CN110602934A - Electromagnetic shielding heat dissipation film and preparation method and application thereof - Google Patents
Electromagnetic shielding heat dissipation film and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrochemical materials, and particularly relates to a preparation method of an electromagnetic shielding heat dissipation film, which comprises the following steps: obtaining a carbon nanotube film and a graphene film; alternately laminating at least one layer of carbon nanotube film and at least one layer of graphene film, and performing hot pressing treatment for 8-10 hours at 2800-3000 ℃ in a protective gas atmosphere to obtain a laminated functional layer of carbon nanotubes and graphene; obtaining a substrate layer, and bonding the laminated functional layer to one side surface of the substrate layer by adopting a bonding agent; and obtaining a heat-conducting adhesive, and coating the heat-conducting adhesive on the surface of the other side, far away from the substrate layer, of the laminated functional layer to form a heat-conducting adhesive layer, so as to obtain the electromagnetic shielding heat dissipation film. The preparation method of the electromagnetic shielding heat dissipation film provided by the invention is simple in process, easy to operate and convenient for industrial production and application.
Description
Technical Field
The invention belongs to the technical field of electrochemical materials, and particularly relates to an electromagnetic shielding heat dissipation film, and a preparation method and application thereof.
Background
With the continuous progress of social science and technology, electronic technology is rapidly developed, and electronic products play more and more important roles in daily production and life. The higher the sensitivity of electronic components, the more susceptible to external electromagnetic interference, and the greater the use of silver-based, copper-based, nickel-based, and other metal-filled shielding materials. However, the silver-based conductive coating has stable performance, but is expensive and mainly applied to a special field, the copper-based conductive coating has low resistivity, but is difficult to disperse due to easy sinking, and has poor oxidation resistance, the nickel-based conductive coating has moderate price and good oxidation resistance, so the silver-based conductive coating becomes the mainstream of the electromagnetic shielding coating, but the nickel has low conductivity, and the electromagnetic shielding performance in a low frequency region and a high frequency region is not ideal, and the oxidation resistance is poor.
Carbon nanotubes have also attracted much attention because of their excellent electromagnetic shielding properties. The carbon nano tube has high conductivity, so that the carbon nano tube can dissipate static charges and even electromagnetic radiation from electromagnetic shielding equipment, and the characteristic has potential application value in the technical field of wave-absorbing shielding.
In addition, the electronic product is a process of continuously generating heat in the using process, and the generated heat energy continuously rises along with the prolonging of the using time. Conventional materials for shielding electromagnetic waves often dissipate wave energy by the reflection or absorption of electromagnetic waves by electromagnetic shielding materials. When the electromagnetic wave shielding material reflects or absorbs the dissipated wave energy, a part of the electromagnetic wave is converted into heat energy, which further causes the temperature of the electronic product to rise, not only can the shielding effect of the electromagnetic wave shielding material on the electromagnetic wave be reduced, but also the power consumption of the electronic product can be increased, and the stability of the electronic product can be reduced. The prior art lacks a carbon nanotube electromagnetic shielding and heat dissipating film which has high electromagnetic wave shielding efficiency, high heat conductivity, high conductivity, low thickness and flexible application.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a preparation method of an electromagnetic shielding heat dissipation film, and aims to solve the technical problem that an electromagnetic shielding heat dissipation film which has the characteristics of high electromagnetic wave shielding conductivity, high conductivity, good heat dissipation performance, flexibility and convenience in application and the like cannot be prepared in the prior art.
Another object of the present invention is to provide an electromagnetic shielding heat dissipation film.
Means for solving the problems
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of the electromagnetic shielding heat dissipation film comprises the following steps:
obtaining a carbon nanotube film and a graphene film;
alternately laminating at least one layer of carbon nanotube film and at least one layer of graphene film, and performing hot pressing treatment for 8-10 hours at 2800-3000 ℃ in a protective gas atmosphere to obtain a laminated functional layer of carbon nanotubes and graphene;
obtaining a substrate layer, and bonding the laminated functional layer to one side surface of the substrate layer by adopting a bonding agent;
and obtaining a heat-conducting adhesive, and coating the heat-conducting adhesive on the surface of the other side, far away from the substrate layer, of the laminated functional layer to form a heat-conducting adhesive layer, so as to obtain the electromagnetic shielding heat dissipation film.
Preferably, the carbon nanotube film is a carbon nanotube array film, and the length of the carbon nanotubes in the carbon nanotube film is 100-1200 microns, and the diameter of the carbon nanotubes in the carbon nanotube film is 6-10 nanometers.
Preferably, the step of obtaining the graphene thin film comprises: obtaining a graphene organic dispersion solution, and performing suction filtration on the graphene organic dispersion solution on filter paper in a suction filtration mode to obtain a graphene film; and then soaking the filter paper with the formed graphene film in water to separate the graphene film from the filter paper, thereby obtaining the graphene film.
