CN110389479B - Electrodeposition method for coating electrochromic films - Google Patents
Electrodeposition method for coating electrochromic films Download PDFInfo
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- CN110389479B CN110389479B CN201910572787.1A CN201910572787A CN110389479B CN 110389479 B CN110389479 B CN 110389479B CN 201910572787 A CN201910572787 A CN 201910572787A CN 110389479 B CN110389479 B CN 110389479B
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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
- G02F1/1506—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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
Abstract
An electrodeposition process for coating an electrochromic film, said electrodeposition process comprising the steps of: providing a conductive substrate; pretreating the conductive substrate to remove pollutants on the surface of the conductive substrate; preparing an electrodeposition solution, wherein the electrodeposition solution is a mixture of hydrochloric acid, sodium tungstate dihydrate, oxalic acid and metal chloride salt; preparing a counter electrode; disposing the counter electrode on the conductive substrate; and vertically immersing the conductive substrate and the counter electrode into the electrodeposition solution, and applying voltage to the counter electrode and the conductive substrate, wherein the counter electrode is set to be positively biased, and the conductive substrate is set to be negatively biased so as to form a uniform tungsten-based blue film on the surface of the cathode conductive substrate to manufacture the electrochromic device. The electrodeposition process has at least one or more of the following advantages: the method has the advantages of no vacuum, easy control, rapid prototyping, material saving and high cost performance. The invention also includes an electrochromic device prepared by the above method.
Description
Technical Field
The invention belongs to the technical field of electrochromism, in particular to an electrodeposition method for coating an electrochromism film.
Background
Currently, most of the sunglasses with adjustable colors use photochromic materials. However, the transition between the clear and tinted states of a photochromic lens requires 5 minutes or more and is not manually controllable, resulting in a poor user experience. Therefore, the electrochromic material with higher color changing speed and artificially controllable provides better technical support for the color-changing lens. Meanwhile, the electrochromic material can be triggered to change color by light in a mode of embedding a photoresistor, and two modes of manual control and automatic control are realized. The electrochromic material is also applied to other fields, for example, when the electrochromic material is used on a smart window, heat can be automatically blocked, so that the energy consumption of an air conditioner is reduced; the anti-glare rearview mirror of the automobile can quickly change color to absorb the light of a high beam of a vehicle behind, and reduce the impact of the vehicle lights behind on the vision of a driver when the driver drives at night; as another example, electrochromic material compatible optical display systems may provide hardware support for enhancing visual performance of head-up displays (HUDs) and Augmented Reality (ARs). Based on the above broad application prospects, electrochromic devices have been widely used in the industrial and academic fieldsAttention is paid to the method. Among them, tungsten trioxide (WO)3) Is the most widely studied electrochromic material, and the color of the electrochromic device can be changed by changing the voltage applied to the tungsten trioxide.
At present, electrochromic tungsten trioxide thin films are generally prepared by one of a cvd (chemical Vapor deposition) method, a sputtering method, an electron beam evaporation method, a plasma polymerization method, and a spin coating method. However, each of the above methods has disadvantages that affect the application thereof. For example, the CVD method requires very expensive equipment and high temperature of about 500 ℃ to maintain the deposition rate, and it is also difficult to obtain highly conformal films (conformal films) in a particular shape. The sputtering method requires complicated equipment, a vacuum chamber, and inert or reactive gas, which increases manufacturing costs without doubt. Electron beam evaporation may contaminate the sample surface, since X-rays cause ionization of gas molecules. The plasma polymerization process also needs to be performed under vacuum conditions, which will certainly increase the cost, and for large-sized thin films, the plasma polymerization process has a low deposition rate characteristic resulting in deposition of only very thin films. Finally, with regard to the spin coating method, although a vacuum environment and expensive equipment are not used or are less used in manufacturing a thin film coating layer, the spin coating process is limited by a rotating plate, and thus only a small-sized sample can be coated. Meanwhile, the method has high requirements on the dropping mode and the skill of the spin-coating liquid of operators.
Disclosure of Invention
In view of the above, the present invention provides an electrodeposition method for coating an electrochromic film and an electrochromic device that are simple and low in manufacturing cost, to solve the above problems.
