CN112822803B - Bendable heating device of adhesive tape structure and preparation method thereof - Google Patents

Bendable heating device of adhesive tape structure and preparation method thereof Download PDF

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Publication number
CN112822803B
CN112822803B CN202110175544.1A CN202110175544A CN112822803B CN 112822803 B CN112822803 B CN 112822803B CN 202110175544 A CN202110175544 A CN 202110175544A CN 112822803 B CN112822803 B CN 112822803B
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coating
graphene oxide
conductive
layer
heating device
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CN112822803A (en
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耿宏章
赵惠
邓洪
耿文浩
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Taian Zhongyan Composite Materials Technology Co ltd
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Taian Zhongyan Composite Materials Technology Co ltd
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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
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • 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
    • 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—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater 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
    • H05B3/14—Heater 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 the material being non-metallic
    • H05B3/145—Carbon only, e.g. carbon black, graphite
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]

Abstract

The invention discloses a bendable heating device with an adhesive tape structure and a preparation method thereof, and the main steps are as follows: firstly, cleaning a polyester film substrate for standby; and uniformly coating the acrylic adhesive and the conductive mixed solution on a substrate film coiled material in sequence by using a coating machine, and coating conductive silver paste or pasting a conductive metal foil and then packaging to prepare the flexible transparent conductive film. And coating a layer of acrylic glue on the uncoated side of the flexible transparent conductive film by using a coating machine, and coiling for standby. When the heating device is applied, the coiled material with proper width is cut out to a required length, then the wires are connected to the silver electrodes or the metal foils at the two ends, and finally the heating device which is easy to paste and bendable is formed. The heating device prepared by the method has the characteristics of good stability, low surface resistance, uniform surface coating, controllable size, flexibility, easy adhesion and the like. The film has simple preparation process, short period, high film conductivity, low surface resistance as low as 20-200 ohm/sq and heating power of 100-2400W/m 2 。

Description

Bendable heating device of adhesive tape structure and preparation method thereof
Technical Field
The invention relates to a bendable heating device with an adhesive tape structure and a preparation method thereof, and belongs to the field of conductive heating films.
Background
Heat energy is one of the important energy modes for human survival, and in the history of human development, people use sun, fire and electricity to obtain heat energy. Currently, electric heating is the most widely used method for obtaining thermal energy. The conductive heating film is used as one of electric heating modes and is widely applied in life. The conductive heating film is a sheet film type device for converting electric energy into heat energy, and has important application in the fields of military, industry, agriculture, transportation, household use and the like. Conductive heating films can be classified into non-transparent conductive heating films and transparent conductive heating films according to optical properties. Among them, the non-transparent conductive heating film has been widely used in the actual life or industry as a conventional electric heating means. The transparent conductive heating film can meet the requirements of different industries and has a wider application prospect. With the progress of science and technology, electronic products gradually develop towards intelligence, functionalization and flexibility, and transparent conductive heating films used for the devices must also have mechanical flexibility and other characteristics. The transparent flexible heating film is a special film with higher optical transmittance in the visible light range and good bending resistance. The transparent flexible heating film is mainly composed of two parts, namely a conductive heating material and a substrate material, as other conductive heating films; but all materials used must have excellent optical transmittance and mechanical flexibility.
In recent years, films prepared from carbon nanotubes and graphene oxide have been paid attention to because of the advantages of high electric conductivity, high heat conductivity, high light transmittance, good flexibility, large-area preparation and the like, and have wide application in the fields of touch screens, sensors, solar cells and the like. In recent years, films prepared from carbon nanotubes and graphene oxide have been studied as conductive heating materials in the field of transparent flexible heating films, and excellent performances are exhibited.
