CN110868769B - Novel heating film and preparation method and application thereof - Google Patents
Novel heating film and preparation method and application thereof Download PDFInfo
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- CN110868769B CN110868769B CN201911184496.1A CN201911184496A CN110868769B CN 110868769 B CN110868769 B CN 110868769B CN 201911184496 A CN201911184496 A CN 201911184496A CN 110868769 B CN110868769 B CN 110868769B
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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
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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—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
Abstract
The invention relates to the field of two-dimensional material application, in particular to a novel heating film and a preparation method and application thereofThe film comprises a two-dimensional nano composite material, a carbon nano tube and a high polymer material, the thickness of the coating is 1-100 mu m, and the thermal diffusion coefficient is 5-20 cm2(ii)/S, the thermal conductivity is 1000 to 3000W/(m "k). During preparation, the two-dimensional nano composite material, the carbon nano tube and the high polymer material are firstly prepared into the composite material, and then membrane preparation is carried out, so as to obtain the composite material. The novel heating film can be applied to the electric heating field as an electric heating film, has excellent thermal efficiency and heat conductivity, and simultaneously has excellent stability and mechanical property. And the raw material cost is lower during preparation, the preparation process has high repeatability, the process is simple, the consumed time is less, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to the field of two-dimensional material application, in particular to a novel heating film and a preparation method and application thereof.
Background
The current commonly used heating materials have low resistivity (-10)–6Omega/m), low electrothermal conversion efficiency, low heating rate, short service life and the like. And the two-dimensional nano material, such as graphene, has excellent properties, such as, electrical properties: the electron mobility can reach 2 multiplied by 105cm2/Vs at room temperature, and the heat conduction performance is as follows: 5000W/(mK), extraordinary specific surface area (2630m2/g), Young's modulus (1100GPa) and breaking strength (125 GPa); the good mechanical property and the lower density of the graphene enable the graphene to have the potential of replacing metal in the field of electric heating materials.
At present, the graphene electrothermal film or the heating film appears on the market, uneven distribution easily appears in the adding component in the heating film, or the condition that the contact with graphene is not good, therefore often need great addition, cause defects such as heavy filming weight, poor flexibility, and the whole graphene dispersion that adopts of heating member, manufacturing cost is also higher. In view of the technical defects, a novel heating film based on a novel two-dimensional nano composite material is developed, and the novel heating film is simple in structure, convenient to use, low in manufacturing cost, uniform in dispersion, light in weight and good in electric heating efficiency and a production method thereof.
Disclosure of Invention
In order to solve the problems, the invention provides a novel heating film which is simple in structure, convenient to use, good in flexibility, low in manufacturing cost, uniform in dispersion, light in weight and good in electric heating efficiency, and a preparation method and application thereof.
The first purpose of the invention is to provide a novel heating film, the technical scheme is as follows:
a novel heating film comprises a two-dimensional nano composite material, a carbon nano tube and a high polymer material, wherein the thickness of a coating is 1-100 mu m, and the thermal diffusion coefficient is 5-20 cm2(ii)/S, thermal conductivity of 1000 to 3000W/(m "k);
the mass of the two-dimensional nano composite material accounts for 0.1-10% of the total mass; the mass of the carbon nano tube accounts for 0.1-10% of the total mass, and the mass of the high polymer material accounts for 99.8-20% of the total mass.
Preferably, the mass of the two-dimensional nanocomposite material accounts for 0.5-2% of the total mass.
Preferably, the mass of the carbon nano tube accounts for 0.5 to 2 percent of the total mass.
Preferably, the mass of the polymer accounts for 90-98% of the total mass.
As a preferred scheme of the invention, the two-dimensional nanocomposite material has a sandwich structure and consists of an intermediate layer and an upper layer and a lower layer, wherein the intermediate layer is made of one or a mixture of graphene, BN, black scale, two-dimensional sulfide and two-dimensional carbide; preferably graphene; the materials of the upper layer and the lower layer are one or a mixture of silver, iron, copper, aluminum nitride, aluminum oxide, conductive polymer and cellulose.