Preferably, the organic solvent in the graphene organic solution is selected from: at least one of N-methylpyrrolidone, tetrahydrofuran and N, N-dimethylformamide; and/or the presence of a gas in the gas,
the concentration of the graphene organic solution is 0.01-2 mg/L; and/or the presence of a gas in the gas,
the thickness of the graphene film is 0.5-50 microns.
Preferably, the mass ratio of the carbon nanotube film to the graphene film in the laminated functional layer of the carbon nanotube and the graphene is (5-8): (2-5).
Preferably, the matrix layer is selected from: one of polyester film, polyethylene film, polyvinyl chloride and polypropylene film; and/or the presence of a gas in the gas,
the binder is selected from: a hot melt adhesive or the thermally conductive adhesive; and/or the presence of a gas in the gas,
the thermally conductive adhesive is selected from: at least one of organic silica gel binder, epoxy resin binder and acrylate binder; and/or the presence of a gas in the gas,
the heat conductivity coefficient of the heat conduction bonding layer is larger than 40W/mK.
The electromagnetic shielding heat dissipation film is prepared by the preparation method of the electromagnetic shielding heat dissipation film.
Preferably, the laminated functional layer comprises at least one layer of carbon nanotube film and at least one layer of graphene film which are alternately laminated, and the mass ratio of the carbon nanotube film to the graphene film is (5-8): (2-5), the carbon nanotube film is a carbon nanotube array film, the tube length of the carbon nanotubes in the carbon nanotube film is 100-1200 microns, and the tube diameter is 6-10 nanometers.
Preferably, the electromagnetic shielding and heat dissipating film comprises:
preferably, the electromagnetic shielding heat dissipation film further includes: the release layer is arranged on the other side surface, away from the laminated functional layer, of the heat conduction bonding layer, and the thickness of the release layer is 25-40 micrometers; the release layer is selected from: one of a polyethylene terephthalate release layer, a polyethylene release layer and an o-phenylphenol release layer; and/or the presence of a gas in the gas,
the material of the bonding layer is selected from: a thermally conductive adhesive or a hot melt adhesive; and/or the presence of a gas in the gas,
the heat conductivity coefficient of the heat conduction bonding layer is more than 40W/mK; and/or the presence of a gas in the gas,
the material of the heat-conducting bonding layer is at least one selected from organic silicon, epoxy resin and acrylate; and/or the presence of a gas in the gas,
the substrate layer is selected from: polyester film, polyethylene film, polyvinyl chloride, polypropylene film.
Effects of the invention
The preparation method of the electromagnetic shielding heat dissipation film provided by the invention takes the carbon nanotube film and the graphene film as raw materials, wherein the carbon nanotube film has higher thermal conductivity and electrical conductivity and better electromagnetic shielding effect; the graphene film has a unique electronic structure, small resistance, high conductivity, large specific surface area and strong stability. The carbon nanotube film and the graphene film are alternately stacked, so that two-dimensional sheet structures of the graphene are connected by a continuous network structure of the carbon nanotube film to form a three-dimensional net structure, the respective advantages of the carbon nanotube film and the graphene are fully exerted, a synergistic effect is formed, and then the two-dimensional sheet structures are subjected to hot pressing treatment for 8-10 hours in a protective gas atmosphere at 2800-3000 ℃, so that impurities and oxidation groups on the surfaces of the carbon nanotube and the graphene are reduced, the structural integrity of the carbon nanotube and the graphene is improved, the heat conduction efficiency and the electric conduction efficiency are further improved, the electromagnetic shielding efficiency is improved, and a stacked functional layer with excellent performance is obtained. And then, the laminated functional layer is adhered to the substrate layer by adopting an adhesive, and a heat conduction adhesive layer is formed on the surface of the other side of the laminated functional layer to obtain the electromagnetic shielding heat dissipation film. The electromagnetic shielding heat dissipation film prepared by the preparation method provided by the invention has the characteristics of high electromagnetic wave shielding conductivity, high conductivity, good heat dissipation performance, flexible and convenient application and the like, and the preparation method is simple in preparation process, easy to operate and convenient for industrial production and application.
The electromagnetic shielding heat dissipation film provided by the invention is prepared by the preparation method of the electromagnetic shielding heat dissipation film, and also comprises the following components in percentage by mass: (2-5) laminated functional layers formed by alternately laminating the graphene films, wherein the graphene films have unique electronic structures, small resistance, high conductivity, large specific surface area and strong stability; the carbon nanotube film has low volume resistivity and high electric and heat conduction efficiency. Therefore, the electromagnetic shielding heat dissipation film provided by the embodiment of the invention has the characteristics of high electromagnetic shielding conductivity, high conductivity, good heat dissipation performance, wide application scene and the like.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides a preparation method of an electromagnetic shielding heat dissipation film, which comprises the following steps:
s10, obtaining a carbon nano tube film and a graphene film;
s20, alternately laminating at least one layer of carbon nanotube film and at least one layer of graphene film, and performing hot pressing treatment for 8-10 hours at 2800-3000 ℃ in a protective gas atmosphere to obtain a laminated functional layer of carbon nanotubes and graphene;
s30, obtaining a substrate layer, and attaching the laminated functional layer to one side surface of the substrate layer by adopting a binder;
s40, obtaining a heat-conducting adhesive, coating the heat-conducting adhesive on the surface of the other side, far away from the substrate layer, of the laminated functional layer to form a heat-conducting adhesive layer, and obtaining the electromagnetic shielding heat dissipation film.
