CN111474792B - Porous electrochromic film, multi-color electrochromic film, electrochromic device and preparation method - Google Patents

Porous electrochromic film, multi-color electrochromic film, electrochromic device and preparation method Download PDF

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CN111474792B
CN111474792B CN202010410536.6A CN202010410536A CN111474792B CN 111474792 B CN111474792 B CN 111474792B CN 202010410536 A CN202010410536 A CN 202010410536A CN 111474792 B CN111474792 B CN 111474792B
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electrochromic
film
electrochromic film
transparent conductive
porous
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CN111474792A (en
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于有海
朱陈杰
钱广涛
姚佳楠
陈春海
刘刚
李慧
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Donghua University
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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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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials

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Abstract

The invention relates to the technical field of electrochromic materials, in particular to a porous electrochromic film and a preparation method thereof, a multi-color electrochromic film and a preparation method thereof, and an electrochromic device and a preparation method thereof. The preparation method of the porous electrochromic film provided by the invention comprises the following steps: providing an electrochromic material mixed solution; and depositing the electrochromic material mixed solution on the surface of a substrate through electrostatic spraying to obtain the porous electrochromic film. The porous electrochromic film prepared by the invention is of a porous structure, is beneficial to ion diffusion, can greatly improve the response speed of the electrochromic film, reduces the working voltage, has good stability and simple preparation process, and the conductive substrate can be randomly replaced according to actual requirements and material properties, so that the porous electrochromic film is suitable for preparing the electrochromic film and related devices in a large area, including intelligent color-changing glass, display devices and flexible or random curved surface devices.

Description

Porous electrochromic film, multi-color electrochromic film, electrochromic device and preparation method
Technical Field
The invention relates to the technical field of electrochromic materials, in particular to a porous electrochromic film and a preparation method thereof, a multi-color electrochromic film and a preparation method thereof, and an electrochromic device and a preparation method thereof.
Background
The electrochromic material has outstanding controllability, environmental protection, higher optical contrast and huge potential in the fields of flexible devices and intelligent wearing, and an electrical stimulation method or related devices depending on an electric energy source have larger development space in the future, so that the electrochromic material is widely concerned and developed in recent years. At present, electrochromic materials and related devices have been applied in the fields of smart windows, optical blinds, automobile rearview mirrors, sunglasses, reflective displays, flexible displays and smart wearing.
In a broad sense, electrochromism is the phenomenon whereby a material undergoes a macroscopically reversible color change under the influence of an external voltage. The performance of the electrochromic film is determined by the material properties and the preparation process, and the research on the process in the prior art is less. The electrochromic film prepared by the traditional modes of spin coating, magnetron sputtering, drop coating, air pressure spraying, vapor deposition and the like still has the problems of slow response speed, poor stability, high cost, unsuitability for large-area preparation and the like.
Disclosure of Invention
The porous electrochromic film prepared by the invention has the advantages of high response speed, good stability and simple process, and is suitable for preparing the electrochromic film in a large area.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a porous electrochromic film, which comprises the following steps:
(1) providing an electrochromic material mixed solution;
(2) and depositing the electrochromic material mixed solution on the surface of a substrate through electrostatic spraying to obtain the porous electrochromic film.
Preferably, the raw materials for preparing the electrochromic material mixed solution comprise an organic electrochromic material, an inorganic intrinsic conductor material and an organic solvent; the mass ratio of the organic electrochromic material to the inorganic intrinsic conductor material to the organic solvent is (4-10): 0.1:100.
Preferably, the organic electrochromic material comprises one or more of polyimide electrochromic materials, polyaniline electrochromic materials, polyamide electrochromic materials, polytriphenylamine electrochromic materials, polythiophene electrochromic materials and polypyrrole electrochromic materials;
the inorganic intrinsic conductor material comprises one or more of silver nanowires, gold nanowires and graphene;
the organic solvent comprises dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone or acetonitrile.
Preferably, the negative voltage of the electrostatic spraying is 0-3 kV, and the positive voltage is 5-15 kV; the environment temperature of the electrostatic spraying is 20-25 ℃, and the environment humidity is less than 30 RH%.
Preferably, when the electrostatic spraying deposition is carried out, the electrochromic material mixed solution is sprayed out from a spray head; the distance between the spray head and the substrate is 10-20 cm; the injection speed of the electrochromic material mixed liquid is 0.03-0.10 mm/min.
The porous electrochromic film prepared by the preparation method provided by the invention is of a porous structure, and the aperture is 300-800 nm.
The invention also provides a preparation method of the multi-color electrochromic film, which comprises the following steps:
the first method is that an inorganic electrochromic film is deposited on the surface of the substrate in the technical scheme, and then the electrochromic material mixed solution is deposited on the surface of the inorganic electrochromic film through electrostatic spraying to obtain the multi-color electrochromic film.
And secondly, depositing the porous electrochromic film on the surface of the substrate according to the preparation method of the technical scheme to obtain the porous electrochromic film, and depositing the inorganic electrochromic film on the surface of the porous electrochromic film to obtain the multi-color electrochromic film.
The invention provides a multicolor electrochromic film prepared by the preparation method in the technical scheme, which comprises a laminated porous electrochromic film and an inorganic electrochromic film.
The invention also provides an electrochromic device which comprises a first transparent conducting layer, an electrochromic film, an electrolyte layer and a second transparent conducting layer which are sequentially stacked, wherein the electrochromic film is the porous electrochromic film or the multi-color electrochromic film.
The invention provides a preparation method of the electrochromic device in the technical scheme, the raw material of the electrolyte layer is gel electrolyte or solid electrolyte, the first transparent conducting layer is transparent conducting glass, the second transparent conducting layer is transparent conducting glass, and the preparation method comprises the following steps:
method I, when the electrolyte in the electrolyte layer is a gel electrolyte:
sequentially laminating transparent conductive glass covered with an electrochromic film, a hot melt adhesive and the transparent conductive glass, wherein the hot melt adhesive is arranged on the periphery of the transparent conductive glass and is heated and bonded to obtain a sandwich structure with a gap; the transparent conductive glass covering the electrochromic film is prepared by the preparation method in the technical scheme;
injecting gel electrolyte into the gap of the sandwich structure, and packaging to obtain an electrochromic device;
method II, when the electrolyte in the electrolyte layer is a solid electrolyte:
preparing an electrochromic film on the surface of first transparent conductive glass by adopting the preparation method in the technical scheme to obtain transparent conductive glass covering the electrochromic film;
preparing a solid electrolyte membrane on the surface of the second transparent conductive glass to obtain transparent conductive glass covering the solid electrolyte membrane;
and adhering the transparent conductive glass covering the electrochromic film and the transparent conductive glass covering the solid electrolyte film by using a hot melt adhesive to ensure that the solid electrolyte film is fully contacted with the electrochromic film, thereby obtaining the electrochromic device.