The disclosed patent technology of a graphene transparent wire film and a preparation method thereof (application number: CN 201410822977.1) provides a graphene modified PET film which is prepared by carrying out surface modification on graphene oxide by using a silane coupling agent, then mixing the graphene oxide with phthalic acid, glycol, a catalyst and a stabilizer, then carrying out reduced pressure polycondensation to obtain a modified polyester PET slice, and casting the slice. The transmittance of the obtained product is improved, but the area resistance is at least 329 omega/sq. The material with higher surface resistance is easy to generate static electricity after friction, is not easy to eliminate, has high energy consumption, seriously affects the appearance and the service performance of the material, and has certain potential safety hazard, so the material cannot be applied to industries requiring smaller surface resistance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a bendable heating material with low surface resistance and high heating efficiency, and the specific technical scheme is as follows:
as a first aspect of the present invention, there is provided a bendable heating device of an adhesive tape structure, where the heating device includes, from top to bottom, a packaging layer, a conductive layer, a heating layer, a first adhesive layer, a substrate, and a second adhesive layer, where the first adhesive layer and the second adhesive layer are both made of acrylic adhesive.
Preferably, the thickness of the first bonding layer and the second bonding layer is 10-200 μm; more preferably, the first adhesive layer has a thickness of 30 μm; the second adhesive layer has a thickness of 50 μm.
The substrate is made of polyethylene glycol terephthalate (PET), polyimide (PI) or glass fiber felt, and has a thickness of 10-500 mu m, preferably 50 mu m; the packaging layer is made of PET material, and has the thickness of 10-500 mu m, preferably 50 mu m; the packaging layer has the functions of preventing water and dust and protecting the heating layer from being interfered by external environment.
The conductive layer is a metal foil, preferably a copper foil, more preferably a conductive coating prepared from conductive silver paste, and is adhered or coated at two ends of the heating layer, so that the purpose of loading voltage at two ends of the heating layer is achieved.
The thickness of the heating layer is 20-1500 mu m, and the components comprise carbon nano tubes, graphene oxide, waterborne polyurethane, sodium dodecyl benzene sulfonate, a thickening agent and a leveling agent, wherein the general thickness is 100 mu m, and the heating layer can be quickly heated after being electrified, so that the heating function is realized.
Preferably, the carbon nanotubes are single-walled carbon nanotubes, the purity of the single-walled carbon nanotubes in the heating layer raw material is more than 75 wt%, the outer diameter is 1-2nm, and the length is 5-30 mu m; the graphene oxide has purity of >75wt.%, thickness of 4-7 nm and diameter of about 80 μm; the solid content of the aqueous polyurethane is 10-45 wt%; the solid content of the thickener is 20 to 55wt.%; the solid content of the leveling agent is 15-60 wt%.
Preferably, the heating layer is formed by coating a conductive mixed solution on the surface of a substrate coated with a first bonding layer in advance and air-drying the substrate; the conductive mixed solution is prepared by the following method:
firstly, taking carbon nano tubes and graphene oxide as raw materials, adding a dispersing agent and distilled water serving as a solvent, mixing the above components, performing ultrasonic treatment for 10-90min by using an ultrasonic dispersing machine, centrifuging for 10-50min at a speed of 5000-12000rpm by using a centrifugal machine, and extracting supernatant to obtain a mixed dispersion liquid of the graphene oxide and the carbon nano tubes;
stirring the mixed dispersion liquid, and then sequentially adding the aqueous polyurethane, the thickening agent and the leveling agent until a conductive mixed solution with uniform viscosity is formed;
and finally, coating the conductive mixed solution on the surface of the substrate coated with the acrylic glue, and air-drying to obtain the heating layer. The graphene oxide in the heating layer can fill gaps of the carbon nanotube network, so that the connection resistance between the carbon nanotubes is reduced, and a stable conductive network is formed.
Preferably, in the first step, an ultrasonic dispersion machine is used to prepare a dispersion liquid of carbon nanotubes and graphene oxide, and the conditions are as follows: the power is 50-400W, and the time is 5-100min. The dispersing agent is one or two selected from sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, sodium dodecyl sulfate and cetyltrimethylammonium bromide.
