CN113963844B - Flexible silver nanowire-based composite transparent film heater and preparation method thereof - Google Patents
Flexible silver nanowire-based composite transparent film heater and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/02—Details
- H05B3/03—Electrodes
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The invention discloses a preparation method of a silver nanowire-based transparent film heater, which comprises the following steps: cleaning a substrate and carrying out hydrophilic treatment; arranging a silver nanowire layer on a substrate by using the silver nanowire ethanol dispersion liquid, and then drying to form a silver nanowire film; arranging an oxide nanoparticle layer on the silver nano film by using the oxide nanoparticle deionized water dispersion liquid, and then drying to obtain the AgNWs/oxide composite transparent conductive film; arranging a conductive polymer layer on the AgNWs/oxide composite transparent conductive film by using the conductive polymer deionized water dispersion liquid, and then drying to obtain the AgNWs/oxide/conductive polymer composite transparent conductive film; the AgNWs/oxide/conductive polymer composite transparent conductive film is prepared into a flexible silver nanowire-based composite transparent film heater. The invention can effectively reduce the contact resistance of the silver nanowire conductive network, improve the photoelectric property of the film and reduce the surface roughness.
Description
Technical Field
The invention belongs to the technical field of transparent conductive films and transparent film heating devices, and particularly relates to a flexible silver nanowire-based composite transparent film heater and a preparation method thereof.
Background
Transparent film heater is a transparent heating device based on transparent conducting film, and when the electric current flowed through whole conducting layer, transparent film heater produced the heat through the joule effect, and very environmental protection is worth promoting. Currently, transparent film heaters are widely used in window defrosters, sensors, defrosters, outdoor panel displays, thermotherapeutic pads, camera lenses, wearable electronics, and other diverse applications (traffic, construction, medical, sports, etc.). The demand for transparent thin film heaters having better performance in different fields is also continuously expanding, and transparent thin film heater materials are receiving wide attention.
Conventionally, Indium Tin Oxide (ITO) shows good compatibility in terms of transparency and conductivity, and is widely used, but is not suitable for the next generation of flexible transparent thin film heaters due to its brittleness, limited supply of indium, and severe manufacturing conditions. Candidate materials to replace ITO are required to have relatively good optical transparency, electrical conductivity, and flexibility, and many materials such as carbon nanotubes, graphene, conductive polymers, metal grids, and metal nanowires have been developed for manufacturing transparent thin film heaters. Of these materials, silver nanowires (agnws) are one of the best candidates to replace ITO due to their perfect flexibility, high conductivity, low visible light absorption, and low cost manufacturing process.
Patent CN 104053256 a uses silver nanowires synthesized by low temperature liquid phase method as raw material, adopts non-vacuum, non-high temperature molding process to coat transparent conductive film, adopts mature and commercialized conductive polymer to improve the heating uniformity of the film, and obtains thin layer protective film by liquid phase coating of cheap organic polymer film, which has the defects of poor film transmittance, expensive sputtering electrode cost and large contact resistance of the pasted electrode.
The patent CN 106131984 a utilizes a cross-coating method to prepare a silver nanowire/graphene oxide composite film heater, although the film prepared in this way has good photoelectric properties and uniformity, the preparation steps are cumbersome, and the spin-coating method is difficult to be applied to uniform preparation of large-area samples; according to the method, the composite heating film of the silver nanowires and the graphene oxide is prepared on the high-temperature-resistant hard substrate, and the nano protective layer is coated on the composite heating film, so that the composite heating film is even in heating and high in use stability, but still based on the hard substrate, and cannot meet the application requirement in a flexible environment.
The main problems of the silver nanowire-based transparent film heater prepared by the existing simple methods of spin coating, blade coating, spray coating and the like are that the binding force between the silver nanowires in the prepared silver nanowire conductive network is weak, higher contact resistance exists, the binding force between the silver nanowires and a substrate is weak, and the pure silver nanowires are easily corroded in a natural environment, so that the conductivity and the light transmittance of the whole conductive network are deteriorated; therefore, the method can improve the contact resistance of the silver nanowire network on the flexible substrate, and the improvement of the weather resistance of the silver nanowire network has important research value for improving the performance of the silver nanowire-based transparent film heating device.
