CN112055509A - Graphene heat dissipation film with uniform heat dissipation, and preparation method and application thereof - Google Patents
Graphene heat dissipation film with uniform heat dissipation, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene heat dissipation film with uniform heat dissipation, and a preparation method and application thereof, and belongs to the preparation of heat conduction materials. The method comprises six steps of graphene oxide aqueous solution preparation, carbon nanotube solution preparation, substrate cleaning, deposition of a graphene oxide film, primary drying, annealing treatment, deposition of carbon nano-tubes, secondary drying and annealing treatment. According to the invention, the acetylene black with different concentrations is coated on the surface of the base material through the thermal distribution diagram of the electronic element, and the density of the carbon nano tube adsorbed on the surface of the graphene oxide is controllable according to the adsorption strength of the acetylene black to the carbon nano tube. The heat of the electronic element can be directly exchanged with air or cooling liquid along the longitudinal direction of the graphene through the carbon nano tube, so that the heat accumulation is avoided, the difference of the surface temperature of the electronic element is reduced, and the efficiency of the electronic element is improved.
Description
Technical Field
The invention belongs to the field of heat conduction materials, and particularly relates to a graphene heat dissipation film with uniform heat dissipation, and a preparation method and application thereof.
Background
With the rapid development of various electronic products, the performance of electronic components has been rapidly developed, and the heat productivity of the electronic components is increased along with the improvement of the performance. For example: the high brightness of the display screen has higher requirements on the increase of the usage amount and the frequency of the light emitting diodes, the high-speed operation of the CPU, the consumption of the electric quantity of the battery is increased, the capacity of the battery is also increased, and the like. When the electronic element works at high speed, the electronic element consumes more energy, generates more heat more quickly and puts higher requirements on the heat dissipation element. If the heat cannot be dissipated in time, the service life of the equipment is shortened.
The heat dissipation capability of copper, aluminum and the alloy thereof is limited, the heat conductivity coefficient of pure copper is 398W/m ∙ K, and the heat conductivity coefficient of pure aluminum is 273W/m ∙ K, so the heat dissipation effect is not good. The graphene has extremely excellent electrical, mechanical and thermal properties, and has great potential in the field of heat dissipation. The existing graphene heat conduction film is basically of a two-dimensional layered structure, the heat conduction rate of each region on the same film is basically consistent, but the heat productivity of each microcircuit in the electronic element is inconsistent, and heat accumulation in a local region can be caused inevitably in the heat dissipation process, so that the load of the microcircuit in the region is overlarge, and the working efficiency of the electronic element is further influenced.
Disclosure of Invention
The purpose of the invention is as follows: the graphene heat dissipation film with uniform heat dissipation, the preparation method and the application thereof are provided to solve the problems involved in the background technology.
The technical scheme is as follows: a preparation method of a graphene heat dissipation film with uniform heat dissipation comprises the following steps:
step 1, preparing electrolyte: adding graphene oxide into deionized water, and uniformly dispersing under the action of ultrasonic waves to obtain a graphene oxide suspension liquid with the concentration of 0.25-2 g/L;
preparing a carbon nanotube solution, namely adding a carbon nanotube into a mixed solution of sodium carboxymethyl cellulose and absolute ethyl alcohol for ultrasonic dispersion to obtain the carbon nanotube solution with the concentration of 1.5-4.5 g/L;
step 2, cleaning the base material: cutting a non-metal substrate into a preset size, and then removing oil by using a cleaning agent and treating by using a roughening liquid to remove oxides and impurities on the surface of the substrate;
and 3, depositing a graphene oxide film: connecting the substrate serving as an anode with an electrophoresis apparatus power supply, and performing second electrophoretic deposition by using the graphene oxide suspension as electrolyte to form a layer of dark brown colloidal substance on the surface of the anode;
and 4, spraying acetylene black: spraying acetylene black solution with a predetermined amount of substance on a predetermined area of the surface of the dark brown colloidal substance;
step 5, primary drying and annealing treatment: putting the base material into a vacuum drying oven for drying, thereby obtaining a graphene oxide-base material composite film;
step 6, deposition of carbon nano-particles: connecting the graphene oxide-substrate composite film serving as an anode with an electrophoresis apparatus power supply, and performing second electrophoretic deposition by using a carbon nanotube solution as an electrolyte to form a layer of black colloidal substance on the surface of the anode;
step 7, primary drying and annealing treatment: and (3) putting the base material into a vacuum drying oven for drying, thereby obtaining the graphene oxide/carbon nanotube-base material composite film.
