CN110804269A - Heat-conducting and electric-conducting film based on liquid metal and preparation method and application thereof - Google Patents
Heat-conducting and electric-conducting film based on liquid metal and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a liquid metal-based heat and electricity conducting film and a preparation method and application thereof, wherein the method comprises the following steps: mixing a heat-conducting filler with dopamine, and generating polydopamine on the surface of the heat-conducting filler to obtain a modified heat-conducting filler; mixing the modified heat-conducting filler, the liquid metal and a polyvinyl alcohol aqueous solution to obtain a mixed solution; and pouring the mixed solution into a mold, and volatilizing moisture to obtain the heat-conducting and electricity-conducting film with the upper layer as the heat-conducting filler and the lower layer as the liquid metal. The film prepared by the preparation method provided by the invention has high heat conduction and electric conduction performance, the liquid metal can be exposed by scratching the polyvinyl alcohol coated on the surface of the liquid metal on the liquid metal enrichment layer to form a conductive circuit which can be connected to an electronic device, the heat generated by the electronic device in the operation process can be rapidly dissipated through the layer enriched by the heat conduction filler, and the heat dissipation effect is good.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a liquid metal-based heat and electricity conducting film and a preparation method and application thereof.
Background
With the development of electronic components toward high power, high energy density and miniaturization, the heat generated by the electronic components per unit area is higher and higher, and the effective heat dissipation area is smaller and smaller. The heat dissipation problem becomes an important factor limiting the development of high-power electronic equipment, large-scale integrated circuits and flexible electronic devices, so that the development of a high-heat-conductivity heat dissipation material is an important problem to be solved urgently in the field of electronic component material industry.
At present, the commonly used heat dissipation technology is to realize heat dissipation by adding a heat conduction gasket or gel to an electronic device, and the method generally has the defects of low heat dissipation efficiency and insufficient heat dissipation area.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide a liquid metal-based heat and electricity conductive film, a preparation method thereof, and an application thereof, and aims to solve the problem of low heat dissipation efficiency of the conventional heat and electricity conductive film.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a liquid metal-based heat and electricity conducting film is disclosed, wherein the method comprises the following steps:
s100, mixing a heat-conducting filler with dopamine, and generating polydopamine on the surface of the heat-conducting filler to obtain a modified heat-conducting filler;
s200, mixing the modified heat-conducting filler, the liquid metal and a polyvinyl alcohol aqueous solution to obtain a mixed solution;
s300, pouring the mixed solution into a mold, and volatilizing moisture to obtain the heat conduction/electric conduction film with the upper layer as the heat conduction filler and the lower layer as the liquid metal.
The preparation method of the liquid metal-based heat-conducting and electricity-conducting film comprises the following steps of mixing the modified heat-conducting filler, the liquid metal and a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified heat-conducting filler to the liquid metal to the polyvinyl alcohol is 5: 1-10: 1-10.
The preparation method of the liquid metal-based heat and electricity conducting film comprises the step of preparing a liquid metal-based heat and electricity conducting film, wherein the heat conducting filler is one or more of hexagonal boron nitride, graphene and graphene oxide.
The preparation method of the high-thermal-conductivity and electric-conductivity film based on the liquid metal comprises the following steps of preparing a liquid metal, and preparing a high-thermal-conductivity and electric-conductivity film based on the liquid metal.
The preparation method of the liquid metal-based heat and electricity conducting film comprises the step of preparing a polyvinyl alcohol aqueous solution, wherein the mass fraction of polyvinyl alcohol in the polyvinyl alcohol aqueous solution is 5-15%.
The preparation method of the liquid metal-based heat-conducting and electric-conducting film comprises the following steps of mixing a heat-conducting filler with dopamine, generating polydopamine on the surface of the heat-conducting filler, and obtaining the modified heat-conducting filler, wherein the preparation method comprises the following steps:
mixing the heat-conducting filler and dopamine in deionized water, reacting under a preset condition, centrifuging after the reaction is finished, washing precipitates with the ionized water and absolute ethyl alcohol respectively, and drying the precipitates in vacuum to obtain the modified heat-conducting filler.
The preparation method of the liquid metal-based heat and electricity conducting film comprises the steps of mixing the heat conducting filler and dopamine in deionized water, adding a buffering agent to adjust the pH value to be 8-9, and reacting for 20-30 hours at the temperature of 25 ℃.
