阅读说明：本技术 一种电致变色薄膜及其制备方法和设备 (Electrochromic film and preparation method and equipment thereof ) 是由 赵强国 郝李伟 丁锋 王晨鑫 王亚飞 贲晓燕 王兰芳 于 2021-10-25 设计创作，主要内容包括：一种电致变色薄膜及其制备方法和设备,其主要涉及功能材料领域。本发明提供的电致变色薄膜制备方法制备的对电极层具有稳定可逆氧化还原反应,与电致变色层性能相兼容,响应速度快,且两极所注入的电荷量相近,各层材料均有较好的匹配性和耐久性；制备所得的电致变色薄膜具备良好的电致变色性能；此薄膜制备设备采用精密涂布方法进行涂布,可精确控制电解质层涂布厚度,使涂布更加均匀稳定,提升产品质量；设备在WO-(3)薄膜涂布电解质层后,可与NiO-(x)薄膜进行复合后直接得到电致变色膜,减少了电解质层被污染的时间,提升产品质量,减少生产成本。故本发明提供的电致变色薄膜及其制备方法和设备,具有重要的工业推广应用价值。(An electrochromic film and a preparation method and equipment thereof, which mainly relate to the field of functional materials. The counter electrode layer prepared by the preparation method of the electrochromic film provided by the invention has stable reversible redox reaction, is compatible with the electrochromic layer in performance, has high response speed, has similar charge quantity injected into the two electrodes, and has better matching property and durability; the prepared electrochromic film has good electrochromic performance; the film preparation equipment adopts a precise coating method for coating, can precisely control the coating thickness of the electrolyte layer, enables the coating to be more uniform and stable, and improves the product quality; the apparatus is described in WO 3 After the thin film is coated with the electrolyte layer, NiO can be added x The electrochromic film is directly obtained after the film is compounded, so that the time for polluting an electrolyte layer is reduced, the product quality is improved, and the production cost is reduced. Therefore, the electrochromic film, the preparation method and the equipment thereof provided by the invention have important functionsThe industrial popularization and application value.)

1. The preparation method of the electrochromic film is characterized by comprising the following steps of: selecting a substrate, and respectively preparing amorphous WO on the substrate by a magnetron sputtering method₃Film and nanocrystalline structure NiO_xA film; mixing EDOT-C₆F₁₃-LiCLO₄Pre-dispersing in a solvent to obtain a pre-dispersion solution; the predispersed solution was filtered and applied to the WO by slot coating₃A film which is thermally cured once with the NiO_xAnd compounding the film, and performing secondary thermosetting to obtain the electrochromic film.

2. The method for preparing electrochromic film according to claim 1, wherein the solvent is one or a mixture of several of methanol, xylene, acetonitrile, toluene, ethyl acetate, acetone, butanone and methyl isobutyl ketone in any proportion.

3. The method for preparing an electrochromic film according to claim 1, wherein the substrates are two sheets and are both ITO transparent conductive films.

4. The method for preparing an electrochromic film according to claim 3, wherein the predispersed solution is filtered and then applied to the WO by slit coating₃Film of the WO₃Forming a first electrolyte layer on the thin film;

with the NiO_xThin film lamination is carried out on the NiO_xForming a second electrolyte layer on the film; the thickness of the first electrolyte layer and the thickness of the second electrolyte layer are both 5-8 mu m.

5. The method for preparing an electrochromic film according to claim 4, wherein the primary thermal curing and the secondary thermal curing are performed at 50 to 150 ℃.

6. The method for preparing an electrochromic film according to any one of claims 1 to 5, wherein the EDOT-C is performed while performing pre-dispersion₆F₁₃-LiCLO₄And the mass ratio of the solvent is 92: 8.

7. an electrochromic film prepared by the method for preparing an electrochromic film according to any one of claims 1 to 6.

8. The electrochromic film according to claim 7, wherein the electrochromic film is formed in a thickness directionSequentially comprises a first ITO conductive film and WO₃Electrochromic layer composed of thin film, first electrolyte layer, second electrolyte layer, NiO_xA counter electrode layer formed of a thin film, and a second ITO conductive film.

9. An apparatus for preparing the electrochromic film according to claim 7, wherein the apparatus comprises, in the process flow direction, a number 1 unwinding device, a slit coating device, a thermosetting device, a laminating device and a winding device, and a number 2 unwinding device is further disposed between the thermosetting device and the laminating device, so that the thermosetting film and the film of the number 2 unwinding device can be laminated in the laminating device.