Disclosure of Invention
The invention aims to provide a flexible silver nanowire-based transparent film heater, which can solve the problems of large contact resistance of silver nanowires and the like.
In order to solve the technical problem, the invention provides a preparation method of a silver nanowire-based transparent thin film heater, which comprises the following steps:
1) cleaning the substrate and carrying out hydrophilic treatment to obtain the substrate with a hydrophilic surface;
the substrate is a transparent flexible substrate;
2) preparing silver nanowire ethanol dispersion liquid with the concentration of 0.2-0.8 mg/ml;
arranging a silver nanowire layer on the substrate with the hydrophilic surface obtained in the step 1) by using the silver nanowire ethanol dispersion, and then drying (removing ethanol) to form a silver nano film (silver nano transparent conductive network);
3) preparing an oxide nanoparticle deionized water dispersion liquid with the concentration of 0.08-0.4 mg/ml;
arranging an oxide nanoparticle layer on the silver nano film obtained in the step 2) by using the oxide nanoparticle deionized water dispersion liquid, and then drying (removing deionized water) to obtain an AgNWs/oxide composite transparent conductive film;
4) preparing a conductive polymer deionized water dispersion liquid with the concentration of 0.5-1 mg/ml;
arranging a conductive polymer layer on the AgNWs/oxide composite transparent conductive film by using the conductive polymer deionized water dispersion liquid, and then drying (removing deionized water) to obtain the AgNWs/oxide/conductive polymer composite transparent conductive film;
5) preparing a conductive electrode:
the AgNWs/oxide/conductive polymer composite transparent conductive film is prepared into a flexible silver nanowire-based composite transparent film heater.
The improvement of the preparation method of the silver nanowire-based transparent thin film heater of the invention is as follows:
in step 3): the composite oxide nano particles are silicon dioxide, titanium dioxide, zinc oxide, zirconium dioxide and ferroferric oxide, and the particle diameter is 10-30 nm (preferably 10-20 nm);
in the step 4): the conductive polymer is poly (3,4 ethylenedioxythiophene) -polystyrene sulfonic acid, polyaniline, or polypyrrole.
The preparation method of the silver nanowire-based transparent thin film heater is further improved as follows: the diameter of the silver nanowire in the step 2) is 20-50 nm.
The preparation method of the silver nanowire-based transparent thin film heater is further improved as follows: the transparent flexible substrate in the step 1) is as follows: the average transmittance in visible light region is not less than 80%, and the average transmittance at 550nm is not less than 90%.
The transparent flexible substrate is specifically any one of: polyethylene terephthalate, polycarbonate, colorless transparent polyimide, polymethyl methacrylate, polydimethylsiloxane, and polyurethane.
The preparation method of the silver nanowire-based transparent thin film heater is further improved as follows:
in the step 2): the number of the silver nanowire layers is 1-4, and the silver nanowire layers are dried for 10-30 min at the temperature of 50-100 ℃ so as to remove ethanol;
in the step 3): the number of the oxide nanoparticle layers is 1-5, and the oxide nanoparticle layers are dried at 50-100 ℃ for 10-30 min to remove deionized water;
in the step 4): the number of the conductive polymer layers is 1-4, and the conductive polymer layers are dried at 50-100 ℃ for 10-30 min so as to remove deionized water.
The preparation method of the silver nanowire-based transparent thin film heater is further improved as follows:
the silver nanowire layer of the step 2) is arranged in a manner (coating manner) as follows: spraying, blade coating, spin coating, slit coating and screen printing;
the oxide nanoparticle layer in the step 3) is arranged in the following manner: spraying, blade coating, spin coating and slit coating;
the conductive polymer layer in the step 4) is arranged in the following manner: spray coating, blade coating, spin coating, slot coating.
The preparation method of the silver nanowire-based transparent thin film heater is further improved as follows: the cleaning and hydrophilization treatment in the step 1) comprises the following steps:
and (3) sequentially and respectively ultrasonically cleaning the transparent flexible substrate in acetone, deionized water and ethanol for 20-30 min, and then cleaning the transparent flexible substrate in an oxygen plasma cleaning machine for 15-20 min to obtain the substrate with the hydrophilic surface.