An electrodeposition process for coating an electrochromic film comprising the steps of:
STEP 1: providing a first conductive substrate and a second conductive substrate;
STEP 2: pretreating the first conductive substrate and the second conductive substrate to remove pollutants on the surfaces of the first conductive substrate and the second conductive substrate;
STEP 3: preparing an electrodeposition solution, wherein the electrodeposition solution is a mixture of hydrochloric acid, sodium tungstate dihydrate, oxalic acid and metal chloride salt;
STEP 4: preparing a counter electrode, namely arranging an anode oxygen evolution reaction catalyst on a first conductive substrate to form the counter electrode;
STEP5: and vertically immersing the second conductive substrate and a counter electrode into the electrodeposition solution, and applying a voltage to the counter electrode and the second conductive substrate, wherein the counter electrode is set to be positively biased, and the second conductive substrate is set to be negatively biased so as to form a uniform tungsten-based blue film on the surface of the second conductive substrate of the cathode to manufacture the electrochromic device.
Further, the first conductive substrate and the second conductive substrate are FTO glass or ITO glass.
Further, in STEP2, the first and second conductive substrates are pretreated by washing the first and second conductive substrates with acetone, ethanol, and deionized water, respectively, in an ultrasonic bath.
Further, the anode oxygen evolution reaction catalyst is IrO2, RuO2 or Fe2O3.
Further, STEP6 is included after STEP5, and the second conductive substrate coated with the tungsten-based blue film is cleaned to remove metal salts on the surface by soaking the tungsten-based blue film in deionized water and drying in air for a period of time in STEP 6.
Further, after STEP6, the first conductive substrate coated with the tungsten-based blue film was annealed in air at 100-500 ℃ for 1-3 hours and cooled to room temperature.
Further, a voltage of at least 0.3V to 1.2V is applied between the anode and the cathode, and after a certain voltage is applied, a constant voltage mode is maintained, and the current naturally drops until changing to the next voltage value.
An electrochromic device includes a conductive substrate, and a tungsten-based blue film coated on the conductive substrate.
Compared with the prior art, the electrodeposition method for coating the electrochromic film provided by the invention has at least one or more of the following advantages: the method has the advantages of no vacuum, easy control, rapid prototyping, material saving and high cost performance. Therefore, the electrodeposition method can facilitate commercialization in the electrochromic industry.
Drawings
FIG. 1 is a flow chart of an electrodeposition process for coating an electrochromic film according to the present invention.
Fig. 2 is a schematic view of a structure of a counter electrode prepared in the course of performing the electrodeposition method for coating an electrochromic film of fig. 1.
Fig. 3 is a schematic structural view of an electrochromic device fabricated by an electrodeposition method for coating an electrochromic film of fig. 1.
Detailed Description
Specific examples of the present invention will be described in further detail below. It should be understood that the description herein of embodiments of the invention is not intended to limit the scope of the invention.
Fig. 1 is a flow chart of an electrodeposition method for coating an electrochromic film according to the present invention. The electrodeposition method for coating an electrochromic film comprises the steps of:
STPE1 a first conductive substrate 10 and a second conductive substrate 11 are provided.
The first and second conductive substrates 10 and 11 may be FTO (F-doped Tin Oxide) glass or ito (indium Tin Oxide) glass. In this embodiment, the first and second conductive substrates 10 and 11 are both FTO glass, and the FTO glass has a sheet resistance of 15 Ω/sq. It is conceivable that the first and second conductive substrates 10 and 11 are not limited to the FTO glass having 15 Ω/sq. For example, in other embodiments of the present invention, the sheet resistance may be 7 Ω/sq to 20 Ω/sq. It will be appreciated that a greater sheet resistance should be coordinated with a higher applied voltage.
STPE2 the first and second conductive substrates 10, 11 are pretreated to remove contaminants from the surfaces of the first and second conductive substrates 10, 11. The contaminants may be dust, grease and other impurities.
When the first and second conductive substrates 10 and 11 are cleaned of contaminants, they must be washed with acetone, ethanol and deionized water in an ultrasonic bath in order.
STPE3 an electrodeposition solution was prepared that was a mixture of hydrochloric acid, sodium tungstate dihydrate, oxalic acid, and a metal chloride salt. Specifically, the preparation method of the electrodeposition solution is to mix hydrochloric acid and a sodium tungstate dihydrate solution to prepare a green-yellow tungstic acid solution. Oxalic acid was added to make a clear and stable solution at room temperature. The metal chloride salt is then added to the solution. The metal chloride salt can be one or more of sodium chloride, potassium chloride, nickel chloride and cobalt chloride.