According to the preparation method of the electromagnetic shielding heat dissipation film, the carbon nanotube film and the graphene film are used as raw materials, wherein the carbon nanotube film is higher in heat conductivity and electric conductivity and better in electromagnetic shielding effect; the graphene film has a unique electronic structure, small resistance, high conductivity, large specific surface area and strong stability. The carbon nanotube film and the graphene film are alternately stacked, so that two-dimensional sheet structures of the graphene are connected by a continuous network structure of the carbon nanotube film to form a three-dimensional net structure, the respective advantages of the carbon nanotube film and the graphene are fully exerted, a synergistic effect is formed, and then the two-dimensional sheet structures are subjected to hot pressing treatment for 8-10 hours in a protective gas atmosphere at 2800-3000 ℃, so that impurities and oxidation groups on the surfaces of the carbon nanotube and the graphene are reduced, the structural integrity of the carbon nanotube and the graphene is improved, the heat conduction efficiency and the electric conduction efficiency are further improved, the electromagnetic shielding efficiency is improved, and a stacked functional layer with excellent performance is obtained. And then, the laminated functional layer is adhered to the substrate layer by adopting an adhesive, and a heat conduction adhesive layer is formed on the surface of the other side of the laminated functional layer to obtain the electromagnetic shielding heat dissipation film. The electromagnetic shielding heat dissipation film prepared by the preparation method provided by the embodiment of the invention has the characteristics of high electromagnetic shielding conductivity, high conductivity, good heat dissipation performance, flexible and convenient application and the like, and the preparation method is simple in preparation process, easy to operate and convenient for industrial production and application.
Specifically, in step S10, a carbon nanotube film and a graphene film are obtained. In a preferred embodiment, the carbon nanotube film is a carbon nanotube array film, and the carbon nanotubes in the carbon nanotube film have a length of 100 to 1200 μm and a diameter of 6 to 10 nm.
The carbon nanotube film is a carbon nanotube array film, carbon nanotubes in the carbon nanotube array film are more ordered and consistent in orientation, heat and electricity conduction can be conducted towards the same direction, the heat conductivity and the electric conductivity are higher, and the electromagnetic shielding effect is better. The carbon nano tube in the carbon nano tube film has the tube length of 100-1200 micrometers, the tube diameter of 6-10 nanometers, large length-diameter ratio and specific surface area, low volume resistivity and high electric and heat conduction efficiency, and is more favorable for conducting and bridging before a graphene sheet layer, so that a laminated functional layer has a better three-dimensional network structure, and the shielding and heat dissipation effects of the electromagnetic shielding heat dissipation film are improved. In some embodiments, the carbon nanotubes in the carbon nanotube film have a tube length of 100 to 500 μm and a tube diameter of 6 to 10 nm.
In some embodiments, the carbon nanotube film has a width of 1-20 cm and a length of 1-20 cm. The size of the carbon nanotube film in the embodiment of the invention can be selected in a wide range, and the carbon nanotube films with different sizes can be obtained according to the actual application requirements. In some embodiments, the carbon nanotubes in the carbon nanotube film have a tube length of 100 to 1200 μm and a tube diameter of 6 to 10 nm; the carbon nanotube film has a width of 1-20 cm and a length of 1-20 cm.
In some embodiments, after the carbon nanotube film is obtained, the carbon nanotube film is infiltrated by an organic solvent to make the carbon nanotube film relatively compact, which is beneficial to the alternate lamination and compaction of the subsequent graphene film.
As a preferred embodiment, the step of obtaining the graphene thin film includes: obtaining a graphene organic dispersion solution, and performing suction filtration on the graphene organic dispersion solution on filter paper in a suction filtration mode to obtain a graphene film; and then soaking the filter paper with the formed graphene film in water to separate the graphene film from the filter paper, thereby obtaining the graphene film. According to the graphene film disclosed by the embodiment of the invention, the graphene film with a certain thickness is formed on the filter membrane by carrying out suction filtration treatment on the organic dispersion solution of graphene, and then the graphene film is separated from the filter paper by carrying out soaking treatment, so that the graphene film is obtained. The method has the advantages of simple obtaining steps, easiness in operation, high flexibility and capability of controlling the thickness of the graphene film by controlling the suction filtration amount of the graphene organic dispersion liquid.