The preparation method of the silver nanowire-based transparent thin film heater is further improved as follows: in the step 5): and (3) printing conductive silver paste on two ends (namely, printing 1 silver electrode on each of the two ends) of the composite transparent conductive film obtained in the step (4) by utilizing screen printing, and treating at 120-150 ℃ for 30-60 min to obtain the flexible silver nanowire-based composite transparent film heater.
The invention also provides a silver nanowire-based transparent film heater prepared by any one of the methods.
The preparation method of the flexible silver nanowire-based composite transparent film heater comprises the following steps: cleaning a substrate, carrying out hydrophilic treatment, coating a silver nanowire ethanol dispersion liquid on the substrate, drying, then continuously coating oxide nanoparticles, drying again, then continuously coating a conductive polymer, drying, preparing a flexible silver nanowire-based multi-element composite transparent conductive film, printing silver electrodes at two ends of the transparent conductive film, and finally obtaining the stably-heated flexible silver nanowire-based composite transparent conductive film heater. Namely, in the invention, the transparent conductive network is composed of silver nanowires, the diameter of the silver nanowires is 20-50 nm, then oxide nanoparticles are compounded on the silver nanowire-based transparent conductive network, and after the silver nanowires and the oxide particles are coated, a layer of conductive polymer is coated.
The invention has the following technical advantages:
1) the AgNWs/oxide/conductive polymer composite transparent conductive film strengthens the welding effect on the silver nanowires through the capillary force and the like generated in the evaporation process of an oxide particle solvent, and the conductive polymer increases a conductive path and effectively reduces the sheet resistance.
2) The added oxide nanoparticles have an anti-reflection effect, and can improve the transmittance of the silver nanowire transparent conductive film; and the silver nanowires can be welded at the junctions of the silver nanowires through the surface tension of the silver nanowires so as to reduce the contact resistance (the bonding strength between the silver nanowires is also improved, and the bending resistance is improved).
3) The oxide particles and the conductive polymer can coat part of the surface layer of the silver nanowires, so that the oxidation corrosion of the silver nanowires in the air is reduced, namely, the corrosion resistance and oxidation resistance of the silver nanowires are improved; the stability of the silver nanowire conductive network is enhanced, and the surface roughness is reduced.
Meanwhile, the oxide particles and the conductive polymer have good compatibility, and can be commonly used for preparing the silver nanowire composite conductive film.
4) The preparation method is based on a solution method, and has the advantages of simple preparation method, low cost and high sample quality.
5) And the problems of large contact resistance, easy oxidation and the like of the silver nanowires are solved.
In conclusion, the method can effectively reduce the contact resistance of the silver nanowire conductive network, improve the photoelectric property of the film and reduce the surface roughness; the product of the invention has excellent photoelectric property, bending resistance and corrosion resistance, is uniformly and rapidly heated, and is expected to be used as a transparent electric heating defogging device in occasions such as automobile windshields, building outer walls and the like.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a flow chart of the preparation of example 1.
FIG. 2 is an electron microscope topography of the product obtained in example 1.
FIG. 3 is a graph showing the heating effect of example 3 (the heating effects of examples 1 to 3 are substantially the same).
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
the starting materials used in the following examples are all available in a conventional commercial manner:
PSS, poly (3,4 ethylenedioxythiophene) -polystyrene sulfonic acid.
The selected substrate is a transparent flexible substrate, and the following requirements are met: the average transmittance in visible light region is not less than 80%, and not less than 90% at 550nm, and can be polyethylene terephthalate, polycarbonate, colorless transparent polyimide, polymethyl methacrylate, polydimethylsiloxane, and polyurethane.
1) substrate cleaning and hydrophilization treatment:
selecting polyethylene glycol terephthalate as a substrate of a material;
and sequentially and respectively ultrasonically cleaning the substrate in acetone, deionized water and ethanol for 30min according to a conventional mode, and then cleaning the substrate in an oxygen plasma cleaning machine for 15min to obtain the substrate with the hydrophilic surface.
2) Dispersing silver nanowires (with the diameter of 20-50 nm) in ethanol, preparing a silver nanowire ethanol dispersion liquid with the concentration of 0.2mg/ml, coating 4 silver nanowire layers on the substrate obtained in the step 1) by using a spraying technology (when coating, the thickness of each wet film is 8-10 mu m, and after one layer is coated, the next layer is directly coated), and then drying at 80 ℃ for 10min to remove ethanol serving as a solvent, so that the silver nanowire transparent conductive film (silver nanowire conductive network) is formed on the substrate.