10. The apparatus of claim 9, wherein the unwinding device No. 1, the slit coating device, the thermosetting device, the combining device and the winding device are sequentially in transmission connection, and the unwinding device No. 2 and the combining device are in transmission connection; the thermosetting device is also provided with a deviation rectifying device for rectifying the deviation of the film in the thermosetting device; and the outlet end of the composite device is also provided with a static removing device.

Technical Field

The invention relates to the field of functional materials, in particular to an electrochromic film and a preparation method and equipment thereof.

Background

The electrochromic material has the characteristics of capability of controlling light energy, continuous adjustability of transmitted light intensity, capability of eliminating glare of a vehicle rearview mirror, open-circuit memory function and the like, and has wide application prospects in architectural windows and vehicle glass.

In the prior art, the electrochromic material has the following main problems: uneven coloration leads to local coloration close to the electrodes and even irreversible degradation of the material; the color is single, and the optical performance is poor; since the ions need to diffuse through the lattice, the color conversion is slow; the ion implantation and extraction can respectively cause the tensile stress or compressive stress state change of the thin film layer, so that the thin film layer cracks or falls off.

Disclosure of Invention

The invention aims to provide an electrochromic film and a preparation method and equipment thereof, which can solve the problems that the local coloring is caused close to an electrode and even the irreversible degradation of materials occurs due to the 'uneven coloring' in the prior art; the color is single, and the optical performance is poor; since the ions need to diffuse through the lattice, the color conversion is slow; the ion implantation and extraction can respectively cause the tensile stress or compressive stress state change of the thin film layer, so that the thin film layer cracks or falls off. "to the technical problem.

The technical problem to be solved by the invention is realized by adopting the following technical scheme.

The invention provides a preparation method of an electrochromic film, which comprises the following steps: selecting a substrate, and respectively preparing amorphous WO on the substrate by a magnetron sputtering method₃Film and nanocrystalline structure NiO_xA film; mixing EDOT-C₆F₁₃-LiCLO₄Pre-dispersing in a solvent to obtain a pre-dispersion solution; the predispersed solution was filtered and applied to the WO by slot coating₃A film which is thermally cured once with the NiO_xAnd compounding the film, and performing secondary thermosetting to obtain the electrochromic film.

Further, in a preferred embodiment of the present invention, the solvent is one or a mixture of several of methanol, xylene, acetonitrile, toluene, ethyl acetate, acetone, butanone and methyl isobutyl ketone in any proportion.

Further, in the preferred embodiment of the present invention, the substrates are two sheets, and both of the substrates are ITO transparent conductive films.

Further, in a preferred embodiment of the present invention, the predispersed solution is filtered and then applied to the WO by slot coating₃Film of the WO₃Forming a first electrolyte layer on the thin film; with the NiO_xThin film lamination is carried out on the NiO_xForming a second electrolyte layer on the film; the thickness of the first electrolyte layer and the thickness of the second electrolyte layer are both 5-8 mu m.

Further, in a preferred embodiment of the present invention, the first thermal curing and the second thermal curing are performed at 50 to 150 ℃.

Further, in the preferred embodiment of the present invention, the EDOT-C is used in the pre-dispersion₆F₁₃-LiCLO₄And the mass ratio of the solvent is 92: 8.

the embodiment of the invention also provides an electrochromic film, which is prepared by the preparation method of the electrochromic film.

Further, in a preferred embodiment of the present invention, the electrochromic film comprises a first ITO conductive film, and WO in this order along the thickness direction₃Electrochromic layer composed of thin film, first electrolyte layer, second electrolyte layer, NiO_xA counter electrode layer formed of a thin film, and a second ITO conductive film.

The embodiment of the invention also provides equipment for preparing the electrochromic film, which sequentially comprises a No. 1 unwinding device, a slit coating device, a thermosetting device, a compounding device and a winding device along the processing flow direction, wherein a No. 2 unwinding device is arranged between the thermosetting device and the compounding device, so that the film after thermosetting and the film of the No. 2 unwinding device can be compounded in the compounding device.

Further, in a preferred embodiment of the present invention, the number 1 unwinding device, the slit coating device, the thermosetting device, the compounding device and the winding device are sequentially in transmission connection, and the number 2 unwinding device and the compounding device are in transmission connection; the thermosetting device is also provided with a deviation rectifying device for rectifying the deviation of the film in the thermosetting device; and the outlet end of the composite device is also provided with a static removing device.