As a preferred embodiment, the organic solvent in the graphene organic solution is selected from: at least one of N-methyl pyrrolidone, tetrahydrofuran and N, N-dimethylformamide. According to the embodiment of the invention, organic solvents such as N-methyl pyrrolidone, tetrahydrofuran and N, N-dimethylformamide have a good dispersion effect on graphene, and the graphene can be dispersed in the organic solution through high-speed shearing, stirring, homogenizing and the like, so that the graphene organic solution is formed.
In a preferred embodiment, the concentration of the organic solution of graphene is 0.01mg/L to 2 mg/L. The concentration of the graphene organic solution in the embodiment of the invention is 0.01 mg/L-2 mg/L, which is beneficial to forming uniform dispersion and good stability of graphene in the organic solution and forming a uniform graphene film by suction filtration, and if the concentration is too high, the graphene film is easy to be non-uniform and has poor stability.
In a preferred embodiment, the thickness of the graphene film is 0.5-50 micrometers. The thickness value range of the graphene film is large, the graphene film is convenient and flexible to apply, and the graphene film and the carbon nanotube film with different thicknesses can be selected to be alternately stacked according to specific application conditions.
As a more preferable embodiment, the thickness of the graphene film is 0.5-10 microns, and the graphene film with low thickness enables the number of alternate laminations of the graphene film and the carbon nanotube film in the laminated functional layer to be more, the layers to be richer, the formed three-dimensional network structure to be better, and the electric conduction, the heat conduction and the electromagnetic shielding effect of the laminated functional layer to be further ensured.
In some embodiments, the organic solvent in the graphene organic solution is selected from: at least one of N-methylpyrrolidone, tetrahydrofuran and N, N-dimethylformamide; the concentration of the graphene organic solution is 0.01-2 mg/L; the thickness of the graphene film is 0.5-50 microns.
Specifically, in step S20, after at least one layer of the carbon nanotube film and at least one layer of the graphene film are alternately stacked, hot-pressing the carbon nanotube film and the graphene film at 2800 to 3000 ℃ in a protective gas atmosphere for 8 to 10 hours to obtain a stacked functional layer of carbon nanotubes and graphene. According to the embodiment of the invention, the carbon nanotube film and the graphene film are alternately stacked and then compacted, so that the two-dimensional lamellar structures of the graphene are connected by the continuous network structure of the carbon nanotube film to form a three-dimensional network structure, the respective advantages of the two are fully exerted, a three-dimensional network stacked functional layer with a synergistic effect is formed, and the electric conduction, the heat conduction and the electromagnetic shielding effect of the functional layer are further enhanced. And then carrying out hot-pressing treatment for 8-10 hours at 2800-3000 ℃ in a protective gas atmosphere, so that impurities and oxidation groups on the surfaces of the carbon nano tube and the graphene are reduced, the structural integrity of the carbon nano tube and the graphene is improved, defects are reduced, the heat conduction efficiency and the electric conduction efficiency are further improved, the electromagnetic shielding efficiency is further improved, and the laminated functional layer with excellent performance is obtained. The embodiment of the invention does not specifically limit the compaction treatment after the carbon nanotube film and the graphene film are alternately laminated, as long as the composite film layer after the carbon nanotube film and the graphene film are alternately laminated is compact and not easy to fall off and separate, and the application requirement in the electromagnetic shielding film is met.
In some embodiments, the carbon nanotube film and the graphene film are alternately stacked and then compacted, and then hot-pressed for 8 hours, 10 hours or 12 hours under the protection gas condition of nitrogen, argon or helium at 2800 ℃, 2900 ℃ or 3000 ℃ to obtain the stacked functional layer of the carbon nanotube and the graphene.
As a preferred embodiment, the step of compacting after alternately stacking the carbon nanotube film and the graphene film comprises: and after the at least two carbon nanotube films and the at least two graphene films are alternately stacked, compacting the carbon nanotube films and the graphene films into a complete film layer, namely the stacked functional layer.
In a preferred embodiment, the mass ratio of the carbon nanotube film to the graphene film in the laminated functional layer of the carbon nanotubes and the graphene is (5-8): (2-5). According to the embodiment of the invention, the mass ratio of the carbon nanotube film to the graphene film in the laminated functional layer is (5-8): (2-5), and the specific mass ratio ensures that a three-dimensional network laminated functional layer with a synergistic effect is formed between the two-dimensional sheet structure of the graphene and the carbon nanotube film in the laminated functional layer.
Specifically, in step S30, a base layer is obtained, and the laminated functional layer is bonded to one surface of the base layer with an adhesive. According to the embodiment of the invention, the laminated functional layer is adhered to one side surface of the substrate layer through the adhesive, so that the laminated functional layer is stabilized on the substrate layer of the electromagnetic shielding heat dissipation film.