Preferably, the concentration of the carbon nano tube solution in the mixed dispersion liquid of the graphene oxide and the carbon nano tube prepared in the first step is 0.005-5.0mg/ml, and the concentration of the graphene oxide solution is 0.005-5.0mg/ml.
Preferably, in the second step, the mixed solution of graphene oxide and carbon nano tube is stirred at the speed of 100-800rpm, and the aqueous polyurethane, the thickener and the flatting agent are added until a uniform and viscous solution is formed.
Preferably, the mass ratio of the carbon nano tube to the graphene oxide in the conductive mixed solution is 1 (0.05-15), and the mass ratio of the graphene oxide to the aqueous polyurethane is 1 (5-30); the mass ratio of the graphene oxide to the thickener is 1 (0.1-10); the mass ratio of the graphene oxide to the flatting agent is 1 (0.1-10). The heating layer has a single-layer structure, and graphene oxide, carbon nano tubes, waterborne polyurethane, a thickening agent and a leveling agent are uniformly mixed to form a uniform conductive heating coating with high adhesive force on a substrate.
More preferably, the mass ratio of the carbon nano tube to the graphene oxide is 1:0.25, and the mass ratio of the graphene oxide to the aqueous polyurethane is 1:15; the mass ratio of the graphene oxide to the thickener is 1:5; the mass ratio of the graphene oxide to the leveling agent is 1:5.
As a second aspect of the present invention, there is provided a method for producing the heating device, comprising the steps of:
firstly, cutting substrates such as polyethylene glycol terephthalate (PET), polyimide (PI) or glass fiber mats into coiled materials with certain sizes for later use;
pouring the ethanol solution into a coating liquid tank of a coating machine, and then enabling the substrate to sequentially pass through the coating liquid tank and a drying system to remove dust and stains on the surface of the substrate; uniformly coating acrylic glue on the coiled material by using a coating machine to prepare the coiled material with single-sided viscosity;
preparing graphene oxide and carbon nanotubes into a conductive mixed solution according to a certain mass ratio, coating the conductive mixed solution on one sticky surface of a substrate by using a coating machine to prepare a flexible transparent conductive film, and adjusting the coating thickness of the flexible transparent conductive film by adjusting the concentration of the conductive mixed solution and the coating speed of the machine in the process of coating the conductive mixed solution so as to change and adjust the light transmittance and the surface resistance of the flexible transparent conductive film;
step four, sticking the conductive metal foil with double-sided adhesive property on the two ends of the conductive film obtained in the step three before coiling or coating conductive silver paste with certain width on the two ends of the film and drying;
step five, in order to protect the conductive coating of the flexible transparent conductive film, a plastic packaging system is used for packaging the conductive film coated on one side of the conductive mixed solution by using a coiled material with the same width; and coating one side of the flexible transparent conductive film without the coating with a layer of acrylic adhesive by using a coating machine, coating a layer of release protective film, and coiling for standby.
When the heating device is used, a coiled material with proper width is found according to the heating requirement, the required length is cut out, then the copper foils at the two ends are connected with wires, and finally the heating device which is easy to adhere and bendable is formed.
Preferably, the surface resistance of the heating film prepared by the preparation method is as low as 20-200 omega/sq, and the heating power is 100-2400W/m 2 . The surface resistance is mainly determined by the length and the diameter of the carbon nanotubes and the connection mode among the carbon nanotubes, if the heating layer only contains the carbon nanotubes, the carbon nanotubes realize the transmission of carriers through the lap joint among the tubes, and as the lap joint of the carbon nanotubes contains a large number of holes, the connection resistance of the carbon nanotubes is larger, and graphene oxide is filled in the holes of the carbon nanotubes after the graphene oxide is added, so that the connection resistance among the carbon nanotubes can be reduced, and the surface resistance of the heating layer is reduced.