The preparation method of the liquid metal-based heat and electricity conducting film comprises the following steps of mixing the modified heat conducting filler, the liquid metal and a polyvinyl alcohol aqueous solution, and comprises the following steps:
and mixing the modified heat-conducting filler, the liquid metal and the polyvinyl alcohol aqueous solution, and placing the mixture in a cell crusher for ultrasonic treatment for 50-70min to obtain a mixed solution.
A heat-conducting and electric-conducting film is prepared by the preparation method.
The application of the heat-conducting and electricity-conducting film is characterized in that one surface, enriched with liquid metal, of the electricity-conducting and heat-conducting film is scraped to obtain an electricity-conducting circuit, and the electricity-conducting and electricity-conducting film is applied to preparation of electronic devices.
Has the advantages that: according to the invention, liquid metal is added as a conductive material, and the heat-conducting filler is modified by dopamine, so that the hydrophilicity of the heat-conducting filler is improved, and the heat-conducting filler is dispersed in a mixed solution. The liquid metal is settled in the film forming process, the lower layer of the liquid metal is enriched with liquid metal droplets, the upper layer of the liquid metal is a film enriched with heat conducting filler, the prepared film has high heat conducting and electric conducting properties, the liquid metal can be exposed by scraping the polyvinyl alcohol coated on the surface of the liquid metal on the liquid metal enrichment layer to form a conducting circuit which can be connected to an electronic device, the heat generated by the electronic device in the operation process can be rapidly dissipated out through the layer enriched with the heat conducting filler, and the heat dissipation effect is good.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a liquid metal-based heat and electricity conductive film according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flowchart illustrating a method for manufacturing a liquid metal-based heat and electricity conductive film according to a preferred embodiment of the present invention, which includes the following steps:
s100, mixing a heat-conducting filler with dopamine, and generating polydopamine on the surface of the heat-conducting filler to obtain a modified heat-conducting filler;
s200, mixing the modified heat-conducting filler, the liquid metal and a polyvinyl alcohol aqueous solution to obtain a mixed solution;
s300, pouring the mixed solution into a mold, and volatilizing moisture to obtain the heat-conducting and electricity-conducting film with the upper layer being the heat-conducting filler and the lower layer being the liquid metal.
In the embodiment, the heat-conducting filler is mixed with dopamine, the dopamine is subjected to polymerization reaction in a system to form polydopamine, the polydopamine is deposited on the surface of the heat-conducting filler to form the polydopamine modified heat-conducting filler, and hydrophilic hydroxyl groups are introduced into the heat-conducting filler after the heat-conducting filler is modified by the polydopamine, so that the hydrophilicity of the heat-conducting filler is improved. The modified heat-conducting filler, the liquid metal and the polyvinyl alcohol aqueous solution are mixed, poured into a mold for standing, the water volatilizes in the standing process, meanwhile, liquid metal drops settle down and are enriched in the lower layer part of the film, and the heat-conducting filler with good hydrophilicity can be well continuously dispersed in the system and is enriched in the upper layer part of the film, so that the film material with a double-layer film structure and high heat-conducting and electric-conducting performance is formed after the water is completely volatilized.
The film exposes the liquid metal by scraping the polyvinyl alcohol wrapped on the liquid metal enrichment layer to form a conductive circuit, the conductive circuit can be used for packaging electronic devices, and a large amount of heat generated in the operation of the devices can be timely dispersed out through the heat conduction surface of the heat conduction filler enrichment layer, so that efficient heat dissipation is realized. And the film has heat conduction and electric conduction performance, and does not need to be additionally provided with a heat dissipation device, thereby meeting the development trend of miniaturization of the existing electronic device.
In some embodiments, the mass ratio of the modified thermally conductive filler, the liquid metal, and the polyvinyl alcohol is 5: 1-10: 1-10. The heat-conducting and electricity-conducting film prepared in the range has better electricity-conducting and heat-conducting properties.
In some embodiments, the thermally conductive filler is one or more of hexagonal boron nitride, graphene, and graphene oxide. In this embodiment, the heat conductive filler is a two-dimensional heat conductive material, and orientation of the two-dimensional filler is induced by volatilization of moisture in a film forming process, so that an effect of increasing heat conductive performance is achieved.
In some embodiments, the liquid metal is one or more of pure gallium, mercury, bismuth, and alloys thereof. In this embodiment, the liquid metal is a low melting point metal or one or more of alloys thereof.
