CN108440777B - Graphene water-based electrothermal film and preparation method thereof - Google Patents

Graphene water-based electrothermal film and preparation method thereof Download PDF

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CN108440777B
CN108440777B CN201810226112.7A CN201810226112A CN108440777B CN 108440777 B CN108440777 B CN 108440777B CN 201810226112 A CN201810226112 A CN 201810226112A CN 108440777 B CN108440777 B CN 108440777B
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beta
cyclodextrin
electrothermal film
film
graphene
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CN108440777A (en
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王昕�
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Shandong Luther Transportation Technology Co.,Ltd.
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Hebei Zhongxi Technology Co ltd
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Abstract

The application discloses a graphene water-based electrothermal film and a preparation method thereof. The graphene water-based electrothermal film comprises a polyester film and a conductive layer, wherein the conductive layer is coated on the surface of the polyester film and comprises the following raw materials in parts by weight: 1 part of conductive filler, 0.2-5 parts of auxiliary agent, 15-50 parts of water-based resin and 1-50 parts of beta-cyclodextrin derivative. The electric heating film conductive filler slurry solves the technical problems that the conductive filler is unevenly distributed in slurry, the electric heating film conductive efficiency caused by agglomeration is low, and the component compatibility caused by adding a dispersing agent and a thickening agent is low.

Description

Graphene water-based electrothermal film and preparation method thereof
Technical Field
The application relates to a novel electric heating material, in particular to a graphene water-based electric heating film and a preparation method thereof.
Background
The electrothermal film heating system is different from a point heating system represented by a radiator, an air conditioner and a radiator and a line heating system represented by a heating cable, and is a low-carbon heating high-tech product researched and developed by adopting the modern aerospace technology in the field of surface heating.
The heating principle of the electric heating film is that under the action of an electric field, carbon molecular groups in a heating body generate Brownian motion, violent friction and impact occur among carbon molecules, the generated heat energy is transmitted outwards in the form of far infrared radiation and convection, and the conversion rate of electric energy and heat energy is up to more than 98%. The carbon molecule acts to rapidly heat the surface of the system. The electric heating film heating system is arranged on the wall (ground), and the heat energy can be continuously and uniformly transferred to each corner of a room. The electric heating film can rapidly heat the space, and 100 percent of electric energy input is effectively converted into over 66 percent of far infrared radiation energy and 33 percent of convection heat energy. The electrothermal film has wide development prospect because of meeting the policy guidance of emission reduction and low carbon.
The electrothermal film is a special heating product made up by printing and hot-pressing conductive special ink and metal current-carrying strip between two layers of insulating polyester film, and is formed from power supply, temp. controller, connecting piece, insulating layer, electrothermal film and decorative layer. When the electric heating film is used as a heating body, heat is sent into a space in a radiation mode, so that a human body feels warm, and the comprehensive effect of the electric heating film is superior to that of a traditional heating mode.