The electrochromic film, the preparation method and the equipment of the electrochromic film have the advantages that: the counter electrode layer prepared by the film preparation method has stable reversible redox reaction, is compatible with the electrochromic layer, has high response speed, has similar charge quantity injected by the two electrodes, and has better matching property and durability; the film preparation equipment adopts a precise coating method (including but not limited to slit coating, micro-concave coating and the like) for coating, so that the coating thickness of an electrolyte layer can be precisely controlled, the coating is more uniform and stable, and the product quality is improved; the apparatus is described in WO₃After the thin film is coated with the electrolyte layer, NiO can be added_xThe electrochromic film is directly obtained after the film is compounded, so that the time for polluting an electrolyte layer is reduced, the product quality is improved, and the production cost is reduced.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a flow chart of a method for preparing an electrochromic film according to an embodiment of the present invention;

FIG. 2 is a schematic diagram of a structural model of an electrochromic film according to an embodiment of the present invention;

FIG. 3 is a schematic layout diagram of an apparatus for manufacturing an electrochromic film according to an embodiment of the present invention;

FIG. 4 is a graph showing the transmittance of film samples between 380 nm and 1100 nm in the initial stage (a), the coloring stage (b), and the fading stage (c).

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The following describes an electrochromic film, a method for preparing the same, and an apparatus for preparing the same.

Referring to fig. 1, a method for preparing an electrochromic film according to an embodiment of the present invention includes the following steps:

s1, selecting a substrate, and respectively preparing amorphous WO on the substrate by a magnetron sputtering method₃Film and nanocrystalline structure NiO_xA film. Optionally, the substrate is two sheets, and both of the substrates are ITO transparent conductive films.

S2, mixing EDOT-C₆F₁₃-LiClO₄Pre-dispersing in a solvent to obtain a pre-dispersion solution. It is to be noted that, more specifically, EDOT refers to 3, 4-ethylenedioxythiophene; the solvent is one or a mixture of a plurality of methanol, dimethylbenzene, acetonitrile, toluene, ethyl acetate, acetone, butanone and methyl isobutyl ketone in any proportion. In addition, in order to ensure good dispersion effect and solute property of the predispersion solution, in the embodiment of the invention, EDOT-C is adopted during predispersion₆F₁₃-LiClO₄And the mass ratio of the solvent is 92: 8.

s3, filtering the predispersion solution, and coating the predispersion solution on WO by a slit coating method₃Film, thermally cured once with NiO_xCompounding the film, and performing secondary thermosetting to obtain the electrochromic film.

More specifically, the predispersed solution was filtered and applied to WO by the slit coating method₃Films, in WO₃Forming a first electrolyte layer on the thin film; and NiO_xFilm lamination at NiO_xA second electrolyte layer is formed on the film. The first electrolyte layer and the second electrolyte layer are both 5 to 8 μm thick. It should be noted that the "first" and "second" are only divided into two electrolyte layers in this embodiment, and there is no substantial difference in the number or sequence.

In addition, it should be emphasized that in the embodiments of the present invention, in order to ensure good heat curing effect, the first heat curing and the second heat curing are performed at 50 to 150 ℃.

Referring to fig. 2, an embodiment of the present invention further provides an electrochromic film, and the electrochromic film is prepared by the above method for preparing an electrochromic film. Specifically, the electrochromic film comprises a first ITO conductive film and WO in sequence along the thickness direction₃Electrochromic layer composed of thin film, first electrolyte layer, second electrolyte layer, NiO_xA counter electrode layer formed of a thin film, and a second ITO conductive film.

Referring to fig. 3, an embodiment of the present invention further provides an apparatus for preparing the electrochromic film, which sequentially includes a number 1 unwinding device, a slit coating device, a thermosetting device, a laminating device, and a winding device along a processing flow direction, wherein a number 2 unwinding device is further disposed between the thermosetting device and the laminating device, so that the thermosetting film and the film of the number 2 unwinding device can be laminated in the laminating device.

Further specifically, the unwinding device No. 1, the slit coating device, the thermosetting device, the compounding device and the winding device are sequentially in transmission connection, and the unwinding device No. 2 and the compounding device are in transmission connection. It should be noted that the thermosetting device is also provided with a deviation rectifying device for rectifying deviation of the film in the thermosetting device; and the outlet end of the composite device is also provided with a static removing device.