3) Dispersing silicon dioxide nano particles (the particle diameter is 10-15 nm) in deionized water, and preparing a silicon dioxide nano particle deionized water dispersion liquid with the concentration of 0.08 mg/ml; coating 5 silicon dioxide nanoparticle layers (each layer of wet film is 8-10 μm when spraying, and the next layer is directly sprayed after one layer is sprayed) on the silver nanowire transparent conductive film by using a spraying technology, and drying at 80 ℃ for 10min to remove deionized water serving as a solvent; thereby preparing the AgNWs/oxide composite transparent conductive film on the substrate.
4) Uniformly dispersing PEDOT and PSS in deionized water to prepare a conductive polymer deionized water dispersion liquid with the concentration of about 0.5 mg/ml; and (3) coating 4 conductive polymer solution layers on the AgNWs/oxide composite transparent conductive film by a spraying mode (when spraying, the thickness of each wet film is 8-10 mu m, and after one layer is sprayed, the next layer is directly sprayed), and finally drying at 80 ℃ for 10min to remove deionized water serving as a solvent, thereby preparing the AgNWs/oxide/conductive polymer composite transparent conductive film on the substrate.
5) Conductive electrode preparation (conventional technique):
and (3) printing conductive silver paste on two ends of the composite transparent conductive film obtained in the step (4) (namely, printing 1 silver electrode on each of the two ends of the composite transparent conductive film) by utilizing screen printing, and then treating at 150 ℃ for 30min to obtain the flexible silver nanowire-based composite transparent film heater.
Embodiment 2, a method for manufacturing a flexible silver nanowire-based transparent thin film heater, comprising the steps of:
1) substrate cleaning and hydrophilization treatment:
selecting polydimethylsiloxane as a substrate of a material;
and sequentially and respectively ultrasonically cleaning the substrate in acetone, deionized water and ethanol for 20min according to a conventional mode, and then cleaning the substrate in an oxygen plasma cleaning machine for 20min to obtain the substrate with the hydrophilic surface.
2) Dispersing silver nanowires (with the diameter of 20-50 nm) in ethanol, preparing a silver nanowire ethanol dispersion liquid with the concentration of 0.8mg/ml, coating 1 silver nanowire layer (the thickness of a wet film is 8-10 mu m) on the substrate obtained in the step 1) by using a spraying technology, and drying at 50 ℃ for 30min to remove the ethanol serving as a solvent, so that the silver nanowire transparent conductive film (silver nanowire conductive network) formed on the substrate is formed.
3) Dispersing titanium dioxide nano particles (with the particle size of 10-15 nm) in deionized water to prepare a titanium dioxide nano particle deionized water dispersion liquid with the concentration of 0.4 mg/ml; coating 1 titanium dioxide nanoparticle layer (the thickness of a wet film is 8-10 mu m) on the silver nanowire transparent conductive film by using a blade coating technology, and then drying at 50 ℃ for 30min to remove deionized water serving as a solvent; thereby preparing the AgNWs/oxide composite transparent conductive film on the substrate.
4) Uniformly dispersing PEDOT (PSS) in deionized water to prepare a deionized water dispersion solution of conductive polymers with the concentration of about 1mg/ml, and coating 2 layers of conductive polymer solution on the AgNWs/oxide composite transparent conductive film by using a blade coating mode (when blade coating is carried out, the thickness of each layer of wet film is 8-10 mu m; and directly blade-coating the next layer after blade-coating one layer), and finally drying at 50 ℃ for 30min to remove deionized water used as a solvent, thereby preparing the AgNWs/oxide/conductive polymer composite transparent conductive film on the substrate.
5) Preparing a conductive electrode:
and (3) treating at 150 ℃ for 60min, and the rest is equal to the step 5) of the example 1 to obtain the flexible silver nanowire-based composite transparent thin film heater.
Example 3: a preparation method of a flexible silver nanowire-based transparent film heater comprises the following steps:
1) substrate cleaning and hydrophilization treatment:
selecting colorless transparent polyimide as a substrate of the material;
and sequentially and respectively ultrasonically cleaning the substrate in acetone, deionized water and ethanol for 30min according to a conventional mode, and then cleaning the substrate in an oxygen plasma cleaning machine for 20min to obtain the substrate with the hydrophilic surface.