The related technology discloses an electrothermal film, an electrothermal plate and a corresponding manufacturing method, wherein carbon black powder and graphite powder are used as heating materials, and organic solvent, adhesive and KH-560 stabilizer are added and mixed with the heating materials, and the electrothermal film is obtained after baking. However, in the actual use process of the patent, due to the structure of the carbon black and the graphite, the matching degree of the carbon black and the graphite is limited during mixing, so that the heating efficiency is not high, and the heating on the surface of the electrothermal film is not uniform. Meanwhile, the heating performance of the electrothermal film is affected due to the volatilization of the organic solvent. And the KH-560 stabilizer used in the production process is expensive, so that the production cost is increased. In addition, related technologies disclose a graphene tube electrothermal film formed by an ultrasonically dispersed graphene tube solution and an insulating protective layer, and the graphene tube ultrasonically dispersed is mixed with an organic solution, and then a coagulant is added for shaping and drying to obtain the electrothermal film. Although the graphene tube has good conductivity and heating efficiency compared with carbon black powder and graphite powder, the graphene tube has limited dispersion effect on the graphene tube due to the ultrasonic wave, and meanwhile, due to the fact that the graphene tube is not hydrophilic and oleophilic, the graphene tube is not dispersed uniformly and agglomerated in the scheme, so that the conductivity of the electric heating film is reduced, and the heating efficiency of the electric heating film is influenced. Secondly, the related art also discloses a method for preparing an electrothermal film by using the graphene tube aqueous slurry, and the dispersion effect of the graphene tube in the electrothermal film is improved by performing hydrophilic treatment on solid acrylic resin so as to improve the problem of uneven dispersion of the graphene tube and improve the heating efficiency. In the actual use process, the problem still exists that although the acrylic resin is subjected to hydrophilic treatment, the compatibility of all components in the electrothermal film is low due to the addition of the dispersing agent and the thickening agent, and the electrothermal film with all components uniformly distributed cannot be formed. In addition, the problem of uniform dispersion of the graphene tube in the electric heating film cannot be completely solved only by adding a surfactant to perform hydrophilic treatment on the graphene tube. Meanwhile, the film-forming resin with poor conductivity exists, so that the conductivity efficiency of the electrothermal film can be influenced.
Aiming at the problems of uneven distribution of conductive filler in slurry and low electric heating film conductive efficiency caused by agglomeration and low component compatibility caused by adding a dispersing agent and a thickening agent in the prior art, an effective solution is not provided at present.
Disclosure of Invention
The application mainly aims to provide a graphene water-based electrothermal film and a preparation method thereof, and aims to solve the problems of low electric conduction efficiency of the electrothermal film caused by uneven distribution and agglomeration of a conductive filler in slurry and low component compatibility caused by addition of a dispersing agent and a thickening agent.
In order to achieve the above object, according to one aspect of the present application, there is provided a graphene aqueous electrothermal film.
The graphene aqueous electrothermal film comprises: the conductive layer is coated on the surface of the polyester film and comprises the following raw materials in parts by weight: 1 part of conductive filler, 0.2-5 parts of auxiliary agent, 15-50 parts of water-based resin and 1-50 parts of beta-cyclodextrin derivative.
The conductive filler is an additive material prepared from a composite conductive polymer material and composed of a conductive material, is an important component in the composite conductive material, and is mostly metal with good conductive performance and dispersibility, such as silver powder or carbon black powder, or conductive fiber, such as carbon fiber and the like. The conductive filler is generally melt-mixed with the insulating resin by blending, and conducts electric current by mutual contact or proximity between particles or fibers of the conductive filler.
The assistant, also called paint assistant, is an auxiliary material for preparing paint, and can improve the performance of the paint and promote the formation of a coating film. The paint auxiliaries are various and comprise a drier, a flexibilizer, an emulsifier, a thickener, a pigment dispersing agent, an antifoaming agent, a leveling agent, an anti-skinning agent, a flatting agent, a light stabilizer, a heat stabilizer, an antioxidant, a mildew preventive, an antistatic agent and the like. The paint assistant is an indispensable component for paint, and can improve production process, maintain storage stability, improve construction conditions and improve product quality. The reasonable and correct selection of the auxiliary agent can reduce the cost and improve the economic benefit.
The aqueous resin is a novel resin system using water as a dispersion medium instead of an organic solvent. And fusing with water to form a solution, and forming the resin mold material after the water is volatilized. The water resin can improve the bonding strength between the abrasive and the matrix.
The beta-cyclodextrin derivative is a modified beta-cyclodextrin derivative obtained by introducing a modifying group under the condition of keeping the basic skeleton of the macrocycle of the beta-cyclodextrin unchanged so as to modify the beta-cyclodextrin. The beta-cyclodextrin derivative has stronger solubilizing ability compared with parent beta-cyclodextrin. Meanwhile, the special compatibility, solution viscosity and safety of the solution are widely concerned by various industries.