It is emphasized that the methods and apparatus for preparing electrochromic films provided in connection with the above examples are known: by adopting a precise coating method (including but not limited to slit coating, micro-concave coating and the like) for coating, the coating thickness of the electrolyte layer can be precisely controlled, so that the coating is more uniform and stable, and the product quality is improved; WO₃After the thin film is coated with the electrolyte layer, NiO can be added_xThe electrochromic film is directly obtained after the film is compounded, so that the time for polluting an electrolyte layer is reduced, the product quality is improved, and the production cost is reduced; a deviation correcting device is additionally arranged in the equipment, and the stability of the production and operation process of the film is accurately controlled through an infrared sensor, so that the film surface is uniformly and stably coated, and the product quality is improved; the static removing device is additionally arranged in the equipment, the positive and negative charges of the membrane material in the range of 50 cm below the static removing device are kept balanced by ionized air, the product quality is improved, and the safety production is guaranteed.

Referring to fig. 1 to fig. 3, the working principle of the electrochromic film manufacturing apparatus provided in the above embodiment is as follows: first ITO conductive film (with WO)₃Film) starts to be transmitted to a slit coating device for slit coating on the No. 1 unreeling, then the film runs to a thermocuring device to be thermocured through an oven, and the film is stably output to a compounding device under the rectification of a rectifier at a thermocuring outlet, and meanwhile, a second ITO conductive film (attached with NiO) is used_xFilm) is conveyed to the compounding device on the No. 2 unreeling device and enters the compounding device together with the first ITO conductive film, compounding and secondary thermosetting are carried out under the action of an oven in the compounding device, and finally, the static electricity is removed through a static electricity removing instrument at an outlet and then the film is reeled.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

The embodiment provides a preparation method of an electrochromic film, which comprises the following steps:

s1, selecting ITO transparent conductive film asSubstrate on which WO in amorphous state was prepared by magnetron sputtering method, respectively₃Film and nanocrystalline structure NiO_xA film.

S2, mixing EDOT-C₆F₁₃-LiClO₄Pre-dispersing in a solvent to obtain a pre-dispersion solution. Wherein the solvent is methanol; EDOT-C₆F₁₃-LiClO₄And the mass ratio of the solvent is 92: 8.

s3, filtering the predispersion solution, and coating the predispersion solution on WO by a slit coating method₃Film, thermally cured once with NiO_xCompounding the film, performing secondary heat curing to obtain the electrochromic film, wherein the pre-dispersed solution is filtered and coated on WO by a slit coating method₃Films, in WO₃Forming a first electrolyte layer on the thin film; and NiO_xFilm lamination at NiO_xA second electrolyte layer is formed on the film. Wherein the first electrolyte layer and the second electrolyte layer each have a thickness of 6 μm. In addition, the primary thermal curing and the secondary thermal curing are performed under the condition of 100 ℃.

The embodiment also provides an electrochromic film, and the electrochromic film is prepared by the preparation method of the electrochromic film provided by the embodiment. Specifically, the electrochromic film comprises a first ITO conductive film and WO in sequence along the thickness direction₃Electrochromic layer composed of thin film, first electrolyte layer, second electrolyte layer, NiO_xA counter electrode layer formed of a thin film, and a second ITO conductive film.

The embodiment of the invention also provides equipment for preparing the electrochromic film, which sequentially comprises a No. 1 unwinding device, a slit coating device, a thermosetting device, a compounding device and a winding device along the processing flow direction, wherein a No. 2 unwinding device is arranged between the thermosetting device and the compounding device, so that the thermosetting film and the film of the No. 2 unwinding device can be compounded in the compounding device. Specifically, the unwinding device No. 1, the slit coating device, the thermosetting device, the compounding device and the winding device are sequentially in transmission connection, and the unwinding device No. 2 and the compounding device are in transmission connection. It should be noted that the thermosetting device is also provided with a deviation rectifying device for rectifying deviation of the film in the thermosetting device; and the outlet end of the composite device is also provided with a static removing device.

Example 2

The embodiment provides a preparation method of an electrochromic film, which comprises the following steps: s1, respectively preparing amorphous WO on the substrate by adopting ITO transparent conductive film as the substrate and adopting a magnetron sputtering method₃Film and nanocrystalline structure NiO_xA film.