2) Dispersing silver nanowires (with the diameter of 20-50 nm) in ethanol, preparing silver nanowire ethanol dispersion liquid with the concentration of 0.4mg/ml, and coating 2 silver nanowire layers on the substrate by using a spin coating technology (each layer of the spin coating is: 2000rpm, 60s), followed by drying at 80 ℃ for 30min to remove ethanol as a solvent, so that a silver nanowire transparent conductive film (silver nanowire conductive network) was formed on the substrate.
3) Dispersing titanium dioxide nano particles (with the particle size of 10-20 nm) in deionized water to prepare deionized water dispersion liquid of the titanium dioxide nano particles with the concentration of 0.2 mg/ml; 2 layers of titanium dioxide nano particles (each layer of the titanium dioxide nano particles is coated at 2000rpm for 60s) are coated on the silver nanowire transparent conductive film by using a spin coating technology, and then the silver nanowire transparent conductive film is dried at 80 ℃ for 30min to remove deionized water used as a solvent; thereby preparing the AgNWs/oxide composite transparent conductive film on the substrate.
4) PSS is evenly dispersed in deionized water to prepare a conductive polymer deionized water dispersion liquid with the concentration of about 0.5mg/ml, and 4 conductive polymer solution layers are coated on the AgNWs/oxide composite transparent conductive film in a spin coating mode (each layer of spin coating is: 2000rpm, 60s), and finally drying at 80 ℃ for 10min to remove the deionized water used as the solvent, thereby obtaining the AgNWs/oxide/conductive polymer composite transparent conductive film on the substrate.
5) Preparation of conductive electrode
And (3) treating at 120 ℃ for 30min, and obtaining the flexible silver nanowire-based composite transparent thin film heater, wherein the rest is equal to the step 5) of the embodiment 1.
Comparative example 1, step 3) and 4) of example 1 were eliminated, that is, a conductive electrode was provided on the resultant of step 2), and the rest was the same as example 1.
Comparative example 2, step 4) of example 1 was eliminated, that is, a conductive electrode was provided on the resultant of step 3), and the rest was the same as example 1.
Comparative example 3, step 3) of example 1 was eliminated, i.e. step 4) was carried out directly after step 2); the rest is the same as example 1.
Performance experiments were carried out: the film heaters prepared in the above examples 1 to 3 and comparative examples 1 to 3 were subjected to the following performance tests according to the conventional test methods, and the results are shown in the following table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Square resistor | 18～20Ω/sq | 18～20Ω/sq | 18～20Ω/sq | 35～40Ω/sq | 22～26Ω/sq | 28～30Ω/sq |
| Transmittance of light | 95.0％ | 95.0％ | 95.0％ | 93.0％ | 95.0％ | 93.0％ |
| Surface roughness | 12.8nm | 12.7nm | 12.9nm | 21.4nm | 14.1nm | 13.9nm |
| Resist bending | 93％ | 97％ | 94％ | 403％ | 179％ | 287％ |
| Corrosion resistance | 249％ | 253％ | 257％ | 421％ | 301％ | 257％ |
Description of the drawings:
transmittance (substrate removal): measured by DU800 uv-vis spectrophotometer (beckmann, usa);
square resistance: measured by RTS-9 type four-probe tester (the manufacturer is Guangzhou four-probe technology);
surface roughness, as measured by Atomic Force Microscopy (AFM);
the bending resistance is measured by an automatic bending tester, specifically, two sides of a 2cm multiplied by 2cm film sample are fixed and bent into a ring shape, and the bending resistance is measured after repeated bending tests for 1500 times and the change rate of the sheet resistance is calculated, thus the bending resistance is expressed.