Preferably, the graphene oxide needs to be pretreated, and the pretreatment method comprises the following steps: adding 1g of natural flaky graphite powder into a mixed solution containing 0.5-1 g of concentrated sodium nitrate and 45-50 ml of concentrated sulfuric acid, then adding 6-9 g of potassium permanganate, fully stirring, then gradually adding a hydrogen peroxide solution to remove residual potassium permanganate, diluting, centrifuging, washing the obtained graphene oxide with a hydrochloric acid solution and deionized water, and placing the graphene oxide into an atmosphere furnace for vacuum drying.
Preferably, the base material is one of a sapphire substrate, a glass substrate, a silicon carbide substrate and a silicon/silicon dioxide substrate.
Preferably, the roughening liquid treatment process comprises the following steps: one side of the non-metal substrate is sealed by adopting a corrosion-resistant sealant, then the non-metal substrate is cleaned by using a hydrofluoric acid solution, and the non-metal substrate is soaked in a chromic anhydride coarsening solution for 24～After 48 hours, the surface of the mixture turns yellow, the mixture is baked for 30 to 60 minutes in a vacuum oven at the temperature of 105 to 130 ℃, and then is washed by deionized water,removing oxides and impurities on the surface of the base material, and finally preserving in a liquid seal manner in a benzotriazole water solution.
Preferably, the chromic anhydride coarsening liquid comprises: 5-10% of zinc powder, 4-8% of chromic anhydride, 2-4% of potassium ferricyanide, 0.5-2% of phosphoric acid, 1-2% of sodium fluoride, 0.5-1% of surfactant and the balance of water.
Preferably, the sealant is at least one of epoxy resin, polyvinyl fluoride and butyl rubber.
Preferably, the zinc powder is superfine zinc powder, and the particle size of the zinc powder is 2.5-10 mu m;
preferably, the first electrophoretic deposition process: the deposition voltage is 40-80V, the deposition time is 10-15 min, and the relative distance between the electrodes is 10-30 cm; the second electrophoretic deposition process comprises the following steps: the deposition voltage is 20-40V, the deposition time is 20-30 min, and the relative distance between the electrodes is 10-30 cm.
Preferably, in the spraying process of the acetylene black, the spraying amount of the acetylene black in different areas is proportional to the heat accumulation amount of the electronic component in the area.
Preferably, the first drying and annealing treatment comprises the following steps: keeping the air pressure in an atmosphere furnace at 15-20 MPa in a nitrogen protective atmosphere, heating to 300-350 ℃ at 20-25 ℃/min, preserving heat for 1-2 h, and then keeping the furnace temperature to decrease at 3-5 ℃/min until the room temperature; the second drying and annealing treatment comprises the following steps: and (3) keeping the air pressure in the atmosphere furnace at normal pressure in a nitrogen protective atmosphere, heating to 102-120 ℃, preserving the heat for 30-60 min, and naturally cooling to room temperature.
The invention also provides a substrate-graphene oxide composite film material prepared by the preparation method of the graphene heat dissipation film based on uniform heat dissipation.
The invention also provides an application of the substrate-graphene oxide composite film material as a substrate in preparing an electrical element, and the electrical element is prepared on the other side of the substrate-graphene oxide composite film material through gluing and etching.