The invention provides a preparation method of a porous electrochromic film, which adopts an electrostatic spraying deposition method to enable electrochromic material mixed solution to be rapidly deposited on a conductive substrate in the form of tiny droplets, a solvent in the droplets is volatilized in the deposition process, and tiny gaps among spherical particles form small holes through layer-by-layer deposition to obtain the porous electrochromic film. The porous electrochromic film prepared by the invention is of a porous structure, is beneficial to ion diffusion, can greatly improve the response speed of the electrochromic film, reduces the working voltage and has better stability. The preparation method provided by the invention has simple process, the conductive substrate can be replaced at will according to actual requirements and material properties, and the preparation method is suitable for preparing the electrochromic film and related devices in a large area, including intelligent color-changing glass, display devices and flexible or random curved surface devices.
Drawings
FIG. 1 is a diagram of a porous electrochromic film obtained on the surface of transparent conductive glass in example 1;
FIG. 2 is a diagram of example 10 showing the application of a layer of hot melt adhesive to a porous electrochromic film;
FIG. 3 shows the structure of a transparent conductive glass layer, an electrochromic film, and a transparent conductive glass layer in example 10;
FIG. 4 is a cyclic voltammogram of the porous electrochromic film prepared in example 1;
FIG. 5 is the response speed (at 786 nm) of the porous electrochromic film prepared in example 1;
FIG. 6 shows the UV-VIS-IR spectrum electrochemical coupling test results of the porous electrochromic film prepared in example 1;
FIG. 7 is a graph of cyclic voltammetry characteristics for an electrochromic device prepared in example 10;
fig. 8 is a test result of response speed of the electrochromic device prepared in example 10;
fig. 9 is an ultraviolet-visible-infrared chromatogram of a colored state and a bleached state of an electrochromic device prepared in example 10;
FIG. 10 is a graph showing the cyclic voltammetry characteristics of an electrochromic film prepared by a doctor blade method using the same electrochromic mixture as in example 1;
FIG. 11 is a graph showing cyclic voltammetry characteristics of an electrochromic film prepared by a spin coating method using the same electrochromic mixture as in example 1;
FIG. 12 is a graph of cyclic voltammetry for the multi-color electrochromic film of example 2;
fig. 13 is a graph showing cyclic voltammetry characteristics of an electrochromic device prepared by the method of example 10 from the multi-colored electrochromic film of example 8.
Detailed Description
The invention provides a preparation method of a porous electrochromic film, which comprises the following steps:
(1) providing an electrochromic material mixed solution;
(2) and depositing the electrochromic material mixed solution on the surface of a substrate through electrostatic spraying to obtain the porous electrochromic film.
The invention provides an electrochromic material mixed liquid. In the invention, the raw materials for preparing the electrochromic material mixed solution preferably comprise an organic electrochromic material and an organic solvent, and more preferably comprise an organic electrochromic material, an inorganic intrinsic conductor material and an organic solvent; the mass ratio of the organic electrochromic material to the inorganic intrinsic conductor material to the organic solvent is preferably (4-10): 0.1:100, more preferably (6-8): 0.1:100. In a specific embodiment of the present invention, the content of the organic electrochromic material in the electrochromic material mixture is preferably 5 to 10 wt%, and more preferably 6 to 8 wt%; the dosage of the inorganic intrinsic conductor material is preferably not more than 1mg, and more preferably 0.1-1 mg.
In the invention, the organic electrochromic material preferably comprises one or more of polyimide electrochromic materials, polyaniline electrochromic materials, polyamide electrochromic materials, polytriphenylamine electrochromic materials, polythiophene electrochromic materials and polypyrrole electrochromic materials; the polyimide electrochromic material is preferably poly (pyromellitic acid-bis (4-aminophenyl) -9, 9' -dimethylfluorene-imide) or poly (naphthalene-1, 4,5, 8-tetracarboxylic acid-imide); the polyaniline electrochromic material is preferably polyaniline; the polyamide electrochromic material is preferably poly (4,4 '-bis (benzene-3, 5-dimethyl-4', 4 '-diamine-triphenylamine) or poly (1, 4-cyclohexane-diacid-4, 4' -diamine-triphenylamine); the polytriphenylamine electrochromic material is preferably polytriphenylamine ethylene or N, N, N ', N' -tetraphenylbenzidine; the polythiophene electrochromic material is preferably poly (3-methylthiophene) or poly (4, 7-di (2, 3-dihydro-thiophene [3,4-b ] [1,4] dioxin-5-yl) benzo [1,2,5] thiadiazole); the polypyrrole electrochromic material is preferably poly (3, 4-propylene dioxypyrrole) or poly (3, 4-ethylene dioxypyrrole).
In the invention, the inorganic intrinsic conductor material preferably comprises one or more of silver nanowires, gold nanowires and graphene; the length-diameter ratio of the silver nanowires and the gold nanowires is preferably independently larger than 100nm, more preferably 100-500 nm, and further preferably 300-500 nm; the diameters of the silver nanowires and the gold nanowires are preferably 30-100 nm independently, and more preferably 40-50 nm; the lengths of the silver nanowires and the gold nanowires are preferably 20-40 mu m independently, and more preferably 30-40 mu m independently. According to the invention, the inorganic intrinsic conductor material is added into the electrochromic material mixed solution as a conductive reinforcing material, so that the electric field force applied to the electrochromic material mixed solution during electrostatic spraying can be enhanced, and a more microporous and more uniform film is formed.
In the present invention, the organic solvent preferably includes dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, or acetonitrile.
In the present invention, the preparation method of the electrochromic material mixture preferably includes the steps of: and mixing the organic electrochromic material, the inorganic intrinsic conductor material and the organic solvent to obtain electrochromic material mixed liquor. The invention has no special requirement on the mixing temperature and is lower than the boiling point of the organic solvent. In the present invention, the mixing is preferably carried out under stirring conditions, and the present invention has no special requirements on the stirring speed and time, and preferably, the organic electrochromic material and the inorganic intrinsic conductor material are completely dissolved.
In the invention, the viscosity of the electrochromic material mixed solution is preferably 3-6P, and more preferably 4-5P. According to the invention, the viscosity of the electrochromic material mixed solution is controlled within the range, so that the phenomenon of drop casting caused by too low viscosity can be avoided, the adhesive force between the drops and the substrate is improved, and a thin film and a porous structure are rapidly formed; the conditions that the solution blocks a needle head, the spraying process is unstable, liquid drops are not uniform and partial bead-shaped fibers are formed due to overhigh viscosity can be avoided, and the quality of the porous electrochromic film is improved.