As a preferable scheme of the invention, the high polymer material is one or a mixture of polyamide, polyimide, polycarbonate, polyethylene, polyvinyl chloride, polypropylene and polyvinylidene fluoride; polyamides and polyimides are preferred.
The second purpose of the invention is to provide a preparation method of a novel heating film, which adopts the following technical scheme:
a preparation method of a novel heating film comprises the steps of mixing a two-dimensional nano composite material, a carbon nano tube and a high-molecular monomer in a solvent, adding an initiator, carrying out polymerization reaction to obtain a composite material, and preparing a film by using the composite material.
Or the following technical scheme is adopted:
a preparation method of a novel heating film comprises the steps of mixing a two-dimensional nano composite material, a carbon nano tube and a high polymer material to obtain a composite material, and preparing a film by using the composite material.
In a preferred embodiment of the present invention, the polymer monomer is one or a mixture of aromatic diamine, aromatic dianhydride and vinylidene fluoride; aromatic diamines, aromatic dianhydrides are preferred.
In a preferred embodiment of the present invention, the solvent is one or a mixture of ethanol, methanol, tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, etc.; n-methylpyrrolidone is preferred.
As a preferable scheme of the invention, the high polymer material is one or a mixture of polyamide, polyimide, polycarbonate, polyethylene, polyvinyl chloride, polypropylene and polyvinylidene fluoride; polyamides and polyimides are preferred.
As a preferable scheme of the invention, the mixing method is one or more of ultrasonic, stirring and ball milling.
In a preferred embodiment of the present invention, the film-forming method is one or more of extrusion, spraying, brushing, printing, and extrusion.
The invention further provides an application of the novel heating film in the field of electric heating.
Preferably used as an electrothermal film for preparing any one of an electrothermal floor heating, an electrothermal tent, an electrothermal garment, an electrothermal picture, an electrothermal wall, an electric heater and an electric blanket.
On the basis of the common knowledge in the field, the above preferred conditions can be combined with each other to obtain the preferred embodiments of the invention.
The invention has the following beneficial effects:
(1) the novel heating film has excellent thermal efficiency and heat conductivity, has excellent stability and can realize thermal cycle for 10000 times; and the composite material has good mechanical properties, and can be widely applied to the fields of various electric automobiles, aerospace and the like.
(2) The preparation method disclosed by the invention is low in raw material cost, high in repeatability of the preparation process, simple in process, less in time consumption and suitable for industrial production.
Drawings
FIG. 1 is a top view of a topography scanning electron microscope characterization result of the novel heating film of example 1, with the film layer being uniform, dense and flat;
FIG. 2 is a scanning electron microscope cross-sectional view of the topography of the novel heating film of example 1, showing that it is about 2 microns thick;
FIG. 3 is an infrared image of the novel heating film of example 1 when electrically heated.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the following embodiments, the two-dimensional composite nanomaterial is prepared as follows: and (3) repeatedly folding and rolling the intermediate layer material, the upper layer material and the lower layer material in a roller press, and then carrying out ultrasonic treatment in IPA to obtain the product.
Example 1
(1) Mechanically stirring 10g of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane or 4,4 '-diamino-2, 2' -bistrifluoromethyl biphenyl, 0.2g of silver-graphene-silver two-dimensional composite nano material and 0.2g of carbon nano tube in N-methyl pyrrolidone uniformly at room temperature in a nitrogen atmosphere, adding 10g of 1,2,4, 5-pyromellitic dianhydride, and continuously stirring for reacting for 6-12 hours to obtain a graphene/polyamide solution;
(2) and brushing the graphene/polyamide solution to form a film, then placing the film in a vacuum drying box, and performing vacuum drying to obtain the novel heating film.
The top view of the characterization result of the heating film by a shape scanning electron microscope is obtained by detection (see attached figure 1), and the film layer is uniform, compact and flat; and a sectional view of the morphology thereof by a scanning electron microscope (see figure 2) is obtained, which shows that the thickness thereof is about 2 microns; the infrared image during heating is shown in figure 3, the heating speed is high, and the temperature zone distribution is relatively uniform.