Further, the conductive layer comprises the following raw materials in parts by weight: 1 part of conductive filler, 0.26-5 parts of auxiliary agent, 19.5 parts of biological water-based resin and 15-50 parts of beta-cyclodextrin derivative.
When the mass ratio of the conductive filler to the beta-cyclodextrin derivative is less than 1: 15, the solid content in the electrothermal film slurry is lower, and the problem of incomplete coverage of the conductive filler can occur after the film is formed on the surface of the polyester film, so that the connection between the conductive fillers is influenced, and the heating effect is further influenced; when the mass ratio of the conductive filler to the beta-cyclodextrin derivative is more than 1: 50 hours, the resistance of the electric heating film is low, and the heating effect is not ideal; therefore, the mass ratio of the conductive filler to the β -cyclodextrin derivative is set to 1: 15-50, the conductive filler can be completely covered on the polyester film, and a better heating effect is further ensured.
Furthermore, the beta-cyclodextrin derivative is one or more of methylated beta-cyclodextrin, ethylated beta-cyclodextrin, butylated beta-cyclodextrin, carboxymethyl beta-cyclodextrin, glucosyl-beta-cyclodextrin, ethylenediamine-beta-cyclodextrin, hydroxyethyl-beta-cyclodextrin, hydroxypropyl-beta-cyclodextrin, sulfonate-based-beta-cyclodextrin, quaternary ammonium-beta-cyclodextrin or carboxymethyl reticular-beta-cyclodextrin polymer and the like.
Further, the conductive filler includes graphene or carbon nanotubes.
Further, the conductive filler comprises graphene and carbon nanotubes, and the mass ratio of the carbon nanotubes to the graphene is 1: 1-5.
When the graphene and the carbon nano tube are added into the electrothermal film at the same time, the electric conduction efficiency of the electrothermal film is improved compared with that of the electrothermal film which only uses the graphene. The mass ratio of the carbon nanotubes to the graphene is less than 1: 1-5, the improvement of the conductive efficiency is not obvious. The mass ratio of the carbon nanotubes to the graphene is more than 1: 1-5, the agglomeration phenomenon of the two in the electric heating film is more prominent, and the electric conduction efficiency of the electric heating film is reduced. Therefore, the mass ratio of the carbon nanotubes to the graphene is set to 1: 1-5, the improvement of the conductive efficiency is the largest.
Further, the thickness of the polyester film is 50-250 μm; the thickness of the conductive layer is 15-150 μm. The thickness of the polyester film not only affects the time and efficiency of heat transfer, but also affects the weight of the product, and the polyester film material is made into a membrane with the thickness of 50-250 μm, so that the heat transfer efficiency of the product is accelerated, the heat transfer time is reduced, and the polyester film material is suitable for wearing equipment due to light weight, thereby expanding the application range of the product. In addition, the coating thickness of the conductive layer is set to be 15-150 microns, so that the production cost is favorably reduced, and the situation that the electric heating film is broken down under the condition of high-power heating can be avoided under the condition that the heat exchange inside and outside the conductive filler layer is not timely.
Further, it is preferable that a surface of the electric heating film is coated with a tough film. The surface of the electric heating film is laid with a tough film, so that the electric heating film has the characteristics of water resistance, impact resistance, high temperature resistance, insulation, high heat conductivity coefficient and the like.
In order to achieve the above object, according to another aspect of the present application, a method for preparing a graphene aqueous electrothermal film is provided.
The preparation method of the graphene water-based electrothermal film comprises the following steps:
(1) carrying out hydrophilization treatment on the conductive filler in a surfactant, adding a beta-cyclodextrin derivative solution, and carrying out pre-dispersion to obtain a conductive filler solution;
(2) adding an auxiliary agent into the conductive filler solution, and dispersing to obtain a homogeneous dispersion liquid;
(3) adding aqueous resin into the homogeneous dispersion liquid, and stirring and mixing to obtain electrothermal film slurry;
(4) and coating the electrothermal film slurry on a polyester film to form an electrothermal film conducting layer, and drying to obtain an electrothermal film consisting of the electrothermal film conducting layer and a film-forming carrier.