Obtaining the electrochromic material mixed solutionAnd then, depositing the electrochromic material mixed solution on the surface of a substrate through electrostatic spraying to obtain the porous electrochromic film. In the present invention, the negative voltage of the electrostatic spraying is preferably 0 to-3 kV, more preferably-1 to-2 kV; the positive voltage is preferably 5-15 kV, and more preferably 8-12 kV. In the invention, the environment temperature of the electrostatic spraying is preferably 20-25 ℃, the environment humidity is preferably less than 30 RH%, and more preferably 5-20 RH%. When the electrostatic spraying deposition is carried out, the electrochromic material mixed solution is sprayed out by a spray head; the distance between the spray head and the substrate is preferably 10-20 cm, and more preferably 15 cm; the distance between the spray head and the negative electrode is preferably 20-40 cm, and more preferably 25-30 cm; the injection speed of the electrochromic material mixed liquid is preferably 0.03-0.10 mm/min, and more preferably 0.04-0.06 mm/min. In a particular embodiment of the invention, the spray head is preferably a flat-nose needle; when the area of the porous electrochromic film is 50cm2When the diameter of the flat-mouth needle is 0.30 mm; when the area of the porous electrochromic film is more than 50cm2When the needle is used, the diameter of the flat-mouth needle head is preferably 0.40-2.70 mm. The electrochromic material mixed solution is placed in a high-voltage electric field, and the injection speed, the environmental temperature and humidity and the receiving distance are controlled, so that the electrochromic material mixed solution forms a Taylor cone at a nozzle, and at the moment, liquid drops are in a mist shape and are rapidly deposited on a substrate in a high-speed injection mode to form small holes, and further, the porous electrochromic film is obtained.
In a specific embodiment of the present invention, the device used for electrostatic spraying is preferably an electrostatic spinning machine.
In the present invention, the substrate preferably comprises ITO glass, FTO glass, flexible PET film, conductive hydrogel or aluminum foil paper. According to the invention, before the electrostatic spraying deposition, the substrate is preferably subjected to a cleaning treatment. In the present invention, the method of the cleaning treatment preferably includes: sequentially carrying out water washing, acetone washing, ethanol washing and plasma treatment on the substrate; the water washing, the acetone washing and the ethanol washing are independently and preferably carried out under the ultrasonic condition; the power of the plasma treatment is preferably 1500-2500W, and more preferably 2200W. The invention improves the hydrophilicity of the substrate by cleaning the substrate.
In the present invention, after the electrostatic spray deposition, the obtained film is preferably vacuum dried together with the substrate to obtain the porous electrochromic film. In the specific embodiment of the invention, the temperature of the vacuum drying is preferably 100-120 ℃; the vacuum drying time is preferably 8-12 h; the degree of vacuum in the vacuum drying is preferably 0.01MPa or less. The organic solvent is further removed through vacuum drying, and a complete porous electrochromic film is formed.
The porous electrochromic film prepared by the preparation method is of a porous structure, and the aperture is preferably 300-800 nm, more preferably 500-600 nm; the thickness is preferably 400 to 1000nm, and more preferably 600 to 800 nm. The electrochromic film prepared by the invention is of a porous structure, is beneficial to ion diffusion, greatly improves the response speed of the film and reduces the working voltage.
The invention also provides a preparation method of the multi-color electrochromic film, which comprises the following steps:
the first method is that an inorganic electrochromic film is deposited on the surface of the substrate in the technical scheme, and then the electrochromic material mixed solution is deposited on the surface of the inorganic electrochromic film through electrostatic spraying to obtain the multi-color electrochromic film.
And secondly, depositing the porous electrochromic film on the surface of the substrate according to the preparation method of the technical scheme to obtain the porous electrochromic film, and depositing the inorganic electrochromic film on the surface of the porous electrochromic film to obtain the multi-color electrochromic film.
Specifically, the method I is that an inorganic electrochromic film is firstly deposited on the surface of a substrate to obtain an electrochromic substrate; and depositing the electrochromic material mixed solution on the surface of an electrochromic substrate through electrostatic spraying to obtain the multi-color electrochromic film. In the present invention, the method for depositing the inorganic electrochromic film preferably includes a pulling method, a dropping coating method, a spin coating method, a doctor blade coating method, a magnetron sputtering method, a vacuum evaporation method, or an electrochemical polymerization method. The invention has no special requirements on the specific processes of the pulling method, the dropping coating method, the spin coating method, the scraper coating method, the magnetron sputtering method, the vacuum evaporation method or the electrochemical polymerization method, and adopts the preparation process which is well known by the technical personnel in the field. In the present invention, the inorganic electrochromic film is preferably a nickel oxide film or a tungsten oxide film; the thickness of the inorganic electrochromic film is preferably 200-400 nm.
And secondly, depositing an inorganic electrochromic film on the surface of the porous electrochromic film to obtain the multicolor electrochromic film. In the present invention, the method for depositing the inorganic electrochromic film preferably includes a pulling method, a dropping coating method, a spin coating method, a doctor blade coating method, a magnetron sputtering method, a vacuum evaporation method, or an electrochemical polymerization method. The invention has no special requirements on the specific processes of the pulling method, the dropping coating method, the spin coating method, the scraper coating method, the air pressure spraying method, the dipping method, the magnetron sputtering method, the vacuum evaporation method or the electrochemical polymerization method, and can adopt the preparation process known by the technicians in the field. In the present invention, the inorganic electrochromic film is preferably a nickel oxide film or a tungsten oxide film; the thickness of the inorganic electrochromic film is preferably 200-400 nm.
The invention also provides a multi-color electrochromic film prepared by the preparation method in the technical scheme, which comprises a porous electrochromic film and an inorganic electrochromic film which are arranged in a laminated manner. In the present invention, the organic phase and the inorganic phase in the multi-color electrochromic film are closely combined, effectively forming a complementary electrochromic film; among them, the organic phase and the inorganic phase have better dispersibility and stronger interfacial interaction (including covalent bond, coordinate bond, electrostatic interaction, hydrogen bond and pi-pi stacking interaction) which helps to provide an unimpeded ion channel and improve electron conduction between the organic phase and the inorganic phase due to an easy conduction path and a short conduction distance, thereby improving electrochromic properties.
The invention also provides an electrochromic device which comprises a first transparent conducting layer, an electrochromic film, an electrolyte layer and a second transparent conducting layer which are sequentially stackedAnd the electrochromic film is the porous electrochromic film or the multi-color electrochromic film. In the present invention, the first transparent conductive layer and the second transparent conductive layer are preferably transparent conductive glass layers; the transparent conductive glass is preferably ITO glass or FTO glass; the ionic conductivity of the electrolyte used for forming the electrolyte layer is preferably>1×10-4s/cm, the electrolyte is preferably a gel electrolyte or a solid electrolyte. In the present invention, the raw materials for preparing the gel electrolyte preferably include a host material and a salt substance; the main body material preferably comprises one or more of polyvinyl fluoride (PVDF), polymethyl methacrylate (PMMA), polyethylene oxide (PEO) and polyvinylidene fluoride-hexafluoroethylene (PVDF-HFP); the salt substance preferably comprises lithium perchlorate (LiClO)4) One or more of tetrabutylammonium tetrafluoroborate (TBATFB) and tetrabutylammonium perchlorate (TBAP). In a specific embodiment of the present invention, the preparation method of the gel electrolyte is preferably: TBAP, ACN (acetonitrile), PMMA and PC (propylene carbonate) are mixed according to the mass ratio of 15:61:10:14, and are stirred and dissolved for 5 hours at the temperature of 65 ℃, so that the gel electrolyte is obtained.