Has the advantages that: the invention relates to a preparation method of a graphene heat dissipation film with uniform heat dissipation, which comprises the steps of forming a porous surface film on the surface of a non-metal substrate under the combined action of hydrofluoric acid, sodium fluoride and chromic anhydride, forming a chromium-zinc alloy film on the surface of one side of the substrate through mechanical meshing and intermolecular action, enabling the substrate to have excellent conductivity, then preparing a substrate-graphene oxide composite film by taking the substrate as an electrode through electrophoretic deposition, and forming nano spherical particles due to the shrinkage of zinc and chromium elements; the two-dimensional plane of the graphene can be fully utilized for phonon transmission, and the longitudinal thermal conductivity is improved in an increased mode. Through adsorbing the carbon nano tube on the surface of the graphene, as stronger hydrogen bonds and van der waals force interaction can be formed between the carbon nano tube and the graphene, a three-dimensional network structure is formed on the surface of the graphene oxide, the contact area of heat exchange of the heat dissipation film is increased, and the heat dissipation efficiency of the graphene heat dissipation film with uniform heat dissipation is further improved. Through electronic component's calorifics distribution diagram, the acetylene black of different concentrations of substrate surface coating, because acetylene black is different to carbon nanotube's adsorptivity intensity, the density that realizes the carbon nanotube of oxidation graphite alkene surface adsorption is controllable, and electronic component's heat can be directly vertically carry out the heat exchange through carbon nanometer and air or coolant liquid along graphite alkene, has avoided the heat to pile up, reduces electronic component surface temperature's differentiation, and then improves electronic component's efficiency.
Drawings
Fig. 1 is a cross-sectional SEM image of a graphene oxide thin film according to the present invention.
FIG. 2 is a sectional SEM image of a graphene oxide/carbon nanotube film according to the present invention.
FIG. 3 is a temperature step profile of an electronic component of example 7 of the present invention.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
Due to copper, aluminum and combination thereofGold has a limited heat dissipation capability, and pure copper has a thermal conductivity of 398W/m.K and pure aluminum has a thermal conductivity of 273W/m.K, so that the heat dissipation effect is not very good. The graphene has extremely excellent electrical, mechanical and thermal properties, and has great potential in the field of heat dissipation. However, in the prior art, the graphene composite material is generally directly bonded to a substrate to be used as a heat dissipation material. However, the graphene composite material and the substrate need to be connected through an adhesive, which is not favorable for longitudinal heat conduction of heat in the electronic component. According to the invention, a porous surface film is formed on the surface of a non-metal substrate under the combined action of sodium fluoride and chromic anhydride, then a chromium-zinc alloy film is formed on one side surface of the substrate through mechanical meshing and intermolecular action, so that the substrate has excellent conductivity, then the substrate is used as an electrode, oxygen-containing functional groups of graphene oxide can be removed through electrophoretic deposition, active free radicals are formed, and the active free radicals and Zn generated by anode electrolysis are subjected to reaction2+、Cr3+And combining, shortening the spacing between the composite film layers by a sintering process, further removing oxygen-containing functional groups, and simultaneously shrinking zinc and chromium elements to form nano-sphere particles to prepare the substrate-graphene oxide composite film. Due to intermolecular action and mechanical meshing force between the graphene oxide and the base material, the influence of the adhesive on the thermal conductivity is avoided, the two-dimensional plane of the graphene oxide can be fully utilized for phonon transmission, and the longitudinal thermal conductivity is improved greatly. And obtaining the final composite film.
In the research process of the applicant, the existing graphene heat-conducting film is basically of a two-dimensional layered structure, and when the graphene heat-conducting film exchanges with air or cooling liquid, the heat exchange surface is limited. Therefore, the applicant considers that the heat dissipation efficiency of the graphene film is improved by increasing the size of the heat exchange surface. According to the invention, the carbon nano tubes are adsorbed on the surface of the graphene, and a strong hydrogen bond and van der Waals force interaction can be formed between the carbon nano tubes and the graphene, so that a three-dimensional network structure is formed on the surface of the graphene oxide, the contact area of heat exchange of the heat dissipation film is increased, and the heat dissipation efficiency of the graphene heat dissipation film with uniform heat dissipation is greatly improved.
The invention provides a preparation method of a graphene heat dissipation film with uniform heat dissipation, which comprises the following steps: preparing a graphene oxide aqueous solution and a carbon nano tube solution, cleaning a base material, depositing a graphene oxide film, carrying out primary drying and annealing treatment, depositing carbon nano and carrying out secondary drying and annealing treatment.