In some embodiments, the mass fraction of polyvinyl alcohol in the aqueous polyvinyl alcohol solution is 5-15%. In this embodiment, the polyvinyl alcohol is a substrate supporting material in the present invention, and after the moisture of the mixed solution is volatilized to form a film, the polyvinyl alcohol is wrapped on the surface of the liquid metal-enriched layer, so that both surfaces of the film formed after the film formation are insulated, one surface is the polyvinyl alcohol, and the other surface is the heat conductive filler-enriched layer. The polyvinyl alcohol on the surface is scraped, so that the liquid metal enrichment layer can be exposed, the exposed liquid metal route has electric conductivity, and different conductive circuits can be drawn according to different circuit designs. In some embodiments, the mass fraction of polyvinyl alcohol in the aqueous polyvinyl alcohol solution is 10%.
In some embodiments, the step S100 includes:
mixing the heat-conducting filler and dopamine in deionized water, reacting under a preset condition, centrifuging after the reaction is finished, washing precipitates with the ionized water and absolute ethyl alcohol respectively, and drying the precipitates in vacuum to obtain the modified heat-conducting filler.
In some embodiments, the thermally conductive filler and dopamine are mixed in deionized water, a buffer is added to adjust the pH to 8-9, and the mixture is reacted at a temperature of 25 ℃ for 20-30 hours. Dopamine is polymerized in a weak alkaline environment to form polydopamine, and the polydopamine is deposited on the surface of the heat-conducting filler, a plurality of hydrophilic hydroxyl groups are enriched on the surface of the filler, the heat-conducting filler is modified, the hydrophilicity of the heat-conducting filler is improved, the heat-conducting filler can be better dispersed in a mixed solution, and therefore the heat-conducting filler on the formed film is uniformly distributed, and the heat dissipation effect of the film is better. In some embodiments, the pH is 8.5. In some embodiments, the buffer is tris.
In some embodiments, the step S200 includes:
and mixing the modified heat-conducting filler, the liquid metal and the polyvinyl alcohol aqueous solution, and placing the mixture in a cell crusher for ultrasonic treatment for 50-70min to obtain a mixed solution. In the embodiment, the substrate is made into materials and the functional filler can be fully mixed by performing ultrasonic treatment on the cell crusher for 50-70min, and the polyvinyl alcohol is wrapped outside the liquid metal. In some embodiments, the cell disruptor is sonicated for 60 min.
The invention also provides a heat-conducting and electric-conducting film, which is prepared by adopting the preparation method.
The heat conducting and electricity conducting film has the advantages that one surface enriched with the liquid metal is scraped, different electricity conducting circuits can be drawn, the heat conducting and electricity conducting film can be applied to electronic devices, heat generated in the operation process of the electronic devices can be directly and rapidly dissipated through the heat conducting filler enrichment layer, and accordingly heat dissipation efficiency of the electronic devices is improved. The heat-conducting and electricity-conducting film provided by the invention has the performances of electricity conduction and heat conduction, does not need to additionally increase a heat-radiating material, greatly reduces the thickness of an electronic device, and is particularly suitable for preparing a flexible electronic device.
In the preparation method provided by the invention, no organic solvent is used, the principle of environmental protection is met, and the pollution to the environment in the preparation process is greatly reduced.
The present invention will be described in detail below with reference to specific examples.
Example 1
1g of BN and 0.5g of dopamine were weighed into a beaker containing 150ml of deionized water, the pH of the solution was adjusted to 8.5 using tris, and the reaction was carried out at 25 ℃ for 24h with magnetic stirring. After the reaction is finished, the mixture is firstly washed by deionized water for 3 times in a centrifugal mode, then washed by absolute ethyl alcohol for 3 times, and finally the centrifugal product is dried in a vacuum oven at 60 ℃ for 24 hours to obtain the polydopamine modified boron nitride (BN @ PDA).
Preparing 20g of polyvinyl alcohol into a 10% aqueous solution, then putting 5g of the aqueous solution of polyvinyl alcohol into a 30 ml glass bottle, adding 0.1g of BN @ PDA and 0.1g of gallium indium tin liquid metal, ultrasonically dispersing for 60min by using a cell crusher to obtain a mixed solution, then pouring the mixed solution into a mould, and volatilizing moisture in the atmosphere of room temperature and air to obtain the Janus composite film.
And drawing a conducting circuit on the liquid metal enrichment layer of the prepared Janus film in a scratching mode.