In the present invention, the solid electrolyte is preferably LiClO4Or lithium tetrafluoroborate (LiBF)4). In the embodiment of the present invention, the preparation method of the solid electrolyte is preferably: LiClO is added4ACN and PMMA at 1: 5: 4, stirring and dissolving for 5 hours at the temperature of 50 ℃, and then preparing the solid electrolyte membrane by using the obtained solution through a solvent evaporation coating technology.
The invention also provides a preparation method of the electrochromic device in the technical scheme, which comprises a method I or a method II;
method I, when the electrolyte in the electrolyte layer is a gel electrolyte:
sequentially laminating transparent conductive glass covered with an electrochromic film, a hot melt adhesive and the transparent conductive glass, wherein the hot melt adhesive is arranged on the periphery of the transparent conductive glass and is heated and bonded to obtain a sandwich structure with a gap; the transparent conductive glass covering the electrochromic film is prepared by the preparation method in the technical scheme;
injecting gel electrolyte into the gap of the sandwich structure, and packaging to obtain an electrochromic device;
method II, when the electrolyte in the electrolyte layer is a solid electrolyte:
preparing an electrochromic film on the surface of first transparent conductive glass by adopting the preparation method in the technical scheme to obtain transparent conductive glass covering the electrochromic film;
preparing a solid electrolyte membrane on the surface of the second transparent conductive glass to obtain transparent conductive glass covering the solid electrolyte membrane;
and adhering the transparent conductive glass covering the electrochromic film and the transparent conductive glass covering the solid electrolyte film by using a hot melt adhesive to ensure that the solid electrolyte film is fully contacted with the electrochromic film, thereby obtaining the electrochromic device.
Specifically, in the present invention, when the electrolyte in the electrolyte layer is a gel electrolyte: sequentially laminating transparent conductive glass covered with a porous electrochromic film or a multicolor electrochromic film, a hot melt adhesive and the transparent conductive glass, wherein the hot melt adhesive is arranged on the periphery of the transparent conductive glass and is heated and bonded to obtain a sandwich structure with a gap; the transparent conductive glass covered with the porous electrochromic film or the multicolor electrochromic film is prepared by the preparation method of the technical scheme. In a specific embodiment of the present invention, the substrate is defined as transparent conductive glass, and then the preparation method according to the above technical scheme is adopted to directly prepare the porous electrochromic film or the multi-color electrochromic film on the surface of the transparent conductive glass, so as to obtain the transparent conductive glass covering the porous electrochromic film or the multi-color electrochromic film. In the present invention, the source of the hot melt adhesive preferably comprises TPU (polyurethane) hot melt adhesive, EVA adhesive, PA adhesive, PES adhesive or PO adhesive, more preferably TPU hot melt adhesive or EVA adhesive.
In the present invention, the temperature of said heated bonding is preferably determined according to the temperature required by the hot melt adhesive used, and in a particular embodiment of the invention is preferably 120 ℃.
In the invention, the hot melt adhesive is arranged at the periphery of the transparent conductive glass, the hot melt adhesive is not arranged at the middle parts of the transparent conductive glass and the transparent conductive glass which cover the porous electrochromic film or the multicolor electrochromic film, and the hot melt adhesive is melted in the heating and bonding process, so that a gap is formed at the middle part.
After the sandwich structure with the gaps is obtained, gel electrolyte is injected into the gaps of the sandwich structure for packaging, and the electrochromic device is obtained. In the present invention, the method of implanting preferably comprises: adding the gel electrolyte from one end of the sandwich structure, and pumping the gel electrolyte from the other end of the sandwich structure by using a vacuum pump until the electrolyte completely fills the gap. In the present invention, the method of encapsulation preferably includes: and dripping ultraviolet curing glue on the periphery of the sandwich structure, and performing ultraviolet curing packaging. In the preparation of electrochromic devices, the present invention preferably pre-drills two diagonal holes in the conductive glass to facilitate the injection of the gel electrolyte, as shown in the structure of fig. 3.
Specifically, in the present invention, when the electrolyte in the electrolyte layer is a solid electrolyte: the preparation method of the technical scheme is adopted to prepare the porous electrochromic film or the multicolor electrochromic film on the surface of the first transparent conductive glass, so as to obtain the transparent conductive glass covering the porous electrochromic film or the multicolor electrochromic film. In a specific embodiment of the present invention, the substrate is defined as transparent conductive glass, and then the preparation method according to the above technical solution is adopted to directly prepare the porous electrochromic film or the multi-color electrochromic film on the surface of the transparent conductive glass, so as to obtain transparent conductive glass covering the porous electrochromic film or the multi-color electrochromic film, that is, the transparent conductive glass covering the electrochromic film.
According to the invention, the solid electrolyte membrane is prepared on the surface of the second transparent conductive glass, so that the transparent conductive glass covering the solid electrolyte membrane is obtained. In the present invention, the method for producing a solid electrolyte membrane is preferably solvent evaporation coating or magnetron sputtering. In the detailed description of the inventionIn the examples, when the composition of the solid electrolyte membrane is LiClO4In the method, a solvent evaporation coating method is adopted to prepare the solid electrolyte membrane on the surface of the second transparent conductive glass, the specific technological parameters of the solvent evaporation coating are not specially limited, and the conventional process of a person skilled in the art is adopted; when the components of the solid electrolyte membrane are lithium phosphorus oxynitride or garnet containing lithium, the solid electrolyte membrane is prepared on the surface of the second transparent conductive glass by adopting magnetron sputtering.
After the transparent conductive glass covering the electrochromic film and the transparent conductive glass covering the solid electrolyte membrane are obtained, the transparent conductive glass covering the electrochromic film and the transparent conductive glass covering the solid electrolyte membrane are bonded by the hot melt adhesive, so that the solid electrolyte membrane and the electrochromic film are fully contacted, and the electrochromic device is obtained. In the present invention, the source of the hot melt adhesive preferably comprises TPU (polyurethane) hot melt adhesive, EVA adhesive, PA adhesive, PES adhesive or PO adhesive, more preferably TPU hot melt adhesive or EVA adhesive. In the invention, the temperature for realizing the full contact between the solid electrolyte membrane and the electrochromic film is preferably 80-140 ℃, and more preferably 100-120 ℃. The present invention preferably encapsulates the obtained structure to obtain the electrochromic device, and the present invention does not specifically limit the specific process of the encapsulation, and the encapsulation process known to those skilled in the art can be adopted.
The preparation process of the electrochromic device provided by the invention can greatly reduce the bubble occurrence rate and the residual rate, improve the precision and the cycling stability of the electrochromic device, and solve the defects of poor air tightness due to the charge of the traditional electrochromic device process.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope 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.