Further, preferably, the surfactant in step (1) is at least one of sodium cholate, sodium deoxycholate, sodium taurodeoxycholate, polyethylene glycol octyl phenyl ether, tetradecyl trimethyl ammonium bromide, sodium dodecyl sulfonate or sodium dodecyl benzene sulfonate.
Further, preferably, the auxiliary agent in the step (2) is one or more of a defoaming agent, a leveling agent, a film-forming auxiliary agent, an adhesion promoter, a base material wetting agent, an antifreezing agent or a mildew preventive.
Further, in the step (3), the aqueous resin is preferably at least one of aqueous polyurethane, aqueous acrylic resin, aqueous epoxy resin, aqueous vinyl chloride-vinyl acetate resin, or aqueous saturated or polyester resin.
Further, the coating method in the step (4) is preferably one of a concave roller, coating or silk-screen printing, and the method can enable the electric heating film slurry to be uniformly distributed on the film forming carrier, thereby being beneficial to improving the heating performance of the heating body.
Further, the temperature of the drying process in the step (4) is 50-160 ℃.
In the embodiment of the application, the beta-cyclodextrin derivative with the functions of dispersing, film forming and thickening is added to replace two important components of a dispersing agent and a thickening agent, so that the use of an auxiliary agent is reduced, the compatibility of the whole system is greatly improved, the dispersion of graphene and carbon nanotubes is facilitated, the occurrence of an agglomeration phenomenon is reduced, and the using amount of film forming resin is greatly reduced. And the beta-cyclodextrin derivative has small influence on system resistance, has obvious advantages compared with film-forming resin, and has a large selectable range, and in addition, the beta-cyclodextrin derivative has low toxicity and is easy to degrade, thereby being beneficial to the application of the beta-cyclodextrin derivative. Therefore, the conductive filler and the beta-cyclodextrin derivative solution can be uniformly mixed through pre-dispersion, a good dispersion effect is achieved, and a homogeneous solution is formed.
Therefore, by adding the beta-cyclodextrin derivative, the prepared product has uniform dispersion of the conductive filler and high component compatibility, and further solves the problems of low electric heating film conductive efficiency caused by uneven distribution and agglomeration of the conductive filler in slurry and low component compatibility caused by adding a dispersing agent and a thickening agent in the prior art.
Detailed Description
In order to make the technical solutions in the embodiments of the present application better understood, the technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present application, not all embodiments. 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 application.
It should be noted that the term "comprises/comprising" and any variations thereof is intended to cover non-exclusive inclusions, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail with reference to examples.
The following examples of the electric heating film described in this application are partly listed:
example 1
A graphene aqueous electrothermal film comprises: the conductive layer is coated on the surface of the polyester film and comprises the following raw materials in parts by weight: 1 part of graphene, 0.2 part of defoaming agent, 15 parts of waterborne polyurethane and 1 part of methylated beta-cyclodextrin.
The preparation method of example 1 is as follows:
(1) carrying out hydrophilization treatment on graphene in sodium taurodeoxycholate, then adding a methylated beta-cyclodextrin solution, and carrying out pre-dispersion to obtain a graphene solution;
(2) adding a defoaming agent into the graphene solution, and dispersing to obtain a homogeneous dispersion liquid;
(3) adding waterborne polyurethane into the homogeneous dispersion liquid, and stirring and mixing to obtain electrothermal film slurry;
(4) and coating the electrothermal film slurry on a polyester film to form an electrothermal film conductive layer, and drying at the temperature of 50 ℃ to obtain an electrothermal film consisting of the electrothermal film conductive layer and a film-forming carrier.
Example 2
A graphene aqueous electrothermal film comprises: the conductive layer is coated on the surface of the polyester film and comprises the following raw materials in parts by weight: 1 part of graphene, 5 parts of a leveling agent, 50 parts of water-based acrylic resin and 50 parts of carboxymethyl beta-cyclodextrin.