Compared with the prior art, the invention has the beneficial effects that:
1. the bendable heating device of the adhesive tape structure prepared from the carbon nano tube and the graphene oxide provided by the invention consists of the first adhesive layer, the substrate, the second adhesive layer, the heating layer, the conducting layer and the packaging layer, can be adhered to a region needing heating, and has the advantages of easiness in fixing, high heating efficiency, safety, reliability, changeable device geometric shape, wide application range, wider voltage application range and the like;
2. when the adhesive tape is applied, the heating film of the rolled adhesive tape structure can be cut out to a specific length according to actual needs, the heating film is adhered to the surface of an article to be heated, then electric wires are connected to the conductive copper foils at the two sides of the conductive heating film, and then the adhesive tape is heated according to the loading voltage of the heating device; the device has the advantages of light weight, low cost, high deicing efficiency and low energy consumption, and also has excellent anti-icing and deicing functions in application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a flow chart of a bendable heating device with an adhesive tape structure;
FIG. 2 is a schematic diagram of a bendable heating device with an adhesive tape structure according to the present invention;
fig. 3 is an SEM image of the carbon nanotubes and graphene oxide added in example 1, wherein a is an SEM of the pure carbon nanotubes, b is an SEM image of the graphene oxide added, and a hatched plane portion in b is the graphene oxide;
fig. 4 is a graph showing the change of the area resistance of a heating layer of a bendable heating device with an adhesive tape structure according to the mass ratio of carbon nanotubes to graphene oxide;
FIG. 5 is a schematic diagram showing the temperature rise at different voltages when the heating layer resistance of the bendable heating device with the adhesive tape structure is 40 Ω/sq;
fig. 6 is a graph showing the heating stability at-5 ℃ when the voltage of the heating layer of the bendable heating device with the adhesive tape structure is 70V.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments.
The invention provides a preparation method of a bendable heating device with an adhesive tape structure, as shown in fig. 1, comprising the following steps:
firstly, cutting substrates such as polyethylene glycol terephthalate (PET), polyimide (PI) or glass fiber mats into coiled materials with the widths of 10, 20, 30, 40 and 50cm and the lengths of 50m for later use;
pouring the ethanol solution into a coating liquid tank of a coating machine, and then enabling the substrate to sequentially pass through the coating liquid tank and a drying system to remove dust and stains on the surface of the substrate; uniformly coating acrylic glue on the coiled material by using a coating machine to prepare the coiled material with single-sided viscosity;
preparing graphene oxide and carbon nanotubes into a conductive mixed solution according to a certain mass ratio, coating the conductive mixed solution on one sticky surface of a substrate by using a coating machine to prepare a flexible transparent conductive film, and adjusting the coating thickness of the flexible transparent conductive film by adjusting the concentration of the conductive mixed solution and the coating speed of the machine in the process of coating the conductive mixed solution, so that the surface resistance of the flexible transparent conductive film is changed and adjusted;
step four, sticking the conductive metal foil with double-sided adhesive property on the two ends of the conductive film obtained in the step three before coiling or coating conductive silver paste with certain width on the two ends of the film and drying; the method comprises the steps of carrying out a first treatment on the surface of the
Step five, in order to protect the conductive coating of the flexible transparent conductive film, a plastic packaging system is used for packaging the conductive film coated on one side of the conductive mixed solution by using a coiled material with the same width; and coating a layer of acrylic glue on the uncoated side of the flexible transparent conductive film by using a coating machine, and coiling for standby.
When the heating device is used, a coiled material with proper width is found according to the heating requirement, the required length is cut out, then the copper foils at the two ends are connected with wires, and finally the heating device which is easy to adhere and bendable is formed.