Example 1
Poly (4,4' -diphenyloxide-4-methoxy-triphenylamine) (TPA-OMe-PA) was prepared by referring to the preparation method in "Chang C-W, Liou G-S, Hsiao S-H.high dry stable and inorganic green aromatic polyamides: synthesis and electrochemical properties [ J ]. Journal of materials Chemistry"; the TPA-OMe-PA is green at 0.7-0.9V;
mixing the TPA-OMe-PA, the silver nanowires (AgNWs) and N, N-dimethylacetamide (DMAc) according to a mass ratio of 10:0.1:100, stirring for 6 hours at 120 ℃, and cooling to room temperature to obtain an electrochromic mixed solution; the viscosity of the electrochromic material mixed solution is 5P;
controlling the environment temperature of electrostatic spraying to be 20-25 ℃ and the humidity to be 20-25 RH%, absorbing 2mL of the electrochromic material mixed solution by using a needle tube, using a flat-end needle with the diameter of 0.30mm as a spray head, and adjusting the distance between the needle and a negative electrode to be 25 cm; setting the injection speed to be 0.04mm/min, adjusting voltage (negative voltage is-2 kV, positive voltage is 7.6kV) until stable Taylor cones appear on liquid drops at the nozzle, and spraying for a period of time to remove more impurities and unstable parts of the needle head part; adopting transparent conductive glass as a substrate for receiving, wherein the receiving distance is 10 cm; the transparent conductive glass is cleaned by ultrasonic oscillation of deionized water, acetone and ethanol in sequence before use, and is subjected to surface cleaning treatment for 120s by a plasma processor with the power of 2200W; the receiving time of the substrate is 3min, then the film obtained by receiving is placed in a vacuum drying oven, and drying is carried out for 10h at the temperature of 120 ℃, so that the porous electrochromic film with the thickness of 800nm and the pore diameter of 300-800 nm is obtained.
Example 2
Reference is made to "Xu Z, Kong L, Wang Y, Wang B, Zhao J. tuning band gap, color switching, optical constrast, and redox stability in solution-processing BDT-based electrochromic materials [ J ]. Organic electronics.2018; 54:94-103 'to obtain poly (2, 6-bis (trimethylstannane) -4, 8-bis (2-octyldecyloxy) benzo [1, 2-b: 4,5-b' ] dithiophene-5, 6-dioctyloxy-2, 1, 3-benzothiadiazole) (PBDT); the PBDT is light yellow at 1.7V;
the PBDT, TPA-OMe-PA from example 1 and DMAc were mixed as 1: 1: 20, stirring for 8 hours at the temperature of 60 ℃, and cooling to room temperature to obtain electrochromic mixed liquor; the viscosity of the electrochromic material mixed solution is 5P;
controlling the environment temperature of electrostatic spraying to be 20-25 ℃ and the humidity to be 20-25 RH%, absorbing 5mL of the electrochromic material mixed solution by using a needle tube, using a flat-end needle with the diameter of 0.30mm as a spray head, and adjusting the distance between the needle and a negative electrode to be 20 cm; setting the injection speed to be 0.03mm/min, and adjusting the voltage (negative voltage is-2.01 kV, positive voltage is 6.8kV) until the stable Taylor cone appears on the liquid drop at the nozzle; adopting transparent conductive glass as a substrate for receiving, wherein the receiving distance is 15cm, the transparent conductive glass is cleaned by ultrasonic oscillation of deionized water, acetone and ethanol in sequence before use, and is subjected to surface cleaning treatment for 120s by a plasma processor with the power of 2200W; the receiving time of the substrate is 3min, then the film obtained by receiving is placed in a vacuum drying oven, and drying is carried out for 10h at the temperature of 120 ℃, so that the porous electrochromic film with the thickness of 600nm and the pore diameter of 300-800 nm is obtained.
Because the PBDT and TPA-OMe-PA have different response voltages, the scanning of the circulating voltage in-1.5V to 1.7V can show different colors.
Example 3
Poly (pyromellitic acid-bis (4-aminophenyl) -9, 9' -dimethylfluorene-imide), AgNWs and N-methylpyrrolidone (NMP) were mixed in the following 1: 0.01: 20, stirring for 5 hours at the temperature of 60 ℃, and cooling to room temperature to obtain electrochromic mixed liquor; the viscosity of the electrochromic material mixed solution is 6P;
controlling the environment temperature of electrostatic spraying to be 20-25 ℃ and the humidity to be 20-25 RH%, absorbing 5mL of the electrochromic material mixed solution by using a needle tube, using a flat-end needle with the diameter of 0.30mm as a spray head, and adjusting the distance between the needle and a negative electrode to be 20 cm; setting the injection speed to be 0.04mm/min, and adjusting the voltage (the negative voltage is-2.12 kV, and the positive voltage is 8.15kV) until the stable Taylor cone appears on the liquid drop at the nozzle; adopting transparent conductive glass as a substrate for receiving, wherein the receiving distance is 5cm, the transparent conductive glass is cleaned by ultrasonic oscillation of deionized water, acetone and ethanol in sequence before use, and is subjected to surface cleaning treatment for 120s by a plasma processor with the power of 2200W; the receiving time of the substrate is 5min, then the film obtained after receiving is placed in a vacuum drying oven, and drying is carried out for 12h at the temperature of 120 ℃, so that the porous electrochromic film with the thickness of 900nm and the pore diameter of 300-900 nm is obtained.
Example 4
PVTPA (polytriphenylamine ethylene), DMAc, and AgNWs were mixed as 20: 80: mixing according to the mass ratio of 0.1, stirring for 8 hours at the temperature of 120 ℃, and cooling to room temperature to obtain electrochromic mixed liquor; the viscosity of the electrochromic material mixed solution is 6P;
controlling the environment temperature of electrostatic spraying to be 20-25 ℃ and the humidity to be 20-25 RH%, absorbing 5mL of the electrochromic material mixed solution by using a needle tube, using a flat-end needle with the diameter of 0.30mm as a spray head, and adjusting the distance between the needle and a negative electrode to be 20 cm; setting the injection speed to be 0.04mm/min, and adjusting the voltage (negative voltage is-2.02 kV, positive voltage is 6.80kV) until the liquid drops at the nozzle are in a stable Taylor cone; adopting transparent conductive glass as a substrate for receiving, wherein the receiving distance is 15cm, the transparent conductive glass is cleaned by ultrasonic oscillation of deionized water, acetone and ethanol in sequence before use, and is subjected to surface cleaning treatment for 120s by a plasma processor with the power of 2200W; the receiving time of the substrate is 3min, then the film obtained by receiving is placed in a vacuum drying oven, and drying is carried out for 12h at the temperature of 120 ℃, so that the porous electrochromic film with the thickness of 800nm and the pore diameter of 300-500 nm is obtained.