The preparation method of the embodiment 2 comprises the following steps:
(1) carrying out hydrophilization treatment on graphene in tetradecyl trimethyl ammonium bromide, then adding a carboxymethyl beta-cyclodextrin solution, and carrying out pre-dispersion to obtain a graphene solution;
(2) adding a leveling agent into the graphene solution, and dispersing to obtain a homogeneous dispersion liquid;
(3) adding aqueous acrylic resin into the homogeneous dispersion liquid, and stirring and mixing to obtain electrothermal film slurry;
(4) and coating the electrothermal film slurry on a polyester film to form an electrothermal film conductive layer, and drying at 160 ℃ to obtain an electrothermal film consisting of the electrothermal film conductive layer and the polyester film.
Example 3
A graphene aqueous electrothermal film comprises: the conductive layer is coated on the surface of the polyester film and comprises the following raw materials in parts by weight: 1 part of carbon nano tube, 0.26 part of base material wetting agent, 19.5 parts of aqueous vinyl chloride-vinyl acetate resin and 15 parts of glucosyl-beta-cyclodextrin.
The preparation method of example 3 is as follows:
(1) carrying out hydrophilization treatment on the carbon nano tube in polyethylene glycol octyl phenyl ether, then adding a carboxymethyl beta-cyclodextrin solution, and carrying out pre-dispersion to obtain a carbon nano tube solution;
(2) adding a base material wetting agent into the carbon nano tube solution, and dispersing to obtain a homogeneous dispersion liquid;
(3) adding aqueous vinyl chloride-vinyl acetate copolymer into the homogeneous dispersion liquid, and stirring and mixing to obtain electrothermal film slurry;
(4) and coating the electrothermal film slurry on a polyester film to form an electrothermal film conductive layer, and drying at the temperature of 100 ℃ to obtain an electrothermal film consisting of the electrothermal film conductive layer and the polyester film.
Example 4
A graphene aqueous electrothermal film comprises: the conductive layer is coated on the surface of the polyester film and comprises the following raw materials in parts by weight: 0.5 part of carbon nano tube, 0.5 part of graphene, 0.13 part of base material wetting agent, 0.13 part of antifreezing agent, 8 parts of aqueous vinyl chloride-vinyl acetate resin, 8 parts of aqueous saturated or polyester resin, 8 parts of glucosyl-beta-cyclodextrin and 8 parts of hydroxypropyl-beta-cyclodextrin.
The preparation method of example 4 is as follows:
(1) carrying out hydrophilization treatment on the carbon nano tube and the graphene in tetradecyl trimethyl ammonium bromide, then adding a mixed solution of carboxymethyl beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin, and carrying out pre-dispersion to obtain a conductive filler solution;
(2) adding a base material wetting agent and an antifreezing agent into the conductive filler solution, and dispersing to obtain a homogeneous dispersion liquid;
(3) adding aqueous vinyl chloride-vinyl acetate copolymer and polyester resin into the homogeneous dispersion liquid, and stirring and mixing to obtain electrothermal film slurry;
(4) and coating the electrothermal film slurry on a polyester film to form an electrothermal film conductive layer, and drying at the temperature of 100 ℃ to obtain an electrothermal film consisting of the electrothermal film conductive layer and the polyester film.
Example 5
A graphene aqueous electrothermal film comprises: the conductive layer is coated on the surface of the polyester film and comprises the following raw materials in parts by weight: 0.75 part of carbon nano tube, 0.25 part of graphene, 0.13 part of base material wetting agent, 0.13 part of antifreezing agent, 8 parts of aqueous vinyl chloride-vinyl acetate resin, 8 parts of aqueous saturated or polyester resin, 8 parts of glucosyl-beta-cyclodextrin and 8 parts of hydroxypropyl-beta-cyclodextrin.