The preparation method of the heating layer comprises the following steps: carbon nanotubes and graphene oxide are used as raw materials, sodium dodecyl benzene sulfonate is used as a dispersing agent, and distilled water is used as a solvent. Ultrasonic dispersing for 10-90min, centrifuging at 5000-12000rpm for 10-50min, and collecting supernatant to obtain mixed dispersion liquid with graphene oxide and carbon nanotube ratio of 1-100. And stirring the mixed dispersion liquid, and then sequentially adding the aqueous polyurethane, the thickener and the flatting agent until a viscous and uniform conductive mixed solution is formed.
In particular embodiments, the dispersant is sodium dodecyl benzene sulfonate, unless specifically indicated;
the ultrasonic power is 150W; the hiking speed of the machine is 0.5-100m/min.
The solid content of the aqueous polyurethane is about 35%; the thickener is acrylic acid polymer with solid content of 40% -45%;
the leveling agent is acrylic polymer, and the solid content is 40% -45%; the carbon nano tube has the length of 5-30 mu m, the diameter of 1-2nm, the purity of the carbon nano tube is 95 wt%, the purity of the graphene oxide is 85 wt%, the thickness of the graphene oxide is 5nm, and the diameter is about 80 mu m.
Unless otherwise indicated, units are g; the ultrasonic time unit is min; distilled water was added in volume ml.
Example 1:
as shown in FIG. 2, a bendable heating device of an adhesive tape structure comprises a first adhesive layer, a substrate, a second adhesive layer, a heating layer, a conductive copper foil and a packaging layer. The first adhesive layer is made of acrylic adhesive with the thickness of 30 mu m, and can enable the heating layer to be tightly adhered to the surface of a heated object. The substrate is made of PET and has a thickness of 50 μm; the second adhesive layer is made of acrylic adhesive with a thickness of 50 μm, and can tightly adhere the heating layer to the surface of the substrate. The heating layer consists of carbon nano tubes, graphene oxide, waterborne polyurethane, a thickening agent and a leveling agent, the thickness of the heating layer is 100 mu m, and the heating layer can be quickly heated after being electrified, so that the heating function is realized. The conductive copper foil is stuck at two ends of the heating layer, so that the purpose of loading voltage at two ends of the heating layer is realized; the packaging layer is made of PET, has a thickness of 50 μm, and has the functions of preventing water and dust and protecting the heating layer from being interfered by external environment.
Wherein the heating layer is prepared by coating a conductive mixed solution, and the conductive mixed solution is prepared by the following method: single-wall carbon nano tube and graphene oxide are used as raw materials, sodium dodecyl benzene sulfonate is used as a dispersing agent, and distilled water is used as a solvent. And (3) carrying out ultrasonic treatment for 20min by using an ultrasonic dispersion machine, centrifuging for 40min at a speed of 8000rpm by using a centrifugal machine, and extracting supernatant to obtain a mixed dispersion liquid of graphene oxide and carbon nano tubes. And stirring the mixed dispersion liquid, and then sequentially adding the aqueous polyurethane, the thickener and the flatting agent until a viscous and uniform conductive mixed solution is formed. The mass ratio of the carbon nano tube to the graphene oxide is 1:10, and the mass ratio of the graphene oxide to the waterborne polyurethane is 1:15; the mass ratio of the graphene oxide to the thickener is 1:5; the mass ratio of the graphene oxide to the leveling agent is 1:5. And finally, coating the conductive mixed solution on the surface of the substrate coated with the acrylic glue, and air-drying to obtain the heating layer.
The area resistance of the product was 150 Ω/sq.
SEM comparison of pure carbon nanotubes and graphene oxide added is shown in fig. 3.
When the adhesive tape is applied, the heating film of the rolled adhesive tape structure can be cut out to a specific length according to actual needs, the heating film is adhered to the surface of a to-be-heated object, then electric wires are connected to the conductive copper foils at the two sides of the conductive heating film, and then the adhesive tape is heated according to the loading voltage of the heating device. The device has the advantages of light weight, low cost, high deicing efficiency and low energy consumption, and also has excellent anti-icing and deicing functions in application.