Example 5
Polyaniline (PANI), dimethyl sulfoxide (DMSO), and AgNWs were mixed as follows: 100: mixing according to the mass ratio of 0.1, stirring for 8 hours at the temperature of 80 ℃, and cooling to room temperature to obtain electrochromic mixed liquor; the viscosity of the electrochromic material mixed solution is 6P;
controlling the environment temperature of electrostatic spraying to be 20-25 ℃ and the humidity to be 20-25 RH%, absorbing 5mL of the electrochromic material mixed solution by using a needle tube, using a flat-end needle with the diameter of 0.30mm as a spray head, and adjusting the distance between the needle and a negative electrode to be 15 cm; setting the injection speed to be 0.06mm/min, and adjusting the voltage (the negative voltage is-2.02 kV, and the positive voltage is 8.15kV) until the stable Taylor cone appears on the liquid drop at the nozzle; adopting transparent conductive glass as a substrate for receiving, wherein the receiving distance is 15cm, the transparent conductive glass is cleaned by ultrasonic oscillation of deionized water, acetone and ethanol in sequence before use, and is subjected to surface cleaning treatment for 120s by a plasma processor with the power of 2200W; the receiving time of the substrate is 5min, then the film obtained after receiving is placed in a vacuum drying oven, and drying is carried out for 12h at the temperature of 120 ℃, so that the porous electrochromic film with the thickness of 1200nm and the pore diameter of 200-800 nm is obtained.
Example 6
Preparing a nickel oxide (NiO) film on the surface of the ITO glass by an electrochemical polymerization method: using ITO glass as working electrode, platinum (Pt) sheet as counter electrode, Ag/AgCl as reference electrode to make electrochemical polymerization, and using NiSO as electrolyte solution4(0.005mol/L) and (NH)4)2SO4(0.02mol/L), adding a proper amount of ammonia water until the pH value of the solution is alkalescent (the pH value is 8), performing electrodeposition for 5min at a circulating voltage of-0.5-1V (50mV/s), performing heat treatment on the electrodeposition film at 250 ℃ for 1h, and annealing to obtain a NiO film;
depositing a polyaniline film on the surface of the NiO film by electrostatic spraying: polyaniline (PANI), dimethyl sulfoxide (DMSO), and AgNWs were mixed as follows: 100: mixing according to the mass ratio of 0.1, stirring for 8 hours at the temperature of 80 ℃, and cooling to room temperature to obtain electrochromic mixed liquor; the viscosity of the electrochromic material mixed solution is 4.5P;
controlling the environment temperature of electrostatic spraying to be 20-25 ℃ and the humidity to be 20-25 RH%, absorbing 5mL of the electrochromic material mixed solution by using a needle tube, using a flat-end needle with the diameter of 0.30mm as a spray head, and adjusting the distance between the needle and a negative electrode to be 15 cm; setting the injection speed to be 0.06mm/min, and adjusting the voltage (the negative voltage is-2.02 kV, and the positive voltage is 8.15kV) until the stable Taylor cone appears on the liquid drop at the nozzle; the ITO glass deposited with the NiO film is used as a substrate for receiving, and the receiving distance is 10 cm; the substrate receiving time is 5min, then the received film is placed in a vacuum drying oven and dried for 12h at 120 ℃ to obtain a porous electrochromic film with the thickness of 1000nm and the pore diameter of 300-800 nm, and finally the multicolor electrochromic film is obtained on the surface of the ITO glass.
Example 7
Preparing tungsten oxide on the surface of ITO glass by magnetron sputtering method (WO)3) The specific process of the film is as follows: firstly, the sputtering chamber is vacuumized in the atmospheric state to ensure that the vacuum degree in the sputtering chamber reaches 10-1Pa; filling gas into the sputtering chamber, wherein argon is used as working gas, oxygen is used as reaction gas, and adjusting the gas inflow to a required value through a gas flow adjusting knob; firstly, pre-sputtering for 10min by using pure argon to remove pollutants on the surface of the target material, and starting formal sputtering after the pre-sputtering is finished; the WO is prepared by a direct current sputtering method3A film;
by electrostatic spraying on said WO3Depositing a polyaniline film on the surface of the film: polyaniline (PANI), dimethyl sulfoxide (DMSO), and AgNWs were mixed as follows: 100: mixing according to the mass ratio of 0.1, stirring for 8 hours at the temperature of 80 ℃, and cooling to room temperature to obtain electrochromic mixed liquor; the viscosity of the electrochromic material mixed solution is 6P;
controlling the environment temperature of electrostatic spraying to be 20-25 ℃ and the humidity to be 20-25 RH%, absorbing 5mL of the electrochromic material mixed solution by using a needle tube, using a flat-end needle with the diameter of 0.30mm as a spray head, and adjusting the distance between the needle and a negative electrode to be 15 cm; setting the injection speed to be 0.06mm/min, and adjusting the voltage (the negative voltage is-2.02 kV, and the positive voltage is 8.15kV) until the stable Taylor cone appears on the liquid drop at the nozzle; with said deposition of WO3The ITO glass of the film is used as a substrate for receiving, and the receiving distance is 15 cm; the substrate receiving time is 5min, then the film obtained after receiving is placed in a vacuum drying oven, drying is carried out for 12h at the temperature of 120 ℃, a porous electrochromic film with the thickness of 1200nm and the pore diameter of 200-800 nm is obtained, and finally the multicolor electrochromic film is obtained on the surface of the ITO glass.
Example 8
Electrochemical polymerization was performed using the porous electrochromic film prepared in example 1 as a substrate to prepare tungsten oxide (WO)3) The specific process of the membrane is as follows: the transparent conductive glass to which the porous electrochromic film described in example 3 was attached was used as a working electrode, a platinum sheet (Pt) was used as a counter electrode, Ag/AgCl was used as a reference electrode, and an aqueous solution containing 30% ethanol and 70% tungsten (tungsten powder was dissolved in 30% H)2O2Aqueous solution containing 50mmol/L tungsten) as electrolyte, performing cathodic electrodeposition for 0.5h at fixed potential (-0.45V for Ag/AgCl), and finally obtaining the multicolor electrochromic film on the surface of the transparent conductive glass.
Example 9
Using the porous electrochromic film prepared in example 5 as a substrate, electrochemical polymerization was performed to prepare tungsten oxide (WO)3) The specific process of the membrane is as follows: the transparent conductive glass to which the porous electrochromic film described in example 5 was attached was used as a working electrode, a platinum sheet (Pt) was used as a counter electrode, Ag/AgCl was used as a reference electrode, and an aqueous solution containing 30% ethanol and 70% tungsten (tungsten powder was dissolved in 30% H)2O2Aqueous solution containing 50mmol/L tungsten) as electrolyte, performing cathodic electrodeposition for 6h at fixed potential (-0.45V for Ag/AgCl), and finally obtaining WO on the surface of transparent conductive glass3the/PANI multi-color electrochromic film can realize multi-color conversion of colorless to green to blue, and can improve the switching speed.