The preparation method of example 5 is as follows:
(1) carrying out hydrophilization treatment on the carbon nano tube and the graphene in tetradecyl trimethyl ammonium bromide, then adding a mixed solution of carboxymethyl beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin, and carrying out pre-dispersion to obtain a conductive filler solution;
(2) adding a base material wetting agent and an antifreezing agent into the conductive filler solution, and dispersing to obtain a homogeneous dispersion liquid;
(3) adding aqueous vinyl chloride-vinyl acetate copolymer and polyester resin into the homogeneous dispersion liquid, and stirring and mixing to obtain electrothermal film slurry;
(4) and coating the electrothermal film slurry on a polyester film to form an electrothermal film conductive layer, and drying at the temperature of 100 ℃ to obtain an electrothermal film consisting of the electrothermal film conductive layer and the polyester film.
Example 6
A graphene aqueous electrothermal film comprises: the conductive layer is coated on the surface of the polyester film and comprises the following raw materials in parts by weight: 0.83 part of carbon nano tube, 0.17 part of graphene, 0.13 part of base material wetting agent, 0.13 part of antifreezing agent, 8 parts of aqueous vinyl chloride-vinyl acetate resin, 8 parts of aqueous saturated or polyester resin, 8 parts of glucosyl-beta-cyclodextrin and 8 parts of hydroxypropyl-beta-cyclodextrin.
The preparation method of example 6 is as follows:
(1) carrying out hydrophilization treatment on the carbon nano tube and the graphene in tetradecyl trimethyl ammonium bromide, then adding a mixed solution of carboxymethyl beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin, and carrying out pre-dispersion to obtain a conductive filler solution;
(2) adding a base material wetting agent and an antifreezing agent into the conductive filler solution, and dispersing to obtain a homogeneous dispersion liquid;
(3) adding aqueous vinyl chloride-vinyl acetate copolymer and polyester resin into the homogeneous dispersion liquid, and stirring and mixing to obtain electrothermal film slurry;
(4) and coating the electrothermal film slurry on a polyester film to form an electrothermal film conductive layer, and drying at the temperature of 100 ℃ to obtain an electrothermal film consisting of the electrothermal film conductive layer and the polyester film.
Comparative example 1
Adding 140 parts of deionized water and 10 parts of ammonia water into 60 parts of acrylic resin, and uniformly dissolving the acrylic resin at the temperature of 60 ℃ in a stirring manner to obtain water-soluble acrylic resin; adding 1 part of graphene subjected to hydrophilization treatment by sodium polystyrene sulfonate and 5 parts of wetting dispersant into water-soluble acrylic resin to obtain a mixed solution, and then performing high-speed magnetic stirring, dispersing and mixing on the mixed solution to obtain a homogeneous dispersion solution; adding water-emulsion resin into the homogeneous dispersion liquid, and stirring and mixing to obtain graphene water-based slurry; coating the graphene aqueous slurry on the surface of a 75-micrometer polyester film in a screen printing mode to form a graphene conducting layer, drying the graphene conducting layer at the temperature of 60 ℃ in a step-by-step heating and heat preservation mode of heating up to 10 ℃ per minute and preserving heat for 1 minute, and drying to obtain an electrothermal film consisting of the graphene conducting layer and a film forming carrier.