Example 2:
as shown in FIG. 2, a bendable heating device of an adhesive tape structure comprises a first adhesive layer, a substrate, a second adhesive layer, a heating layer, a conductive copper foil and a packaging layer. The first adhesive layer is made of acrylic adhesive with the thickness of 30 mu m, and can enable the heating layer to be tightly adhered to the surface of a heated object. The substrate is made of PET and has a thickness of 30 μm; the second adhesive layer is made of acrylic adhesive with a thickness of 70 μm, and can tightly adhere the heating layer to the surface of the substrate. The heating layer consists of carbon nano tubes, graphene oxide, waterborne polyurethane, a thickening agent and a leveling agent, the thickness of the heating layer is 80 mu m, and the heating layer can be quickly heated after being electrified, so that the heating function is realized. The conductive copper foil is stuck at two ends of the heating layer, so that the purpose of loading voltage at two ends of the heating layer is realized; the packaging layer is made of PET, has a thickness of 30 μm, and has the functions of preventing water and dust and protecting the heating layer from being interfered by external environment.
Wherein the heating layer is prepared by coating a conductive mixed solution, and the conductive mixed solution is prepared by the following method: single-wall carbon nano tube and graphene oxide are used as raw materials, sodium dodecyl benzene sulfonate is used as a dispersing agent, and distilled water is used as a solvent. And (3) carrying out ultrasonic treatment for 10min by using an ultrasonic dispersion machine, centrifuging for 30min at a speed of 6000rpm by using a centrifugal machine, and extracting supernatant to obtain a mixed dispersion liquid of graphene oxide and carbon nano tubes. And stirring the mixed dispersion liquid, and then sequentially adding the aqueous polyurethane, the thickener and the flatting agent until a viscous and uniform conductive mixed solution is formed. The mass ratio of the carbon nano tube to the graphene oxide is 1:15, and the mass ratio of the graphene oxide to the waterborne polyurethane is 1:20; the mass ratio of the graphene oxide to the thickener is 1:10; the mass ratio of graphene oxide to the leveling agent is 1:10. And finally, coating the conductive mixed solution on the surface of the substrate coated with the acrylic glue, and air-drying to obtain the heating layer.
The product had a pastry resistance of 170Ω/sq.
Examples 3 to 14:
the preparation method provided by the invention is adopted, wherein the number of raw materials, the thickness of each layer and the operation conditions are listed as follows, and the list is not the same as that of the example 1:
table 1 preparation method and composition summary table of heating layer of examples 3 to 14
Table 2 method for producing heating devices and composition summary tables of examples 3 to 14
The surface resistance detection result curves of the heating device products in examples 3 to 8 are shown in fig. 4, with the graphene oxide/carbon nanotube weight ratio as the abscissa and the corresponding surface resistance as the ordinate:
it can be seen that the area resistance of the resulting product does not increase or decrease with the graphene oxide/carbon nanotube weight ratio, and according to the present invention it was found that at a graphene oxide/carbon nanotube weight ratio of 0.25 (example 4), the area resistance was reduced to 20 Ω/sq for the following analytical reasons: the carbon nanotubes realize carrier transport through the overlap joint between the tubes, and as can be seen from SEM images of the carbon nanotube heating layer, the Carbon Nanotube (CNT) network contains many holes and is a spider-like structure. While Graphene Oxide (GO) sheets deposited in the CNT network may encapsulate and fill the CNTs to densify the CNT network. Although GO has insulating properties, it can still act as a bridge between CNT bundles, forming several new electron transport channels, ultimately reducing the contact resistance between CNTs. Since graphene oxide is non-conductive, a proper amount of graphene oxide can be used as a bridge for carrier transmission to promote carrier transmission, and excessive graphene oxide can block electron transmission, so that the surface resistance of the heating layer is reduced and then increased with the increase of the addition amount of graphene oxide.