Example 10
Mixing TBAP, ACN, PMMA and PC according to the mass ratio of 15:61:10:14, and stirring at 65 ℃ at the stirring speed of 150rpm/min to dissolve for 5 hours to obtain a gel electrolyte;
pretreatment: before use, the transparent conductive glass is cleaned by ultrasonic oscillation of deionized water, acetone and ethanol in sequence, and is subjected to surface cleaning treatment for 120s by a plasma processor with the power of 2200W;
thermal bonding: a rectangular frame with a proper size is manufactured by hot melt adhesive along four sides of the pretreated transparent conductive glass, the hot melt adhesive and the conductive glass coated with the electrochromic film (the porous electrochromic film prepared in the embodiment 1) are attached, and the transparent conductive glass, the hot melt adhesive and the conductive glass coated with the electrochromic film are placed on a heating table to be heated and bonded at 120 ℃. Forming a transparent conductive glass layer, an electrochromic film and a transparent conductive glass layer structure; the intermediate void is used for gel electrolyte filling (as shown in fig. 2 and 3).
Injecting gel electrolyte: the prepared gel electrolyte is heated again to be convenient for injection, a proper amount of the gel electrolyte is taken to completely cover one corner of the small hole, the other end of the gel electrolyte is extracted by a vacuum pump, and the gap is filled completely and slowly by the electrolyte;
packaging: after the above process is completed, a proper amount of ultraviolet curing glue is dripped on four sides of the two transparent conductive glass sheets, and ultraviolet curing is rapidly used to completely encapsulate the two transparent conductive glass sheets, so that the electrochromic device is obtained.
Test example 1
Example 1 a porous electrochromic film obtained on the surface of transparent conductive glass is shown in fig. 1, and as can be seen from fig. 1, there is a film prepared by electrostatic spraying on transparent conductive glass, and the porous electrochromic films in the other examples are prepared in the same manner.
Test example 2
After electrochemical workstation and spectrometer tests, the porous electrochromic film prepared in example 4 is found to have oxidation-reduction potential reduced to 0.84V/0.59V, coloring time greatly reduced to 1.2s, bleaching time greatly reduced to 0.8s, and coloring efficiency effectively improved to 500cm2And C, the optical contrast is kept above 90%. Based on the preparation method, the stability of the electrochromic device is improved to 150 cycles by using the gel electrolyte.
Test example 3
Electrochromic films prepared by using the Electrochromic material mixture provided in example 1 as a raw material, using a doctor blade method as comparative example 1, using an Ultrasonic deposition method (refer to Liu H-S, Chang W-C, Chou C-Y, Pan B-C, Chou Y-S, Liou G-S, et al. controllable Electrochromic Polymer Film and Device Produced by surface Ultrasonic Spray-coating [ J ] Scientific reports.2017; 7(1):11982) as comparative example 2, using a spin coating method (refer to ChaC-W, Liou G-S, iao S-H. high grade inorganic polymeric films as comparative examples 2007; 3-1007) as Electrochromic films, and using the Electrochromic materials mixtures of examples 1-15, the results are shown in Table 1 and FIGS. 4-6;
TABLE 1 results of performance test of electrochromic films of example 1 and comparative examples 1 to 3
Method Optical contrast Bleaching time Colouring time Oxidation potential Reduction potential
Comparative example 1 94％(0～94％) 4.4s 4.4s 1.15V 0.33V
Example 1 87％(3％～90％) 0.8s 1.2s 0.84V 0.59V
Comparative example 2 >90％ 3.4s 1.8s 0.9～1.1V 0.3～0.6
Comparative example 3 85％ 1.5s 4.5s 0.97V 0.64V
A three-electrode system is adopted, conductive glass attached with the porous electrochromic film prepared in example 1 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum wire is used as a counter electrode, 0.1mol/L tetrabutylammonium perchlorate/acetonitrile solution is used as electrolyte, and an electrochemical workstation tests a cyclic voltammetry characteristic curve, as shown in FIG. 4; FIG. 5 is the response speed (at 786 nm) of the porous electrochromic film prepared in example 1; fig. 6 is a uv-vis-ir-electrochemical coupling test result of the porous electrochromic film prepared in example 1, in which a solid line in fig. 6 represents a spectrum diagram of an oxidation state and a dotted line in fig. 6 represents an original state;
as can be seen from table 1 and fig. 4 to 6, the electrochromic film prepared by electrostatic spraying has the shortest bleaching time and coloring time, and the optical contrast is less different from other methods, so that the obtained electrochromic film has the fastest response speed, the lower the oxidation potential is, the higher the reduction potential is, the closer the oxidation potential is, the lower the voltage required to be provided is when the electrochromic film is used, and the cost is reduced; it can be seen from fig. 6 that the porous electrochromic film prepared in example 1 can be completely reduced to an original state after undergoing an oxidation reaction under a cyclic voltage, and has excellent cyclic stability.
Test example 4
Using "Chen X, Zhang W, Zhu S, Wang S, Wu X, Wang Y, et al, High-performance electrochemical device based on polythiothem/poly (3-thiobenzene boron acid) bilayer file [ J]Organic electronics 2019; comparative example 4 was ITO/P3TBA/PT/Gel/ITO supplied at 75:105373 "; with "Zhang S, Chen S, Hu F, Xu R, Yan B, Jiang M, et al, spray-process, large-area, patterned and all-solid-state electrochemical devices based on silicon/polyaniline nanocomposites [ J]Solar Energy Materials and Solar cells.2019; ITO/SiO solid provided by 200:109951 ″2PANI/Gel/PEDOT comparative example 5; as a result, the microorganism is represented by "ZHao S, Huang W, Guan Z, Jin B, Xiao D.A novel bis (dihydroxyxypyl) viron-based all-in-one electrochromism device with high circulation status and coloration effect [ J]Electrochimica acta.2019; 298:533-40 "provided ITO/PVA-borax/Gel/ITO as comparative example 6; with "Zhuang W, Chen X, Zhuang G, Wang S, Zhu S, Wu X, et al.connecting Polymer/silver nanowire stacking composite films for high-performance electrochemical devices [ J]Solar Energy Materials and Solar cells, 2019; 200: 109919' provided ITO/P3TE/AgNWs/Gel/ITO is comparative example 7, the performance of the electrochromic devices of example 10 and comparative examples 4-7 is tested, and the obtained results are shown in Table 2 and FIGS. 7-13;
TABLE 2 Properties of electrochromic devices of example 10 and comparative examples 4 to 7
Electrochromic device Optical contrast Measuring wavelength Bleaching time Colouring time
Example 10 51％ 786nm 1.2s 3.2s
Comparative example 4 48％ 742nm 0.48s 5.27s
Comparative example 5 62％ 700nm 5.7s 3.2s
Comparative example 6 60％ 520nm 2.1s 4.5s
Comparative example 7 19％ 750nm 0.9s 8.7s
Fig. 7 is a graph showing cyclic voltammetry characteristics of the electrochromic device prepared in example 10, fig. 8 is a test result of response speed of the electrochromic device prepared in example 10, figure 9 is a uv-vis-ir chromatogram of the colored state and the bleached state of the electrochromic device prepared in example 10, FIG. 10 is a graph showing the cyclic voltammetry characteristics of an electrochromic film prepared by a doctor blade method using the same electrochromic mixture as in example 1, FIG. 11 is a graph showing cyclic voltammetry characteristics of an electrochromic film prepared by a spin coating method using the same electrochromic mixture as in example 1, fig. 12 is a cyclic voltammetry curve of the multi-colored electrochromic film of example 2, and fig. 13 is a cyclic voltammetry curve of an electrochromic device prepared by the method of example 10 from the multi-colored electrochromic film of example 8.