Taking example 1 as an example, the two types of composite materials prepared in example 1 and the comparative example were used to prepare an electrothermal film conductive layer on a 75 μm polyester film by using a 25 μm doctor bar, and the conductivity thereof was measured by using a four-probe method, and the compatibility thereof was measured by using a contact angle test, and the solubility of the conductive filler was also measured. Specific experimental results are shown in table 1:
TABLE 1 Experimental results for the examples and comparative examples
Group of Electrical conductivity of Contact angle Solubility in water
Example 1 0.30Ω˙cm 96.13° 0.58mg/L
Example 2 0.29Ω˙cm 99.41° 0.58mg/L
Example 3 0.30Ω˙cm 95.92° 0.56mg/L
Example 4 0.29Ω˙cm 95.20° 0.54mg/L
Example 5 0.28Ω˙cm 94.82° 0.62mg/L
Example 6 0.27Ω˙cm 94.06° 0.66mg/L
Comparative example 0.80Ω˙cm 115.85° 0.11mg/L
It was found through the experiment that the average resistivity of the electric heating films of examples was less than 0.30 Ω & cm, and the resistivity of comparative examples was 0.8 Ω & cm. Meanwhile, the compatibility index in the invention mainly refers to the contact angle of the mixed solution, the average contact angle of the graphene tube solution in the contact angle test is 97.72 degrees, the average contact angle of the carbon nanotube solution in the contact angle test is 95.92 degrees, and the contact angle in the embodiment is 115.85 degrees. In addition, the solubility of the graphene tube subjected to hydrophilization treatment can reach nearly 0.58mg/L, the solubility of the carbon nanotube can reach 0.56mg/L, and the solubility of the carbon nanotube is only 0.11mg/L in the embodiment.
Meanwhile, as can be seen from examples 3 to 5, when the mass ratio of graphene to carbon nanotubes is 1: 1-5, the electrical conductivity of the electrothermal film is higher than when either is added alone. Therefore, the electrothermal film paste provided by the embodiment of the invention can be effectively used for printing and manufacturing the high-conductivity electrothermal film.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (5)

1. A graphene water-based electrothermal film is characterized by comprising: the conductive layer is coated on the surface of the polyester film and comprises the following raw materials in parts by weight: the conductive filler comprises, by mass, 1 part of conductive filler, 0.2-5 parts of an auxiliary agent, 15-50 parts of water-based resin and 1-50 parts of a beta-cyclodextrin derivative, wherein the conductive filler comprises graphene and carbon nanotubes, and the mass ratio of the carbon nanotubes to the graphene is 1: 1-5, wherein the thickness of the polyester film is 50-250 μm, and the thickness of the conductive layer is 15-150 μm;
the beta-cyclodextrin derivative is one or more of methylated beta-cyclodextrin, carboxymethyl beta-cyclodextrin, glucosyl-beta-cyclodextrin, ethylenediamine-beta-cyclodextrin, hydroxyethyl-beta-cyclodextrin, hydroxypropyl-beta-cyclodextrin, sulfonate-beta-cyclodextrin, quaternary ammonium-beta-cyclodextrin or carboxymethyl reticular-beta-cyclodextrin polymer derivative.
2. A preparation method of the graphene aqueous electrothermal film of claim 1, characterized by comprising the following steps:
(1) carrying out hydrophilization treatment on the conductive filler in a surfactant, adding a beta-cyclodextrin derivative solution, and carrying out pre-dispersion to obtain a conductive filler solution;
(2) adding an auxiliary agent into the conductive filler solution, and dispersing to obtain a homogeneous dispersion liquid;
(3) adding aqueous resin into the homogeneous dispersion liquid, and stirring and mixing to obtain electrothermal film slurry;
(4) and coating the electrothermal film slurry on a polyester film to form an electrothermal film conducting layer, and drying to obtain an electrothermal film consisting of the electrothermal film conducting layer and a film-forming carrier.
3. The preparation method of the graphene aqueous electrothermal film according to claim 2, wherein the addition amount of the auxiliary agent in the step (2) is 0.15-5% of the mass of the homogeneous dispersion liquid.
4. The preparation method of the graphene aqueous electrothermal film according to claim 2, wherein the amount of the aqueous resin added in the step (3) is 5-25% of the mass of the homogeneous dispersion liquid.
5. The preparation method of the graphene aqueous electrothermal film according to claim 2, wherein the temperature of the drying process in the step (4) is 50-160 ℃.
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CN110769528A (en) * 2019-10-11 2020-02-07 深圳天元羲王材料科技有限公司 Graphene aqueous heating film conductive paste
CN111212488B (en) * 2020-01-13 2021-06-18 广西师范大学 Preparation method of graphene/graphite composite aqueous electrothermal film conductive agent
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