The test method is to put the sample into hydrogen sulfide gas to be sealed and stored for 90min, then test the sheet resistance and calculate the sheet resistance change rate to show the corrosion resistance.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (10)
1. The preparation method of the silver nanowire-based transparent film heater is characterized by comprising the following steps of:
1) cleaning the substrate and carrying out hydrophilic treatment to obtain the substrate with a hydrophilic surface;
the substrate is a transparent flexible substrate;
2) preparing silver nanowire ethanol dispersion liquid with the concentration of 0.2-0.8 mg/ml;
arranging a silver nanowire layer on the substrate with the hydrophilic surface obtained in the step 1) by using the silver nanowire ethanol dispersion, and then drying to form a silver nanowire film;
3) preparing an oxide nanoparticle deionized water dispersion liquid with the concentration of 0.08-0.4 mg/ml;
arranging an oxide nanoparticle layer on the silver nano film obtained in the step 2) by using the oxide nanoparticle deionized water dispersion liquid, and then drying to obtain an AgNWs/oxide composite transparent conductive film;
4) preparing a conductive polymer deionized water dispersion liquid with the concentration of 0.5-1 mg/ml;
arranging a conductive polymer layer on the AgNWs/oxide composite transparent conductive film by using the conductive polymer deionized water dispersion liquid, and then drying to obtain the AgNWs/oxide/conductive polymer composite transparent conductive film;
5) preparing a conductive electrode:
the AgNWs/oxide/conductive polymer composite transparent conductive film is prepared into a flexible silver nanowire-based composite transparent film heater.
2. The method of manufacturing a silver nanowire-based transparent thin film heater according to claim 1, wherein:
in the step 3): the composite oxide nano particles are silicon dioxide, titanium dioxide, zinc oxide, zirconium dioxide and ferroferric oxide, and the particle diameter is 10-30 nm;
in the step 4): the conductive polymer is poly (3,4 ethylenedioxythiophene) -polystyrene sulfonic acid, polyaniline and polypyrrole.
3. The method of manufacturing a silver nanowire-based transparent thin film heater according to claim 2, wherein:
the diameter of the silver nanowire in the step 2) is 20-50 nm.
4. The method of claim 3, wherein the silver nanowire-based transparent thin film heater comprises:
the transparent flexible substrate in the step 1) is as follows: the average transmittance in a visible light region is not less than 80%, and the average transmittance in a 550nm region is not less than 90%.
5. The method of claim 4, wherein the silver nanowire-based transparent thin film heater comprises:
the transparent flexible substrate is any one of: polyethylene terephthalate, polycarbonate, colorless transparent polyimide, polymethyl methacrylate, polydimethylsiloxane, and polyurethane.
6. The method for manufacturing a silver nanowire-based transparent thin film heater according to any one of claims 1 to 5, characterized in that:
in the step 2): the number of the silver nanowire layers is 1-4, and the silver nanowire layers are dried for 10-30 min at the temperature of 50-100 ℃ so as to remove ethanol;
in the step 3): the number of the oxide nanoparticle layers is 1-5, and the oxide nanoparticle layers are dried at 50-100 ℃ for 10-30 min to remove deionized water;
in the step 4): the number of the conductive polymer layers is 1-4, and the conductive polymer layers are dried at 50-100 ℃ for 10-30 min so as to remove deionized water.
7. The method of claim 6, wherein the silver nanowire-based transparent thin film heater comprises:
the silver nanowire layer in the step 2) is arranged in the following mode: spraying, blade coating, spin coating, slit coating and screen printing;
the oxide nanoparticle layer in the step 3) is arranged in the following manner: spraying, blade coating, spin coating and slit coating;
the conductive polymer layer in the step 4) is arranged in the following manner: spray coating, blade coating, spin coating, slot coating.
8. The method for manufacturing a silver nanowire-based transparent film heater according to any one of claims 1 to 7, wherein the cleaning and hydrophilization treatment in the step 1) is:
and (3) sequentially and respectively ultrasonically cleaning the transparent flexible substrate in acetone, deionized water and ethanol for 20-30 min, and then cleaning the transparent flexible substrate in an oxygen plasma cleaning machine for 15-20 min to obtain the substrate with the hydrophilic surface.
9. The method for manufacturing a silver nanowire-based transparent thin film heater according to any one of claims 1 to 7, characterized in that:
in the step 5): printing conductive silver paste on two ends of the composite transparent conductive film obtained in the step 4) by utilizing screen printing, and processing for 30-60 min at 120-150 ℃ to obtain the flexible silver nanowire-based composite transparent film heater.
10. A silver nanowire-based transparent thin film heater prepared by the method of any one of claims 1 to 9.
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