As a preferred embodiment, the matrix layer is selected from: polyester film, polyethylene film, polyvinyl chloride, polypropylene film. The polyester film, the polyethylene film, the polyvinyl chloride film or the polypropylene film adopted by the embodiment of the invention are used as the substrate layers, have surface insulation and protection functions, are good in flexibility, can be bent and wound, are easy to process into any shape, and are beneficial to the subsequent application of the electromagnetic shielding heat dissipation film to electromagnetic shielding in various scenes.
As a preferred embodiment, the binder is selected from: a hot melt adhesive or the thermally conductive adhesive. In the embodiment of the invention, the laminated functional layer is bonded on the substrate layer by adopting a hot-melt adhesive or a heat-conducting adhesive, and the adopted adhesive only needs to realize good bonding effect of the laminated functional layer and the substrate layer, has high stability and does not influence the electric conduction, the heat conduction and the electromagnetic shielding effect of the electromagnetic shielding heat dissipation film. In particular embodiments, epoxy adhesives, polyurethane adhesives, amino resin adhesives, and the like may be used. In addition, the amount of the binder used in the embodiment of the present invention is not particularly limited, and the amount of the binder used is only required to be able to firmly attach the laminated functional layer to the substrate layer, and does not need to be used excessively, and an appropriate amount may be selected according to the thickness of the laminated functional layer and the type of the substrate layer in a specific application.
In some embodiments, the substrate layer is selected from: one of polyester film, polyethylene film, polyvinyl chloride and polypropylene film; the binder is selected from: hot melt adhesives or thermally conductive adhesives.
Specifically, in step S40, a heat conductive adhesive is obtained, and the heat conductive adhesive is coated on the other side surface of the laminated functional layer away from the substrate layer to form a heat conductive adhesive layer, so as to obtain the electromagnetic shielding heat dissipation film. The embodiment of the invention forms the heat conduction bonding layer on the laminated functional layer, not only can reduce the thermal resistance between the electromagnetic shielding heat dissipation film and a heat source while conducting heat, but also has the bonding effect, can ensure that the electromagnetic shielding heat dissipation film is directly adhered to an electronic component in subsequent application, and has flexible and convenient application.
As a preferred embodiment, the thermally conductive adhesive is selected from the group consisting of: at least one of organic silica gel binder, epoxy resin binder and acrylate binder. The organic silicon layer provided by the embodiment of the invention can well reduce the thermal resistance between the electromagnetic shielding heat dissipation film and a heat source, and has good bonding performance.
As a preferred embodiment, the thermal conductivity coefficient of the thermal conductive bonding layer is more than 40W/mK. The heat conduction bonding layer with the heat conductivity coefficient larger than 40W/mK effectively ensures the effect of reducing the thermal resistance between the electromagnetic shielding heat dissipation film and the heat source by the heat conduction bonding layer, and is favorable for improving the heat dissipation effect and the shielding effect stability of the electromagnetic shielding heat dissipation film.
In some embodiments, the substrate layer is selected from: one of polyester film, polyethylene film, polyvinyl chloride and polypropylene film; the binder is selected from: a hot melt adhesive or a thermally conductive adhesive; the heat-conducting adhesive is selected from organic silica gel adhesive, epoxy resin adhesive or acrylate adhesive with the heat conductivity coefficient of more than 40W/mK.
Correspondingly, the embodiment of the invention also provides the electromagnetic shielding heat dissipation film, and the electromagnetic shielding heat dissipation film is prepared by the preparation method of the electromagnetic shielding heat dissipation film.
The electromagnetic shielding heat dissipation film provided by the invention is prepared by the preparation method of the electromagnetic shielding heat dissipation film, and also comprises the following components in percentage by mass: (2-5) laminated functional layers formed by alternately laminating the graphene films, wherein the graphene films have unique electronic structures, small resistance, high conductivity, large specific surface area and strong stability; the carbon nanotube film has low volume resistivity and high electric and heat conduction efficiency. Therefore, the electromagnetic shielding heat dissipation film provided by the embodiment of the invention has the characteristics of high electromagnetic shielding conductivity, high conductivity, good heat dissipation performance, wide application scene and the like.
The method comprises a laminated functional layer, wherein the laminated functional layer is composed of at least one layer of carbon nanotube film and at least one layer of graphene film which are alternately laminated, and the mass ratio of the carbon nanotube film to the graphene film is (5-8): (2-5), the carbon nanotube film is a carbon nanotube array film, the tube length of the carbon nanotubes in the carbon nanotube film is 100-1200 microns, and the tube diameter is 6-10 nanometers.
