with the asymmetric electrode structure.
5. The method of claim 4, wherein the easily oxidizable electrochemical material is copper, aluminum, iron, silver; the metal ions easy to oxidize are vanadium ions and chromium ions in low valence state.
6. An electrochromic device prepared by the preparation method of the electrochromic device with the asymmetric electrode structure as claimed in any one of claims 1 to 5.
7. Use of an electrochromic device according to claim 6 in smart windows.
8. Use of an electrochromic device according to claim 6 in an automatically controlled anti-glare rear view mirror.
9. Use of an electrochromic device according to claim 6 in a reflective display.
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| CN113219753B (en) * | 2021-05-08 | 2022-05-13 | 山东大学 | Reversible self-driven electrochromic flexible display device and preparation method and application thereof |
| CN113568235A (en) * | 2021-06-28 | 2021-10-29 | 浙江工业大学 | A kind of electrochromic device and preparation method based on multifunctional hydrogel electrolyte |
| CN113568236A (en) * | 2021-06-29 | 2021-10-29 | 浙江工业大学 | Electrochromic device based on high-performance hydrogel electrolyte and preparation method and application |
| CN116266022B (en) * | 2021-12-17 | 2025-04-08 | 南京林业大学 | An all-in-one liquid electrochromic device and preparation method thereof |
| CN115196885B (en) * | 2022-08-15 | 2024-01-26 | 安徽理工大学 | A multi-color high cycle stability CeO2/PANI electrochromic film and its preparation method |
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