Test example 1, voltage and temperature curve measurement at product temperature rise:
the experimental device comprises: a temperature measuring gun, a heating film with the surface resistance of 40 ohm/sq, an electric wire and a voltage regulator.
The experimental method comprises the following steps: the voltage regulator was connected to two electrodes of the heating film, gradually heated from 50V to 130V at-25 ℃ at a rate of 2 ℃ per minute, then the temperature of the heating film was measured using a temperature measuring gun, and finally a heating curve was drawn.
Conclusion of experiment: as shown in fig. 5, the bendable heating device of the adhesive tape device can be rapidly heated at-25 deg.c, and the temperature increases with increasing applied voltage. When the applied voltage is 130V, the temperature may be raised to 87 ℃. It is explained that the device can achieve different heating temperatures by adjusting the voltage.
Test example 2, test for measuring thermal stability of product:
the experimental device comprises: a temperature measuring gun, a heating film with the surface resistance of 40 ohm/sq, an electric wire and a voltage regulator.
The experimental method comprises the following steps: the voltage regulator is connected to two electrodes of the heating film, 70V voltage is loaded on two sides of the heating device at the temperature of minus 6 ℃, then a temperature measuring gun is used for measuring the temperature of the heating film, and finally a heating stability curve is drawn.
Conclusion of experiment: as shown in fig. 6, the bendable heating device of the adhesive tape device can rapidly raise the temperature at-6 ℃, and when the loading voltage is 70V, the temperature can be stably maintained at 15 ℃; only less than 10 minutes is needed to raise the initial temperature to the stable temperature; when the heating is carried out for 80min, the power is cut off, the temperature is rapidly reduced, and the time for reducing the temperature to the original temperature is less than 10 min. The device has stable heating performance.
When the adhesive tape is applied, firstly, acrylic acid glue is coated on one surface of PET, then, a carbon nano tube conductive mixed solution is coated, after drying and before coiling, a conductive copper foil with double-sided adhesion is attached to two ends of a conductive film, then, a layer of PET is packaged, finally, acrylic acid glue is continuously coated on the other surface of the conductive film, and the adhesive tape is coiled to obtain the heating device with an adhesive tape structure. The heating device with the adhesive tape structure prepared by the method has the characteristics of easy adhesion and convenient fixation similar to an adhesive tape, and the preparation method has the characteristics of simple process, short period, high conductivity of a film, good stability, uniform surface coating, controllable size, flexibility and the like.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. The bendable heating device of the adhesive tape structure is characterized by comprising a packaging layer, a conductive layer, a heating layer, a first bonding layer, a substrate and a second bonding layer from top to bottom in sequence;
the first bonding layer and the second bonding layer are both made of acrylic rubber;
the thickness of the first bonding layer and the second bonding layer is 10-200 mu m;
the substrate is made of polyethylene glycol diformate, polyimide or glass fiber felt, and the thickness is 10-500 mu m; the packaging layer is made of PET material and has the thickness of 10-500 mu m;
the conductive layer is a silver paste coating or a metal foil and is adhered to two ends of the heating layer;
the thickness of the heating layer is 20-1500 mu m, and the components comprise carbon nano tubes, graphene oxide, waterborne polyurethane, sodium dodecyl benzene sulfonate, a thickening agent and a leveling agent;
the heating layer is formed by coating a conductive mixed solution on the surface of a substrate coated with a first bonding layer in advance and air-drying the substrate; the conductive mixed solution is prepared by the following method:
step 1, taking carbon nano tubes and graphene oxide as raw materials, adding sodium dodecyl benzene sulfonate and distilled water serving as a solvent, mixing the above components, performing ultrasonic treatment for 10-90min by using an ultrasonic dispersing machine, centrifuging for 10-50min by using a centrifugal machine at a rotation speed of 5000-12000rpm, and extracting supernatant to obtain a mixed dispersion liquid of the graphene oxide and the carbon nano tubes;
step 2, stirring the mixed dispersion liquid, and then sequentially adding the aqueous polyurethane, the thickening agent and the leveling agent until a conductive mixed solution with uniform viscosity is formed;
the mass ratio of the carbon nano tube to the graphene oxide in the conductive mixed solution is 1 (0.05-15), and the mass ratio of the graphene oxide to the waterborne polyurethane is 1 (5-30); the mass ratio of the graphene oxide to the thickener is 1 (0.1-10); the mass ratio of the graphene oxide to the leveling agent is 1 (0.1-10).