Example 2
(1) Ultrasonically stirring 13g of 1,2, 6-hexanetriol, 30g of triethylamine, 6g of alumina-BN-alumina two-dimensional composite nanosheet and 1g of carbon nanotube in 500ml of acetone, uniformly mixing, adding 30g of glutaryl chloride, continuously stirring for reacting for 3-4 hours, removing the solvent by rotary evaporation, and then washing with distilled water to obtain a two-dimensional composite nanosheet-polyester mixture.
(2) And rolling the two-dimensional composite nanosheet-polyester mixture into a film, and then placing the film in a drying oven for drying to obtain the novel heating film.
Example 3
(1) In the room temperature and nitrogen atmosphere, ultrasonically stirring 10g of 4,4' -diaminodiphenylmethane, 0.02g of polypyrrole-molybdenum disulfide-polypyrrole two-dimensional nanosheet and 0.5g of carbon nanotube in tetrahydrofuran uniformly, adding 10g of 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride, and continuously stirring for reacting for 6-12 hours to obtain a molybdenum disulfide two-dimensional composite nanosheet/polyamide solution;
(2) and spraying the molybdenum disulfide two-dimensional composite nanosheet/polyamide solution to form a film, and then drying through supercritical to obtain the novel heating film.
Example 4
(1) In the room temperature and nitrogen atmosphere, mechanically stirring 50g of bisphenol A diether tetracarboxylic dianhydride, 26g of dimethyl diphenylmethane diisocyanate, 5g of iron-graphene-iron two-dimensional composite nanosheet and 5g of carbon nano tube uniformly, reacting for 1.5 hours at 70 ℃, adding 1g of s-triazine, heating to 160 ℃, continuing to react for 12-16 hours, adding 10g of 1,2,4, 5-s-benzenetetracarboxylic dianhydride, continuing to stir and react for 6-12 hours, filtering, and drying to obtain a two-dimensional composite nanosheet/polyimide mixture;
(2) and extruding the two-dimensional composite nanosheet/polyimide mixture into a film, then placing the film in a vacuum drying oven, and performing vacuum drying to obtain the novel heating film.
Example 5
(1) Uniformly mixing 1g of cellulose-graphene-cellulose two-dimensional composite nanosheets, 1g of carbon nanotubes and 8g of polyethylene by stirring and dispersing;
(2) and (2) preparing the composite material obtained in the step (1) into a film by adopting extrusion molding, and carrying out heat treatment to obtain the novel heating film.
Example 6
(1)1g of aluminum nitride-black scale-aluminum nitride two-dimensional composite nanosheet, 1g of carbon nanotube and 98g of polyimide are dispersed and mixed uniformly by a ball milling method;
(2) and (3) preparing the composite material obtained in the step (1) into a film by adopting a rolling method, and carrying out heat treatment to obtain the novel heating film.
Example 7
(1)0.1g of copper-MXene-copper two-dimensional composite nanosheet, 0.1g of carbon nanotube and 99.8g of polyvinyl chloride are dispersed and mixed uniformly by adopting a stirring method;
(2) and (3) preparing the composite material obtained in the step (1) into a film by adopting an extrusion method, and carrying out heat treatment to obtain the novel heating film.
Example 8
(1) Dispersing and mixing 10g of alumina-BN-alumina two-dimensional composite nanosheet, 10g of carbon nanotube and 80g of polypropylene uniformly by adopting an ultrasonic stirring method;
(2) and (2) preparing a film from the composite material obtained in the step (1) by adopting an extrusion method, and carrying out heat treatment to obtain the novel heating film.