As can be seen from Table 2, the device prepared by the porous electrochromic film prepared by the invention has excellent comprehensive performance, although the performance is reduced, the device still has better performance compared with data in other documents, particularly, the device has obvious advantage in response speed, the optical contrast is kept above 50%, and the response speed is fastest.
FIG. 7 shows a graph comparing FIG. 4 in which the oxidation peak and the reduction peak are broadened due to the effects of the double-layer conductive glass resistance and the electrolyte viscosity in the porous electrochromic device; as can be seen from fig. 9, the difference between the bleached state and the original state indicates that the color change of the electrochromic device can be restored, and a larger absorption peak appears at 786nm, which is different from the case of example 1, i.e., fig. 4, in that the overall decrease in absorbance (the value of the ordinate) and the appearance of a plurality of absorption peaks are reflected, which is mainly caused by the decrease in the efficiency of the redox reaction of the active material of the electrochromic thin film due to the increase in the overall impedance value of the device.
As shown by comparing fig. 10 to 11 with fig. 4, the difference between the oxidation-reduction potentials of the films prepared by the doctor blade method and the spin coating method is large, and the high working potential increases the use cost, which can be effectively solved by preparing the film by the electrostatic spraying method, as can be seen from the comparison in table 1 (the repeated curve is the result of repeated tests); two distinct oxidation peaks in fig. 11 indicate successful preparation of a multi-color electrochromic film with two color changes, while the reduction in oxidation potential indicates the performance characteristics of the porous film-lower operating voltage, which reduces use costs.
The two pairs of redox peaks in fig. 12 indicate successful fabrication of devices with multi-color electrochromic films.
The response speed characteristic of the electrochromic film is improved from the appearance form and the internal structure of the electrochromic film, the traditional method is usually a template method or a core-shell structure, the two methods are complex in process and high in cost, the porous electrochromic film can be efficiently prepared through electrostatic spraying deposition, the effect is excellent, the applicable material is wide, and the cost can be greatly reduced compared with the traditional method.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A preparation method of a porous electrochromic film comprises the following steps:
(1) providing an electrochromic material mixed solution; the raw materials for preparing the electrochromic material mixed solution comprise an organic electrochromic material, an inorganic intrinsic conductor material and an organic solvent; the inorganic intrinsic conductor material is a silver nanowire; the organic electrochromic material comprises one or more of polyimide electrochromic materials, polyaniline electrochromic materials, polyamide electrochromic materials, polytriphenylamine electrochromic materials, polythiophene electrochromic materials and polypyrrole electrochromic materials;
the organic solvent comprises dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone or acetonitrile;
the viscosity of the electrochromic material mixed solution is 3-6P;
(2) depositing the electrochromic material mixed solution on the surface of a substrate through electrostatic spraying to obtain a porous electrochromic film; the substrate comprises ITO glass, FTO glass, a flexible PET film, conductive hydrogel or aluminum foil paper.
2. The preparation method according to claim 1, wherein the mass ratio of the organic electrochromic material to the inorganic intrinsic conductor material to the organic solvent is (4-10): 0.1:100.
3. The method according to claim 1, wherein the electrostatic coating has a negative voltage of 0 to-3 kV and a positive voltage of 5 to 15 kV; the environment temperature of the electrostatic spraying is 20-25 ℃, and the environment humidity is less than 30 RH%.
4. The manufacturing method according to claim 1 or 3, wherein the electrochromic material mixture is ejected from a nozzle during the electrostatic spray deposition; the distance between the spray head and the substrate is 10-20 cm; the injection speed of the electrochromic material mixed liquid is 0.03-0.10 mm/min.
5. The porous electrochromic film prepared by the preparation method of any one of claims 1 to 4 is of a porous structure and has a pore diameter of 300 to 800 nm.
6. A preparation method of a multi-color electrochromic film comprises the following steps:
depositing an inorganic electrochromic film on the surface of the substrate of any one of claims 1 to 4, and then depositing the electrochromic material mixed solution on the surface of the inorganic electrochromic film through electrostatic spraying to obtain a multi-color electrochromic film;
and secondly, depositing the porous electrochromic film on the surface of the substrate according to the preparation method of any one of claims 1 to 4 to obtain the porous electrochromic film, and depositing the inorganic electrochromic film on the surface of the porous electrochromic film to obtain the multicolor electrochromic film.
7. The multi-color electrochromic film prepared by the preparation method of claim 6 comprises a porous electrochromic film and an inorganic electrochromic film which are laminated.
8. An electrochromic device comprising a first transparent conductive layer, an electrochromic film, an electrolyte layer and a second transparent conductive layer which are sequentially stacked, wherein the electrochromic film is the porous electrochromic film of claim 5 or the multi-color electrochromic film of claim 7.
9. The method for producing an electrochromic device according to claim 8, wherein a raw material of the electrolyte layer is a gel electrolyte or a solid electrolyte, the first transparent conductive layer is transparent conductive glass, the second transparent conductive layer is transparent conductive glass, and the production method includes method I or method II:
method I, when the electrolyte in the electrolyte layer is a gel electrolyte:
sequentially laminating transparent conductive glass covered with an electrochromic film, a hot melt adhesive and the transparent conductive glass, wherein the hot melt adhesive is arranged on the periphery of the transparent conductive glass and is heated and bonded to obtain a sandwich structure with a gap; the transparent conductive glass covering the electrochromic film is prepared by the preparation method of any one of claims 1 to 4 or the preparation method of claim 6;
injecting gel electrolyte into the gap of the sandwich structure, and packaging to obtain an electrochromic device;
method II, when the electrolyte in the electrolyte layer is a solid electrolyte:
preparing an electrochromic film on the surface of first transparent conductive glass by adopting the preparation method of any one of claims 1-4 and 6 to obtain transparent conductive glass covering the electrochromic film;
preparing a solid electrolyte membrane on the surface of the second transparent conductive glass to obtain transparent conductive glass covering the solid electrolyte membrane;
and adhering the transparent conductive glass covering the electrochromic film and the transparent conductive glass covering the solid electrolyte film by using a hot melt adhesive to ensure that the solid electrolyte film is fully contacted with the electrochromic film, thereby obtaining the electrochromic device.
CN202010410536.6A 2020-05-15 2020-05-15 Porous electrochromic film, multi-color electrochromic film, electrochromic device and preparation method Expired - Fee Related CN111474792B (en)

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