2. The bendable heating device with the adhesive tape structure according to claim 1, wherein the carbon nanotubes are single-walled carbon nanotubes, the purity of the single-walled carbon nanotubes in the raw material of the heating layer is more than 75 wt%, the outer diameter is 1-2nm, and the length is 5-30 μm; the graphene oxide has the purity of more than 75 wt%, the thickness of 4-7 nm and the diameter of about 80 mu m; the solid content of the waterborne polyurethane is 10-45 wt%; the solid content of the thickener is 20-55wt%; the solid content of the leveling agent is 15-60 wt%.
3. The bendable heating device with the adhesive tape structure according to claim 1, wherein the step 1 adopts an ultrasonic dispersion machine to prepare the carbon nanotube and graphene oxide dispersion liquid, provided that: power 50-400W.
4. The bendable heating device with the adhesive tape structure according to claim 1, wherein the concentration of the carbon nanotubes in the mixed dispersion of the graphene oxide and the carbon nanotubes prepared in the step 1 is 0.005-5.0mg/ml, and the concentration of the graphene oxide is 0.005-5.0mg/ml.
5. The bendable heating device with the adhesive tape structure according to claim 1, wherein in the step 2, the mixed dispersion liquid of graphene oxide and carbon nanotubes is added with stirring at a speed of 100-800rpm until a uniform and viscous solution is formed.
6. The bendable heating device of the adhesive tape structure according to claim 1, wherein the mass ratio of the carbon nanotubes to the graphene oxide is 1:0.25, and the mass ratio of the graphene oxide to the aqueous polyurethane is 1:15; the mass ratio of the graphene oxide to the thickener is 1:5; the mass ratio of the graphene oxide to the leveling agent is 1:5.
7. The method for manufacturing the bendable heating device with the adhesive tape structure according to any one of claims 1 to 6, comprising the steps of:
firstly, cutting a polyethylene glycol diformate, polyimide or glass fiber felt substrate into coiled materials with a certain size for standby;
pouring the ethanol solution into a coating liquid tank of a coating machine, and then enabling the substrate to sequentially pass through the coating liquid tank and a drying system to remove dust and stains on the surface of the substrate; uniformly coating acrylic glue on the coiled material by using a coating machine to prepare the coiled material with single-sided viscosity;
preparing graphene oxide and carbon nanotubes into a conductive mixed solution according to a certain mass ratio, coating the conductive mixed solution on one sticky surface of a substrate by using a coating machine to prepare a flexible transparent conductive film, and adjusting the coating thickness of the flexible transparent conductive film by adjusting the concentration of the conductive mixed solution in the process of coating the conductive mixed solution and the coating speed of the machine so as to change and adjust the light transmittance and the surface resistance of the flexible transparent conductive film;
step four, sticking metal foils with double-sided adhesive properties on two ends of the conductive film obtained in the step three before coiling, or coating conductive silver paste with a certain width on two ends of the film and drying;
packaging the conductive film coated on one surface of the conductive mixed solution by using a plastic packaging system; and coating one side of the flexible transparent conductive film without the coating with a layer of acrylic adhesive by using a coating machine, coating a layer of release protective film, and coiling for standby.
CN202110175544.1A 2020-12-31 2021-02-07 Bendable heating device of adhesive tape structure and preparation method thereof Active CN112822803B (en)

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