Example 9
(1) Dispersing and mixing 10g of alumina-graphene-alumina two-dimensional composite nanosheets, 1g of carbon nanotubes and 89g of polyvinylidene fluoride uniformly by a ball milling method;
(2) and (3) preparing the composite material obtained in the step (1) into a film by adopting a printing method, and carrying out heat treatment to obtain the novel heating film.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A novel heating film is characterized by comprising a two-dimensional nano composite material, a carbon nano tube and a high polymer material, wherein the thickness of a coating is 1-100 mu m, and the thermal diffusion coefficient is 5-20 cm2S, coefficient of thermal conductivityIs 1000 to 3000W/(m "k);
the mass of the two-dimensional nano composite material accounts for 0.1-10% of the total mass; the mass of the carbon nano tube accounts for 0.1-10% of the total mass, and the mass of the high polymer material accounts for 99.8-20% of the total mass;
the two-dimensional nanocomposite material has a sandwich structure and consists of an intermediate layer and an upper layer and a lower layer, wherein the intermediate layer is made of one or a mixture of graphene, BN, black scale, two-dimensional sulfide and two-dimensional carbide; the materials of the upper layer and the lower layer are one or a mixture of silver, iron, copper, aluminum nitride, aluminum oxide, conductive polymer and cellulose.
2. The heating film according to claim 1, wherein the polymer material is one of polyamide, polyimide, polycarbonate, polyethylene, polyvinyl chloride, polypropylene, polyvinylidene fluoride, or a mixture thereof.
3. The method for preparing a heating film according to claim 1 or 2, wherein the two-dimensional nanocomposite, the carbon nanotube and the polymer monomer are mixed in a solvent, an initiator is added, a composite material is obtained after a polymerization reaction, and the composite material is used for preparing a film.
4. The method of claim 1 or 2, wherein the two-dimensional nanocomposite, the carbon nanotube, and the polymer material are mixed to obtain a composite material, and the composite material is used to form a film.
5. The method according to claim 3, wherein the high molecular monomer is one of aromatic diamine, aromatic dianhydride, vinylidene fluoride or a mixture thereof;
the solvent is one or a mixture of ethanol, methanol, tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
6. The method according to any one of claims 3 to 5, wherein the mixing method is one or more of ultrasonic, stirring and ball milling.
7. The method according to any one of claims 3 to 5, wherein the film forming method is one or more of extrusion, spraying, brushing, printing and extrusion.
8. The method of claim 6, wherein the film forming process is one or more of extrusion, spraying, brushing, printing, and extrusion.
9. Use of a heating film according to claim 1 or 2 or a heating film prepared by a method according to any one of claims 3 to 8 in the field of electric heating.
10. The use of claim 9, wherein the heating film is used as an electrothermal film for preparing any one of an electrothermal floor heating, an electrothermal tent, an electrothermal garment, an electrothermal picture, an electrothermal wall, an electric heater, and an electric blanket.
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| CN107525123A (en) * | 2016-06-21 | 2017-12-29 | 苏州汉纳材料科技有限公司 | Highly conductive ultra-thin two-dimension carbon composite face heater and its application |
| CN108751995A (en) * | 2018-07-10 | 2018-11-06 | 中国科学院宁波材料技术与工程研究所 | Nanoparticle in-stiu coating MXenes composite materials, its preparation method and purposes |
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| US10147941B2 (en) * | 2016-03-15 | 2018-12-04 | The Hong Kong Polytechnic University | Synthesis method for cathode material in lithium-sulfur battery |
| GB201616242D0 (en) * | 2016-09-23 | 2016-11-09 | Imperial Innovations Limited | Composite material |
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| CN108822317B (en) * | 2018-04-11 | 2021-04-06 | 杭州牛墨科技有限公司 | Preparation method of graphene polyimide heating film |
| CN110149738B (en) * | 2019-04-22 | 2021-11-05 | 杭州电子科技大学 | Electrothermal film based on graphene/iron oxide composite material and preparation method thereof |
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| CN107525123A (en) * | 2016-06-21 | 2017-12-29 | 苏州汉纳材料科技有限公司 | Highly conductive ultra-thin two-dimension carbon composite face heater and its application |
| CN108751995A (en) * | 2018-07-10 | 2018-11-06 | 中国科学院宁波材料技术与工程研究所 | Nanoparticle in-stiu coating MXenes composite materials, its preparation method and purposes |
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