S2, mixing EDOT-C₆F₁₃-LiClO₄Pre-dispersing in a solvent to obtain a pre-dispersion solution. Wherein, the solvent is dimethylbenzene and acetonitrile; EDOT-C₆F₁₃-LiClO₄And the mass ratio of the solvent is 92: 8.

s3, filtering the predispersion solution, and coating the predispersion solution on WO by a slit coating method₃Film, thermally cured once with NiO_xCompounding the film, performing secondary heat curing to obtain the electrochromic film, wherein the pre-dispersed solution is filtered and coated on WO by a slit coating method₃Films, in WO₃Forming a first electrolyte layer on the thin film; and NiO_xFilm lamination at NiO_xA second electrolyte layer is formed on the film. Wherein the first electrolyte layer and the second electrolyte layer each have a thickness of 5 μm. In addition, the primary thermal curing and the secondary thermal curing are performed under the condition of 50 ℃.

The embodiment also provides an electrochromic film, and the electrochromic film is prepared by the preparation method of the electrochromic film provided by the embodiment.

Example 3

The embodiment provides a preparation method of an electrochromic film, which comprises the following steps:

s1, respectively preparing amorphous WO on the substrate by adopting ITO transparent conductive film as the substrate and adopting a magnetron sputtering method₃Film and nanocrystalline structure NiO_xA film.

S2, mixing EDOT-C₆F₁₃-LiClO₄Pre-dispersing in a solvent to obtain a pre-dispersion solution.Wherein, the solvent is toluene, ethyl acetate, acetone and butanone; EDOT-C₆F₁₃-LiClO₄And the mass ratio of the solvent is 92: 8.

s3, filtering the predispersion solution, and coating the predispersion solution on WO by a slit coating method₃Film, thermally cured once with NiO_xCompounding the film, performing secondary heat curing to obtain the electrochromic film, wherein the pre-dispersed solution is filtered and coated on WO by a slit coating method₃Films, in WO₃Forming a first electrolyte layer on the thin film; and NiO_xFilm lamination at NiO_xA second electrolyte layer is formed on the film. Wherein the first electrolyte layer and the second electrolyte layer each have a thickness of 8 μm. In addition, the primary thermal curing and the secondary thermal curing are performed under the condition of 150 ℃.

The embodiment also provides an electrochromic film, and the electrochromic film is prepared by the preparation method of the electrochromic film provided by the embodiment.

Test examples

In order to verify the technical effect of the electrochromic film provided by the embodiment of the invention, the sample in the embodiment 1 is used as a test example, and the electrochromic performance of the sample is researched:

specifically, the change of the optical property of the sample under the action of an electric field is measured through in-situ spectroscopy, so that the electrochromic property of the sample is researched. The experimental methods and conditions were: connecting the optical fiber spectrum to an electrochemical workstation, and recording the change of the in-situ spectrum of the sample by applying step potential to the sample; the pulse time is 60 s, and the step potential is 3V to-3V.

Further, FIG. 4 is a graph showing a comparison of the transmittance of the sample in the wavelength range of 380 nm to 1100 nm in the initial stage, the coloring stage and the fading stage. The initial stage of the sample after the preparation is light brown, and the color of the sample can be mutually converted between light brown and transparent color in the testing process. The transmittance of the sample in the faded state is significantly improved compared to the initial state, up to 88.2%. The transmittance in the colored state is remarkably reduced compared with the transmittance in the faded state, which shows that the sample has good transmittance adjusting performance and excellent electrochromic performance, and the transmittance adjusting range of the sample at 550 nm can reach 49.2%.

In summary, the counter electrode layer prepared by the preparation method of the electrochromic film provided by the embodiment of the invention has stable reversible redox reaction, is compatible with the electrochromic layer in performance, has high response speed and good electrochromic performance, and has similar charge quantities injected by the two electrodes, and each layer of material has better matching property and durability; the film preparation equipment adopts a precise coating method (including but not limited to slit coating, micro-concave coating and the like) for coating, so that the coating thickness of an electrolyte layer can be precisely controlled, the coating is more uniform and stable, and the product quality is improved; the apparatus is described in WO₃After the thin film is coated with the electrolyte layer, NiO can be added_xThe electrochromic film is directly obtained after the film is compounded, so that the time for polluting an electrolyte layer is reduced, the product quality is improved, and the production cost is reduced.

The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.