The electromagnetic shielding heat dissipation film provided by the embodiment of the invention comprises a laminated functional layer, wherein the laminated functional layer is formed by a carbon nanotube film with the tube length of 100-1200 micrometers and the tube diameter of 6-10 nanometers and a graphene film according to the mass ratio of (5-8): (2-5) alternately laminating the graphene film, wherein the graphene film has a unique electronic structure, small resistance, high conductivity, large specific surface area and strong stability; the carbon nanotube film with the tube length of 100-1200 microns and the tube diameter of 6-10 nanometers is a carbon nanotube array film, so that the carbon nanotube array film has the advantages of large length-diameter ratio and specific surface area, low volume resistivity, high electric conduction and heat conduction efficiency, more ordered carbon nanotubes in the array film, consistent orientation, contribution to the conduction of heat and electricity towards the same direction, higher heat conductivity and electric conductivity and better electromagnetic shielding effect; meanwhile, the long-chain carbon nano is more beneficial to the conduction and bridging action before the graphene sheet layer, so that the laminated functional layer has a better three-dimensional network structure, and the shielding and heat dissipation effects of the electromagnetic shielding heat dissipation film are improved. In addition, in the embodiment of the invention, the carbon nanotube film and the graphene film are as follows (5-8): (2-5) the specific mass ratio further ensures that a three-dimensional network laminated functional layer with a synergistic effect is formed between the two-dimensional lamellar structure of the graphene and the carbon nano tube film.
As a preferred embodiment, the electromagnetic shielding heat dissipation film comprises:
in the electromagnetic shielding heat dissipation film provided by the embodiment of the invention, the laminated functional layer with the thickness of 20-50 microns can effectively ensure the electromagnetic shielding, electric conduction and heat conduction effects of the electromagnetic shielding heat dissipation film. The heat conduction bonding layer is 15-25 microns thick, so that the heat conduction effect and the bonding effect of the heat conduction bonding layer are balanced, and if the heat conduction bonding layer is too thick, the heat conduction effect and the whole thickness are influenced; if it is too thin, the adhesion effect is affected, and direct application is not facilitated. The substrate layer with the thickness of 15-25 microns has a thickness suitable for processing and application, so that the electromagnetic shielding heat dissipation film is quantized favorably, and the application flexibility is improved; and the bonding layer with the thickness of 2-10 microns can firmly bond the laminated functional layer on the substrate layer. The electromagnetic shielding heat dissipation film provided by the embodiment of the invention has the advantages that the thicknesses of all film layers are smaller, so that the electromagnetic shielding heat dissipation film has low thickness and good flexibility on the basis of high electromagnetic wave shielding conductivity, high conductivity and good heat dissipation performance, and is more flexible and convenient to apply.
In some embodiments, the substrate layer is selected from: polyester film, polyethylene film, polyvinyl chloride, polypropylene film.
In some embodiments, the material of the tie layer is selected from: thermally conductive adhesives or hot melt adhesives.
In some embodiments, the material of the thermally conductive adhesive layer is selected from at least one of silicone, epoxy, and acrylate.
In some embodiments, the thermally conductive adhesive layer has a thermal conductivity greater than 40W/mK.
In some embodiments, the substrate layer is selected from: one of polyester film, polyethylene film, polyvinyl chloride and polypropylene film; the binder is selected from: a hot melt adhesive or a thermally conductive adhesive; the heat-conducting adhesive is selected from organic silica gel adhesive, epoxy resin adhesive or acrylate adhesive with the heat conductivity coefficient of more than 40W/mK.
As a preferred embodiment, the electromagnetic shielding heat dissipation film further includes: the release layer is arranged on the other side surface, away from the laminated functional layer, of the heat conduction bonding layer, and the thickness of the release layer is 25-40 micrometers; the release layer is selected from: one of a polyethylene terephthalate release layer, a polyethylene release layer and an o-phenylphenol release layer. The electromagnetic shielding heat dissipation film disclosed by the embodiment of the invention also comprises the release layer, so that the electromagnetic shielding heat dissipation film can be bonded with the heat conduction bonding layer and can be easily separated from the heat conduction bonding layer, the electromagnetic shielding heat dissipation film is protected from being polluted, the electromagnetic shielding heat dissipation film is favorably wound, the electromagnetic shielding heat dissipation film can be prevented from being mutually adhered, and the electromagnetic shielding heat dissipation film is convenient to store, transport, process and apply. The release layer with the thickness of 25-40 microns can play a good protection role on the electromagnetic shielding heat dissipation film, and is also beneficial to operations such as winding of the electromagnetic shielding heat dissipation film.
In addition, the electromagnetic shielding heat dissipation film provided by the embodiment of the invention can be applied to the fields of electronic products, components or vehicle products. The electromagnetic shielding heat dissipation film provided by the embodiment of the invention has the characteristics of high electromagnetic wave shielding conductivity, high conductivity, good heat dissipation performance, low thickness, good flexibility, flexible and convenient application and the like, and can play a better electromagnetic conduction shielding effect, a better heat dissipation effect, a better electric conduction effect and the like when being applied to the fields of electronic products, components, vehicles and the like.
In order to clearly understand the details of the above-mentioned implementation and operation of the present invention for those skilled in the art and to obviously show the advanced performance of the electromagnetic shielding heat dissipation film according to the embodiment of the present invention, the above-mentioned technical solution is exemplified by a plurality of embodiments.