STPE4 preparation of the counter electrode 12 by disposing the anodic oxygen evolution reaction catalyst 121 on a first conductive substrate 10 to form the counter electrode 12, as shown in FIG. 2
In such a two-electrode system, the counter electrode is considered to have a crucial influence on achieving a uniform thin film. The counter electrode 12 functions to promote an anodic Oxygen Evolution Reaction (OER). Since the electrochemical deposition process of the present invention is to perform an electron reduction reaction on the surface of the second conductive substrate 11 as a cathode, i.e., FTO glass, to deposit a tungsten oxide film, an electron-losing oxidation reaction of Oxygen Evolution (OER) occurs correspondingly to the counter electrode as an anode, i.e.: 2H2O→O2And the promotion of the oxygen evolution reaction at the anode promotes the cathode film forming process correspondingly. Therefore, those OER catalysts which can be acid-resistant are preferred. The OER catalyst may be applied to the first conductive substrate 10, i.e., FTO glass, by sputter evaporation or brush coating to form a counter electrode 12, e.g., IrO2，RuO2，Fe2O3. In this example, the OER catalyst is Fe2O3。Fe2O3Has good film promotion.
STEP5 is to vertically dip both the second conductive substrate 11 and the counter electrode 12 into the electrodeposition solution and apply a voltage to the counter electrode 12, wherein the counter electrode 12 is set to be positively biased and the second conductive substrate 11 is set to be negatively biased to form a uniform tungsten-based blue film 13 on the surface of the second conductive substrate 10 as a cathode to produce an electrochromic device, as shown in fig. 3. The voltage and reaction time may also be varied depending on the size of the FTO glass used for the second conductive substrate 12. For example, 0.2V to 1.2V, and a coating time of 2 to 10 minutes, are suitable for 5 x 5FTO glass. The coating time is 1V to 10V and 3 to 15 minutes on 10cm x 10cm FTO glass. In applying the voltage, the voltage may be applied twice, with the voltage applied a first time being less than the voltage applied a second time. Specifically, a voltage of at least 0.3V to 1.2V may be applied between the anode and the cathode, and after a certain voltage is applied, a constant voltage mode is maintained, and the current naturally drops until changing to the next voltage value. It should be noted here that the purpose of vertically immersing the second conductive substrate 11 and the counter electrode 12 in the electrodeposition solution is to place the counter electrode 12 as an anode and the second conductive substrate 11 as a cathode in parallel facing each other. In addition, it is conceivable to sandwich the second conductive substrate 11 and the counter electrode 12 by two conductive clips, respectively, to apply a voltage to the second conductive substrate 11 and the counter electrode 12.
STEP6 the second conductive substrate 11 coated with the tungsten-based blue film 13 is cleaned by soaking the film in deionized water and drying in air for a period of time to remove other metal salts on the surface, such as one or more of sodium chloride, potassium chloride, nickel chloride, cobalt chloride.
After STEP6, the second conductive substrate 11 coated with the tungsten-based blue film 13 can be further annealed in air at 100-500 ℃ for 1-3 hours and cooled to room temperature.
The electrochromic device manufactured by the manufacturing process comprises a conductive substrate and a tungsten-based blue film coated on the conductive substrate.
The prepared electrochromic device was tested by placing it in 0.1M sulfuric acid and applying 3V to the conductive substrate 10 with a platinum wire as the counter electrode 11. The electrochromic device turned blue within 2 seconds and the cathode bleached within 1 second.
Compared with the prior art, the electrodeposition method for coating the electrochromic film provided by the invention has at least one or more of the following advantages: the method has the advantages of no vacuum, easy control, rapid prototyping, material saving and high cost performance. Therefore, the electrodeposition method can facilitate commercialization in the electrochromic industry.
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 scope of the present invention, and any modifications, equivalents or improvements that are within the spirit of the present invention are intended to be covered by the following claims.
Claims (8)
1. An electrodeposition process for coating an electrochromic film comprising the steps of:
STEP 1: providing a first conductive substrate and a second conductive substrate;
STEP 2: pretreating the first conductive substrate and the second conductive substrate to remove pollutants on the surfaces of the first conductive substrate and the second conductive substrate;
STEP 3: preparing an electrodeposition solution, wherein the electrodeposition solution is a mixture of hydrochloric acid, sodium tungstate dihydrate, oxalic acid and metal chloride salt;
STEP 4: preparing a counter electrode, namely arranging an anode oxygen evolution reaction catalyst on a first conductive substrate to form the counter electrode;
STEP5: and vertically immersing the second conductive substrate and the counter electrode in the electrodeposition solution, and applying a voltage to the counter electrode and the second conductive substrate, wherein the counter electrode is set to be positively biased, and the second conductive substrate is set to be negatively biased so as to form a uniform tungsten-based blue film on the surface of the second conductive substrate of the cathode to manufacture the electrochromic device.