Step 1, preparing electrolyte: preparing a graphene oxide aqueous solution, namely adding 1g of natural flaky graphite powder into a mixed solution containing 0.5-1 g of concentrated sodium nitrate and 45-50 ml of concentrated sulfuric acid, then adding 6-9 g of potassium permanganate, fully stirring, then gradually adding a hydrogen peroxide solution to remove residual potassium permanganate, diluting, centrifuging, washing the obtained graphene oxide with a hydrochloric acid solution and deionized water, and placing the graphene oxide in an atmosphere furnace for drying in vacuum. Adding graphene oxide into deionized water, and uniformly dispersing under the action of ultrasonic waves to obtain a graphene oxide suspension liquid with the concentration of 0.25-2 g/L.
And (3) preparing a carbon nanotube solution, namely adding the carbon nanotube into a mixed solution of sodium carboxymethyl cellulose and absolute ethyl alcohol for ultrasonic dispersion to obtain the carbon nanotube solution with the concentration of 1.5-4.5 g/L.
Step 2, cleaning the base material: cutting a non-metal substrate into a preset size, and then removing oil by using a cleaning agent and treating by using a roughening liquid to remove oxides and impurities on the surface of the substrate; the treatment process of the roughening solution comprises the following steps: one side of the non-metal substrate is sealed by adopting a corrosion-resistant sealant, then the non-metal substrate is cleaned by using a hydrofluoric acid solution, and the non-metal substrate is soaked in a chromic anhydride coarsening solution for 24～And (3) after 48 hours, baking the substrate in a vacuum oven at 105-130 ℃ for 30-60 min until the surface turns yellow, then cleaning the substrate by deionized water to remove oxides and impurities on the surface of the substrate, and finally storing the substrate in a benzotriazole water solution in a liquid seal manner. Wherein, the chromic anhydride coarsening liquid comprises: 5-10% of zinc powder, 4-8% of chromic anhydride, 2-4% of potassium ferricyanide, 0.5-2% of phosphoric acid, 1-2% of sodium fluoride, 0.5-1% of surfactant and the balance of water. The sealant is at least one of epoxy resin, polyvinyl fluoride and butyl rubber. The zinc powder is superfine zinc powder, and the particle size of the zinc powder is 2.5-10 mu m.
And 3, depositing a graphene oxide film: connecting the base material serving as an anode with an electrophoresis apparatus power supply, and performing first electrophoretic deposition by using a graphene oxide suspension as an electrolyte, wherein the deposition voltage in the first electrophoretic deposition process is 40-80V; the deposition time is 10-15 min, and the relative distance between the electrodes is 10-30 cm. A layer of dark brown gum was formed on the surface of the anode.
Step 4, primary drying and annealing treatment: removing the sealant on the surface of the substrate, and putting the substrate into a vacuum drying oven for drying, thereby obtaining the graphene oxide-substrate composite film. The first drying and annealing treatment comprises the following steps: raising the temperature to 300-350 ℃ at a speed of 20-25 ℃/min in a nitrogen protective atmosphere, preserving the temperature for 1-2 h, and then keeping the furnace temperature to be reduced at a speed of 3-5 ℃/min until the temperature reaches the room temperature. The drying and annealing conditions can enable the contact between the nano particles and the graphene to be tighter, and enable the contact between the composite material layers with the graphene multilayer structure to be tighter.
And 5, deposition of carbon nano-particles: connecting the graphene oxide-substrate composite film serving as an anode with a power supply of an electrophoresis apparatus, and performing second electrophoretic deposition by using a carbon nanotube solution as an electrolyte, wherein the second electrophoretic deposition process comprises the following steps: the deposition voltage is 20-40V, the deposition time is 20-30 min, and a layer of black colloidal substance is formed on the surface of the anode at the relative distance of 10-30 cm between the electrodes.
And 6, performing secondary drying and annealing treatment, and putting the substrate into a vacuum drying oven for drying, so as to obtain the graphene oxide/carbon nanotube-substrate composite film. The second drying and annealing treatment comprises the following steps: keeping the air pressure in the atmosphere furnace at normal pressure in the nitrogen protective atmosphere, heating to 110 ℃, preserving the heat for 45min, and then naturally cooling to room temperature.