Example 1
An electromagnetic shielding heat dissipation film comprises the following preparation steps:
s10, preparing a carbon nanotube film: and drawing out the carbon nanotube film with the length and the width of 5cm from the carbon nanotube array, and soaking the carbon nanotube film tightly by using an organic solvent to obtain the carbon nanotube film.
S20, preparing a graphene film: and (3) carrying out suction filtration on 2L of 2mg/L graphene N-methyl pyrrolidone solution, compacting, and infiltrating the compacted graphene N-methyl pyrrolidone solution and filter paper in an aqueous solution to obtain the graphene film.
And S30, overlapping 3 layers of the carbon nanotube film in S10 and the graphene film in S20, and carrying out heat treatment at 2800 ℃ for 10 hours under the protection of nitrogen to obtain the laminated functional layer.
And S40, adhering the laminated functional layer in the S30 to a polyethylene terephthalate substrate by adopting an organic silicon heat-conducting adhesive.
And S50, coating an organic silicon heat-conducting adhesive layer on the other side face, far away from the base layer, of the laminated functional layer in the S40, and attaching a layer of release paper to obtain the electromagnetic shielding heat dissipation film.
Comparative example 1
A copper-based electromagnetic shielding film comprises the following preparation steps:
s11, depositing a layer of 20-micron copper film on the polyethylene terephthalate substrate layer to obtain a copper film on the substrate layer;
s21, coating an organic silicon heat-conducting adhesive layer on the surface of one side, away from the substrate layer, of the copper film, and then attaching a polyethylene release layer to obtain the copper-based electromagnetic shielding film.
Comparative example 2
A carbon nano tube electromagnetic shielding film comprises the following preparation steps:
s12, preparing a carbon nanotube film: drawing a carbon nanotube film of 5cm from the carbon nanotube array, and soaking the carbon nanotube film by using an organic solvent to make the carbon nanotube film compact to obtain the carbon nanotube film;
s22, adhering the carbon nanotube film to a polyethylene terephthalate substrate layer by adopting an organic silicon heat-conducting adhesive, and obtaining the carbon nanotube film on the substrate layer;
s32, coating an organic silicon heat-conducting adhesive layer on the surface of one side, away from the substrate layer, of the carbon nanotube film, and then attaching a polyethylene release layer to obtain the carbon nanotube electromagnetic shielding film.
Comparative example 3
A graphene electromagnetic shielding film comprises the following preparation steps:
s13, preparing a graphene film: carrying out suction filtration on 2L of 2mg/L graphene NMP solution, compacting, and infiltrating together with filter paper in an aqueous solution to obtain a graphene film;
s23, adhering the graphene film to a polyethylene terephthalate substrate layer by adopting an organic silicon heat-conducting adhesive, and obtaining the graphene film on the substrate layer;
s33, coating an organic silicon heat-conducting adhesive layer on the surface of one side, away from the substrate layer, of the graphene film, and then attaching a polyethylene release layer to obtain the graphene electromagnetic shielding film.
Further, in order to verify the advancement of the electromagnetic shielding and heat dissipating film prepared in the embodiment of the present invention, the electromagnetic shielding and heat dissipating film of embodiment 1, the copper-based electromagnetic shielding film of comparative example 1, the carbon nanotube electromagnetic shielding film of comparative example 2, and the graphene electromagnetic shielding film of comparative example 3 were tested in the embodiment of the present invention for shielding efficiency, thermal conductivity, electrical conductivity, and the like.
The electromagnetic shielding heat dissipation film of example 1, the copper-based electromagnetic shielding film of comparative example 1, the carbon nanotube electromagnetic shielding film of comparative example 2, and the graphene electromagnetic shielding film of comparative example 3 were cut into 5cm × 5cm thin films having the same size. The shielding efficiency was tested at 2-12.52GHz using an Agilent vector network tester according to ASTM-D-4935. And testing the conductivity of the sample by using a conductivity tester. The thermal conductivity was measured using an LFA 427 laser thermal conductivity meter using the ASTM-E1461 standard. The test results are shown in table 1 below:
TABLE 1
From the above test results, it can be seen that the electromagnetic shielding heat dissipation film prepared in embodiment 1 of the present invention contains a self-supporting thin film made of a high aspect ratio carbon nanotube and graphene through an aqueous dispersion, and a good conductive network is formed by mutual contact between the carbon nanotube and the graphene, so as to exert a synergistic effect, such that the electromagnetic shielding heat dissipation film obtains high electromagnetic shielding efficiency and conductivity, the shielding efficiency reaches 73.7db, and the conductivity reaches 4.78 × 105The carbon nanotube electromagnetic shielding film is far superior to the carbon nanotube electromagnetic shielding film in the comparative example 2 and the graphene electromagnetic shielding film in the comparative example 3, and is close to a copper-based shielding film; meanwhile, the heat dissipation performance is excellent, and the heat conductivity is 1309W.m-1.K-1The electromagnetic shielding film is far superior to the copper-based electromagnetic shielding film in the comparative example 1, the carbon nano tube electromagnetic shielding film in the comparative example 2 and the graphene electromagnetic shielding film in the comparative example 3; and the weight of the electromagnetic shielding film can be greatly reduced, the electromagnetic shielding film is more beneficial to being flexibly applied to the fields of electronic products, automobiles, aerospace and the like, and the electromagnetic shielding film plays roles in electromagnetic shielding, heat dissipation and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the electromagnetic shielding heat dissipation film is characterized by comprising the following steps of:
obtaining a carbon nanotube film and a graphene film;
alternately laminating at least one layer of carbon nanotube film and at least one layer of graphene film, and performing hot pressing treatment for 8-10 hours at 2800-3000 ℃ in a protective gas atmosphere to obtain a laminated functional layer of carbon nanotubes and graphene;
obtaining a substrate layer, and bonding the laminated functional layer to one side surface of the substrate layer by adopting a bonding agent;
and obtaining a heat-conducting adhesive, and coating the heat-conducting adhesive on the surface of the other side, far away from the substrate layer, of the laminated functional layer to form a heat-conducting adhesive layer, so as to obtain the electromagnetic shielding heat dissipation film.