2. The electrodeposition process for coating an electrochromic film according to claim 1, wherein: the first conductive substrate and the second conductive substrate are FTO glass or ITO glass.
3. The electrodeposition process for coating an electrochromic film according to claim 1, wherein: in STEP2, the first and second conductive substrates are pretreated by washing the first and second conductive substrates with acetone, ethanol, and deionized water, respectively, in an ultrasonic bath.
4. The electrodeposition process for coating an electrochromic film according to claim 1, wherein: the anode oxygen evolution reaction catalyst is IrO2，RuO2Or Fe2O3。
5. The electrodeposition process for coating an electrochromic film according to claim 1, wherein: STEP6 is also included after STEP5, and the second conductive substrate coated with the tungsten-based blue film is cleaned to remove metal salts on the surface by soaking the tungsten-based blue film in deionized water and drying in air for a period of time in STEP 6.
6. The electrodeposition process for coating an electrochromic film according to claim 1, wherein: after STEP6, the second conductive substrate coated with the tungsten-based blue film was also annealed in air at 100-500 ℃ for 1-3 hours and cooled to room temperature.
7. The electrodeposition process for coating an electrochromic film according to claim 1, wherein: in STEP5, the voltage is applied in two times, the voltage applied for the first time being smaller than the voltage applied for the second time.
8. The electrodeposition process for coating an electrochromic film according to claim 7, wherein: applying a voltage of at least 0.3V to 1.2V between the anode and the cathode, maintaining a constant voltage mode after applying a certain voltage, the current naturally dropping until changing to the next voltage value.
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| CN113050338A (en) * | 2021-03-16 | 2021-06-29 | 宁波伯宇科技有限公司 | Electrochromic device manufacturing process |
| CN115390171B (en) * | 2022-08-17 | 2023-10-13 | 鹤山市嘉米基光电科技有限公司 | Variable-color high-reflection reflector and preparation method thereof |
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| CN103984177A (en) * | 2014-05-07 | 2014-08-13 | 哈尔滨工业大学 | Electrochromic material structure, preparation method and intelligent window thereof |
| CN107142508A (en) * | 2017-03-31 | 2017-09-08 | 中国航发北京航空材料研究院 | A kind of electrochemical doping method of electrochomeric films |
| CN107153311A (en) * | 2017-06-06 | 2017-09-12 | 中国科学院上海硅酸盐研究所 | Based on tungstic acid and Prussian blue double-function device |
| CN109437241A (en) * | 2018-11-28 | 2019-03-08 | 浙江大学 | Prussian blue/Tungsten Trioxide Electrochromic Films of one kind and preparation method thereof |
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| CN105060733A (en) * | 2015-07-16 | 2015-11-18 | 浙江大学 | Electrochromic film adopting amorphous/crystalline tungsten trioxide core-shell structure and preparation method of film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103984177A (en) * | 2014-05-07 | 2014-08-13 | 哈尔滨工业大学 | Electrochromic material structure, preparation method and intelligent window thereof |
| CN107142508A (en) * | 2017-03-31 | 2017-09-08 | 中国航发北京航空材料研究院 | A kind of electrochemical doping method of electrochomeric films |
| CN107153311A (en) * | 2017-06-06 | 2017-09-12 | 中国科学院上海硅酸盐研究所 | Based on tungstic acid and Prussian blue double-function device |
| CN109437241A (en) * | 2018-11-28 | 2019-03-08 | 浙江大学 | Prussian blue/Tungsten Trioxide Electrochromic Films of one kind and preparation method thereof |
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Effective date of registration: 20220714 Address after: No. 688, FenHu Avenue, Lili Town, Wujiang District, Suzhou, Jiangsu 215211 Patentee after: Suzhou Boyu Photoelectric Technology Co.,Ltd. Address before: 314100 Room 201, building E4, No. 555, Chuangye Road, Dayun Town, Jiashan County, Jiaxing City, Zhejiang Province Patentee before: Jiaxing Flash New Materials Co.,Ltd. |