In a further embodiment, after the step 3, 1.5-3 g/L acetylene black solution is sprayed on the surface of the dark brown colloidal substance, and then the step 4 is performed. The acetylene black is a carbon nano material with high conductivity, good stability and good adsorbability, and can be combined with the graphene oxide through the action of pi-pi bonds, so that the graphene oxide can be prevented from being agglomerated in the second electrophoretic deposition process. Meanwhile, due to the high conductivity of the acetylene black, more particles with positive charges are arranged on the surface of the acetylene black, the acetylene black has stronger adsorbability on carbon nano tubes than graphene oxide, more carbon nano tubes can be adsorbed on the surface of the acetylene black, the contact area of heat exchange of the heat dissipation film is increased, and the heat dissipation efficiency of the graphene heat dissipation film with uniform heat dissipation is further improved.
In a further embodiment, the acetylene black spraying is performed before the first drying and annealing treatment process, specifically: spraying acetylene black solution with a predetermined amount of substance on a predetermined area of the surface of the dark brown colloidal substance; in the acetylene black spraying process, the spraying amount of the acetylene black in different areas is in direct proportion to the heat accumulation amount of the electronic element in the area. Specifically, acetylene black with relevant concentration is determined according to a heat distribution diagram of the electronic element, so that the density of the carbon nano tube adsorbed on the surface of the graphene oxide is controllable, and the heat of the electronic element can be directly exchanged with air or cooling liquid through the carbon nano tube along the longitudinal direction of the graphene. The heat accumulation is avoided, the difference of the surface temperature of the electronic element is reduced, and the efficiency of the electronic element is improved.
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention.
Example 1
The preparation method of the graphene heat dissipation film with uniform heat dissipation comprises the following steps:
step 1, preparing a graphene oxide aqueous solution: adding 1g of natural flaky graphite powder into a mixed solution containing 0.8g of concentrated sodium nitrate and 47ml of concentrated sulfuric acid, then adding 8g of potassium permanganate, fully stirring, then gradually adding a hydrogen peroxide solution to remove residual potassium permanganate, diluting, centrifuging, washing the obtained graphene oxide with a hydrochloric acid solution and deionized water, and placing the graphene oxide into an atmosphere furnace for drying under vacuum. Adding graphene oxide into deionized water, and uniformly dispersing under the action of ultrasonic waves to obtain a graphene oxide suspension with the concentration of 1.0 g/L.
And (3) preparing a carbon nanotube solution, namely adding the carbon nanotube into a mixed solution of sodium carboxymethyl cellulose and absolute ethyl alcohol for ultrasonic dispersion to obtain the carbon nanotube solution with the concentration of 3.0 g/L.
Step 2, cleaning the base material: cutting a silicon substrate serving as a base material into a preset size, and then removing oil by using a cleaning agent and treating by using a roughening liquid to remove oxides and impurities on the surface of the base material; the treatment process of the roughening solution comprises the following steps: one side of the non-metal substrate is sealed by using a corrosion-resistant sealant, then the non-metal substrate is cleaned by using a hydrofluoric acid solution, the non-metal substrate is soaked in a chromic anhydride coarsening solution for 30 hours until the surface of the non-metal substrate becomes yellow, the non-metal substrate is baked for 45 minutes in a vacuum oven at the temperature of 120 ℃, then is cleaned by deionized water, oxides and impurities on the surface of the substrate are removed, and finally the non-metal substrate is stored in a benzotriazole aqueous solution in a liquid seal manner. Wherein, the chromic anhydride coarsening liquid comprises: 6% of zinc powder, 6% of chromic anhydride, 3% of potassium ferricyanide, 0.8% of phosphoric acid, 1.2% of sodium fluoride, 0.8% of surfactant and the balance of water. The sealant is at least one of epoxy resin, polyvinyl fluoride and butyl rubber. The zinc powder is superfine zinc powder, and the particle size of the zinc powder is 2.5-10 mu m;
and 3, depositing a graphene oxide film: connecting the base material serving as an anode with an electrophoresis apparatus power supply, and performing first electrophoretic deposition by using a graphene oxide suspension as an electrolyte, wherein the first deposition voltage is 60V; depositing for 20min, wherein the relative distance between the electrodes is 20cm, and a layer of dark brown colloidal substance is formed on the surface of the anode;
and 4, carrying out primary drying and annealing treatment, and putting the substrate into a vacuum drying oven for drying so as to obtain the graphene oxide-substrate composite film. Wherein the drying and annealing treatment comprises the following steps: raising the temperature to 320 ℃ at a speed of 20 ℃/min under the protection of nitrogen, preserving the temperature for 1.5h, and then keeping the furnace temperature to be reduced at a speed of 4 ℃/min until the temperature reaches the room temperature.