Example 2
1g of BN and 0.5g of dopamine were weighed into a beaker containing 150ml of deionized water, the pH of the solution was adjusted to 8.5 using tris, and the reaction was carried out at 25 ℃ for 24h with magnetic stirring. After the reaction is finished, the mixture is firstly washed by deionized water for 3 times in a centrifugal mode, then washed by absolute ethyl alcohol for 3 times, and finally the centrifugal product is dried in a vacuum oven at 60 ℃ for 24 hours to obtain the polydopamine modified boron nitride (BN @ PDA).
Preparing 20g of polyvinyl alcohol into a 10% aqueous solution, then putting 5g of the aqueous solution of polyvinyl alcohol into a 30 ml glass bottle, adding 0.3g of BN @ PDA and 0.5g of gallium indium tin liquid metal, ultrasonically dispersing for 60min by using a cell crusher to obtain a mixed solution, then pouring the mixed solution into a mould, and volatilizing moisture in the atmosphere of room temperature and air to obtain the Janus composite film.
And drawing a conducting circuit on the liquid metal enrichment layer of the prepared Janus film in a scratching mode.
Example 3
1g of BN and 0.5g of dopamine were weighed into a beaker containing 150ml of deionized water, the pH of the solution was adjusted to 8.5 using tris, and the reaction was carried out at 25 ℃ for 24h with magnetic stirring. After the reaction is finished, the mixture is firstly washed by deionized water for 3 times in a centrifugal mode, then washed by absolute ethyl alcohol for 3 times, and finally the centrifugal product is dried in a vacuum oven at 60 ℃ for 24 hours to obtain the polydopamine modified boron nitride (BN @ PDA).
Preparing 20g of polyvinyl alcohol into a 10% aqueous solution, then putting 5g of the aqueous solution of polyvinyl alcohol into a 30 ml glass bottle, adding 0.7g of BN @ PDA and 1g of gallium indium tin liquid metal, ultrasonically dispersing for 60min by using a cell crusher to obtain a mixed solution, then pouring the mixed solution into a mold, and volatilizing the water in the atmosphere of room temperature and air to obtain the Janus composite film.
And drawing a conducting circuit on the liquid metal enrichment layer of the prepared Janus film in a scratching mode.
Example 4
1g of graphene and 0.5g of dopamine are weighed into a beaker filled with 150ml of deionized water, the pH of the solution is adjusted to 8.5 by using tris (hydroxymethyl) aminomethane, and the solution is stirred with a magneton at 25 ℃ for reaction for 24 hours. After the reaction is finished, washing the graphene with deionized water for 3 times in a centrifugal mode, then washing the graphene with absolute ethyl alcohol for 3 times, and finally drying the centrifugal product in a vacuum oven at 60 ℃ for 24 hours to obtain the poly-dopamine modified graphene (GNPs @ PDA).
Preparing 20g of polyvinyl alcohol into a 10% aqueous solution, then putting 5g of the aqueous solution of polyvinyl alcohol into a 30 ml glass bottle, adding 0.3g of GNPs @ PDA and 1g of gallium indium tin liquid metal, ultrasonically dispersing for 60min by using a cell crusher to obtain a mixed solution, then pouring the mixed solution into a mold, and volatilizing moisture in the atmosphere of room temperature and air to obtain the Janus composite film.
And drawing a conducting circuit on the liquid metal enrichment layer of the prepared Janus film in a scratching mode.