2. The method for preparing an electromagnetic shielding heat dissipation film according to claim 1, wherein the carbon nanotube film is selected from a carbon nanotube array film, and the carbon nanotubes in the carbon nanotube film have a length of 100 to 1200 μm and a diameter of 6 to 10 nm.
3. The method for preparing an electromagnetic shielding heat dissipation film according to claim 2, wherein the step of obtaining the graphene thin film comprises: obtaining a graphene organic dispersion solution, and performing suction filtration on the graphene organic dispersion solution on filter paper in a suction filtration mode to obtain a graphene film; and then soaking the filter paper with the formed graphene film in water to separate the graphene film from the filter paper, thereby obtaining the graphene film.
4. The method for preparing an electromagnetic shielding heat dissipation film according to claim 3, wherein the organic solvent in the graphene organic solution is selected from the group consisting of: at least one of N-methylpyrrolidone, tetrahydrofuran and N, N-dimethylformamide; and/or the presence of a gas in the gas,
the concentration of the graphene organic solution is 0.01-2 mg/L; and/or the presence of a gas in the gas,
the thickness of the graphene film is 0.5-50 microns.
5. The method for preparing the electromagnetic shielding heat dissipation film according to any one of claims 1 to 4, wherein the mass ratio of the carbon nanotube film to the graphene film in the laminated functional layer of the carbon nanotube and the graphene is (5-8): (2-5).
6. The method for manufacturing an electromagnetic shielding heat dissipating film according to claim 5, wherein the base layer is selected from the group consisting of: one of polyester film, polyethylene film, polyvinyl chloride and polypropylene film; and/or the presence of a gas in the gas,
the binder is selected from: a hot melt adhesive or the thermally conductive adhesive; and/or the presence of a gas in the gas,
the thermally conductive adhesive is selected from: at least one of organic silica gel binder, epoxy resin binder and acrylate binder; and/or the presence of a gas in the gas,
the heat conductivity coefficient of the heat conduction bonding layer is larger than 40W/mK.
7. An electromagnetic shielding heat dissipation film, wherein the electromagnetic shielding heat dissipation film is prepared by the preparation method of the electromagnetic shielding heat dissipation film according to any one of claims 1 to 6.
8. The electromagnetic shielding heat dissipation film according to claim 7, comprising a laminated functional layer, wherein the laminated functional layer is composed of at least one carbon nanotube film and at least one graphene film which are alternately laminated, and the mass ratio of the carbon nanotube film to the graphene film is (5-8): (2-5), the carbon nanotube film is a carbon nanotube array film, the tube length of the carbon nanotubes in the carbon nanotube film is 100-1200 microns, and the tube diameter is 6-10 nanometers.
9. The electromagnetic shielding heat dissipation film of claim 8, wherein the electromagnetic shielding heat dissipation film comprises, in order stacked:
10. the electromagnetic shielding heat dissipation film of claim 9, further comprising: the release layer is arranged on the other side surface, away from the laminated functional layer, of the heat conduction bonding layer, and the thickness of the release layer is 25-40 micrometers; the release layer is selected from: one of a polyethylene terephthalate release layer, a polyethylene release layer and an o-phenylphenol release layer; and/or the presence of a gas in the gas,
the material of the bonding layer is selected from: a thermally conductive adhesive or a hot melt adhesive; and/or the presence of a gas in the gas,
the heat conductivity coefficient of the heat conduction bonding layer is more than 40W/mK; and/or the presence of a gas in the gas,
the material of the heat-conducting bonding layer is at least one selected from organic silicon, epoxy resin and acrylate; and/or the presence of a gas in the gas,
the substrate layer is selected from: polyester film, polyethylene film, polyvinyl chloride, polypropylene film.
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Application publication date: 20191220 |