And 5, deposition of carbon nano-particles: connecting the graphene oxide-substrate composite film serving as an anode with a power supply of an electrophoresis apparatus, and performing second electrophoretic deposition by using a carbon nanotube solution as an electrolyte, wherein the second electrophoretic deposition process comprises the following steps: the deposition voltage is 25V, the deposition time is 10min, and the relative distance between the electrodes is 20cm, so that a layer of black colloidal substance is formed on the surface of the anode.
And 6, performing secondary drying and annealing treatment, and putting the substrate into a vacuum drying oven for drying, so as to obtain the graphene oxide/carbon nanotube-substrate composite film. The second drying and annealing treatment comprises the following steps: keeping the air pressure in the atmosphere furnace at normal pressure in the nitrogen protective atmosphere, heating to 110 ℃, preserving the heat for 45min, and then naturally cooling to room temperature.
Example 2
The preparation method of the graphene heat dissipation film with uniform heat dissipation comprises the following steps:
step 1, preparing a graphene oxide aqueous solution: adding 1g of natural flaky graphite powder into a mixed solution containing 0.8g of concentrated sodium nitrate and 47ml of concentrated sulfuric acid, then adding 8g of potassium permanganate, fully stirring, then gradually adding a hydrogen peroxide solution to remove residual potassium permanganate, diluting, centrifuging, washing the obtained graphene oxide with a hydrochloric acid solution and deionized water, and placing the graphene oxide into an atmosphere furnace for drying under vacuum. Adding graphene oxide into deionized water, and uniformly dispersing under the action of ultrasonic waves to obtain a graphene oxide suspension liquid with the concentration of 0.25 g/L.
And (3) preparing a carbon nanotube solution, namely adding the carbon nanotube into a mixed solution of sodium carboxymethyl cellulose and absolute ethyl alcohol for ultrasonic dispersion to obtain the carbon nanotube solution with the concentration of 1.5 g/L.
Step 2, cleaning the base material: cutting a silicon substrate serving as a base material into a preset size, and then removing oil by using a cleaning agent and treating by using a roughening liquid to remove oxides and impurities on the surface of the base material; the treatment process of the roughening solution comprises the following steps: one side of the non-metal substrate is sealed by using a corrosion-resistant sealant, then the non-metal substrate is cleaned by using a hydrofluoric acid solution, the non-metal substrate is soaked in a chromic anhydride coarsening solution for 48 hours until the surface of the non-metal substrate becomes yellow, the non-metal substrate is baked for 30 minutes in a vacuum oven at the temperature of 130 ℃, then is cleaned by deionized water, oxides and impurities on the surface of the substrate are removed, and finally the non-metal substrate is stored in a benzotriazole aqueous solution in a liquid seal manner. Wherein, the chromic anhydride coarsening liquid comprises: 10% of zinc powder, 8% of chromic anhydride, 4% of potassium ferricyanide, 2% of phosphoric acid, 1% of sodium fluoride, 1% of surfactant and the balance of water. The sealant is at least one of epoxy resin, polyvinyl fluoride and butyl rubber. The zinc powder is superfine zinc powder, and the particle size of the zinc powder is 2.5-10 mu m;
and 3, depositing a graphene oxide film: connecting the base material serving as an anode with a power supply of an electrophoresis apparatus, and carrying out electrophoretic deposition by using the graphene oxide suspension as electrolyte, wherein the deposition voltage is 80V; depositing for 15min, wherein the relative distance between the electrodes is 10cm, and a layer of dark brown colloidal substance is formed on the surface of the anode;
and 4, carrying out primary drying and annealing treatment, and putting the substrate into a vacuum drying oven for drying so as to obtain the graphene oxide-substrate composite film. Wherein the first drying and annealing treatment comprises the following steps: raising the temperature to 320 ℃ at a speed of 20 ℃/min under the protection of nitrogen, preserving the temperature for 1.5h, and then keeping the furnace temperature to be reduced at a speed of 4 ℃/min until the temperature reaches the room temperature.