Performance testing
The thermal conductivity and the resistance of the conductive circuit of the thermal conductive film prepared in the above embodiments 1, 2, 3, and 4 were measured, and the obtained test results are as follows:
| examples | Coefficient of thermal conductivity (W/mK) | Conducting wire resistance (omega) |
| Example 1 | 2.32 | 920 |
| Example 2 | 4.25 | 530 |
| Example 3 | 8.39 | 92 |
| Example 4 | 11.6 | 85 |
In summary, the invention provides a liquid metal-based heat and electricity conductive film, and a preparation method and an application thereof, polyvinyl alcohol is used as a substrate supporting material, liquid metal and heat conductive filler are respectively used as functional fillers for electricity and heat conduction, and the heat conductive filler is modified by polydopamine, so that hydrophilicity is improved, and uniform dispersion of the heat conductive filler in a mixed solution is facilitated. In the process of forming a film by water volatilization, liquid metal is settled to the lower layer to form a liquid metal droplet enrichment layer, the upper layer is a heat-conducting filler enrichment layer, so that a film with high heat conduction and electric conduction performance is formed, the surface of the liquid metal enrichment layer is wrapped by polyvinyl alcohol, therefore, the film is insulated on two sides at first, the liquid metal enrichment layer is exposed by scraping the polyvinyl alcohol on the surface, a conductive circuit can be formed, the liquid metal enrichment layer is connected into an electronic device, heat generated by the electronic device in the operation process can be rapidly dissipated out through the heat-conducting filler enrichment layer, and the heat dissipation effect is good.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a liquid metal-based heat and electricity conducting film is characterized by comprising the following steps:
mixing a heat-conducting filler with dopamine, and generating polydopamine on the surface of the heat-conducting filler to obtain a modified heat-conducting filler;
mixing the modified heat-conducting filler, the liquid metal and a polyvinyl alcohol aqueous solution to obtain a mixed solution;
and pouring the mixed solution into a mold, and volatilizing moisture to obtain the heat-conducting and electricity-conducting film with the upper layer as the heat-conducting filler and the lower layer as the liquid metal.
2. The method for preparing a liquid metal-based heat and electricity conductive film according to claim 1, wherein in the step of mixing the modified heat conductive filler, the liquid metal and the polyvinyl alcohol aqueous solution, the mass ratio of the modified heat conductive filler, the liquid metal and the polyvinyl alcohol is 5: 1-10: 1-10.
3. The method for preparing a liquid metal-based heat and electricity conductive film according to claim 1, wherein the heat conductive filler is one or more of hexagonal boron nitride, graphene and graphene oxide.
4. The method for preparing a liquid metal-based high thermal and electrical conductivity film according to claim 1, wherein the liquid metal is one or more of pure gallium, mercury, bismuth and alloys thereof.
5. The method for preparing a liquid metal-based heat and electricity conductive film according to claim 1, wherein the mass fraction of the polyvinyl alcohol in the aqueous solution of polyvinyl alcohol is 5-15%.
6. The method for preparing a liquid metal-based heat and electricity conductive film according to claim 1, wherein the step of mixing a heat conductive filler and dopamine to generate poly-dopamine on the surface of the heat conductive filler to obtain the modified heat conductive filler comprises the following steps:
mixing the heat-conducting filler and dopamine in deionized water, reacting under a preset condition, centrifuging after the reaction is finished, washing precipitates with the ionized water and absolute ethyl alcohol respectively, and drying the precipitates in vacuum to obtain the modified heat-conducting filler.
7. The method for preparing a liquid metal-based heat and electricity conductive film according to claim 6, wherein the heat conductive filler and dopamine are mixed in deionized water, a buffer is added to adjust the pH value to 8-9, and the mixture is reacted at 25 ℃ for 20-30 h.
8. The method for preparing a liquid metal-based heat and electricity conductive film according to claim 1, wherein the step of mixing the modified heat conductive filler, the liquid metal and the aqueous solution of polyvinyl alcohol comprises:
and mixing the modified heat-conducting filler, the liquid metal and the polyvinyl alcohol aqueous solution, and placing the mixture in a cell crusher for ultrasonic treatment for 50-70min to obtain a mixed solution.
9. A thermally and electrically conductive film, characterized by being produced by the production method as claimed in claims 1 to 8.
10. The application of a heat and electricity conductive film, characterized in that the enriched surface of the liquid metal of the electricity and heat conductive film as claimed in claim 9 is scraped to obtain a conductive circuit, which is applied to the preparation of electronic devices.
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| CN113077942A (en) * | 2021-04-12 | 2021-07-06 | 西北工业大学 | Intelligent flexible conductive film prepared based on power ultrasound and application thereof |
| CN114525002A (en) * | 2022-01-19 | 2022-05-24 | 中国科学院合肥物质科学研究院 | Liquid metal functional composite film and preparation method thereof |
| CN114525002B (en) * | 2022-01-19 | 2023-09-22 | 中国科学院合肥物质科学研究院 | Liquid metal functional composite film and preparation method thereof |
| CN117210712A (en) * | 2023-11-09 | 2023-12-12 | 成都先进金属材料产业技术研究院股份有限公司 | Liquid metal thermal interface composite material and preparation method thereof |
| CN117210712B (en) * | 2023-11-09 | 2024-02-02 | 成都先进金属材料产业技术研究院股份有限公司 | Liquid metal thermal interface composite material and preparation method thereof |
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