And 5, deposition of carbon nano-particles: connecting the graphene oxide-substrate composite film serving as an anode with a power supply of an electrophoresis apparatus, and performing second electrophoretic deposition by using a carbon nanotube solution as an electrolyte, wherein the second electrophoretic deposition process comprises the following steps: the deposition voltage is 20V, the deposition time is 30min, the relative distance between the electrodes is 10cm, and a layer of black colloidal substance is formed on the surface of the anode.
And 6, performing secondary drying and annealing treatment, and putting the substrate into a vacuum drying oven for drying, so as to obtain the graphene oxide/carbon nanotube-substrate composite film. Wherein the second drying and annealing treatment comprises the following steps: keeping the air pressure in the atmosphere furnace at normal pressure in the nitrogen protective atmosphere, heating to 102 ℃, preserving the heat for 60min, and then naturally cooling to room temperature.
Example 3
The preparation method of the graphene heat dissipation film with uniform heat dissipation comprises the following steps:
step 1, preparing a graphene oxide aqueous solution: adding 1g of natural flaky graphite powder into a mixed solution containing 0.8g of concentrated sodium nitrate and 47ml of concentrated sulfuric acid, then adding 8g of potassium permanganate, fully stirring, then gradually adding a hydrogen peroxide solution to remove residual potassium permanganate, diluting, centrifuging, washing the obtained graphene oxide with a hydrochloric acid solution and deionized water, and placing the graphene oxide into an atmosphere furnace for drying under vacuum. Adding graphene oxide into deionized water, and uniformly dispersing under the action of ultrasonic waves to obtain a graphene oxide suspension liquid with the concentration of 2 g/L.
And (3) preparing a carbon nanotube solution, namely adding the carbon nanotube into a mixed solution of sodium carboxymethyl cellulose and absolute ethyl alcohol for ultrasonic dispersion to obtain the carbon nanotube solution with the concentration of 4.5 g/L.
Step 2, cleaning the base material: cutting a silicon substrate serving as a base material into a preset size, and then removing oil by using a cleaning agent and treating by using a roughening liquid to remove oxides and impurities on the surface of the base material; the treatment process of the roughening solution comprises the following steps: one side of the non-metal substrate is sealed by using a corrosion-resistant sealant, then the non-metal substrate is cleaned by using a hydrofluoric acid solution, the non-metal substrate is soaked in a chromic anhydride coarsening solution for 24 hours until the surface of the non-metal substrate becomes yellow, the non-metal substrate is baked for 60 minutes in a vacuum oven at the temperature of 105 ℃, then is cleaned by deionized water, oxides and impurities on the surface of the substrate are removed, and finally the non-metal substrate is stored in a benzotriazole aqueous solution in a liquid seal manner. Wherein, the chromic anhydride coarsening liquid comprises: 5% of zinc powder, 4% of chromic anhydride, 2% of potassium ferricyanide, 0.5% of phosphoric acid, 2% of sodium fluoride, 0.5% of surfactant and the balance of water. The sealant is at least one of epoxy resin, polyvinyl fluoride and butyl rubber. The zinc powder is superfine zinc powder, and the particle size of the zinc powder is 2.5-10 mu m;
and 3, depositing a graphene oxide film: connecting the base material serving as an anode with a power supply of an electrophoresis apparatus, and carrying out electrophoretic deposition by using the graphene oxide suspension as electrolyte, wherein the deposition voltage is 40V; depositing for 10min, wherein the relative distance between the electrodes is 10cm, and a layer of dark brown colloidal substance is formed on the surface of the anode;
and 4, carrying out primary drying and annealing treatment, and putting the substrate into a vacuum drying oven for drying so as to obtain the graphene oxide-substrate composite film. Wherein the first drying and annealing treatment comprises the following steps: raising the temperature to 320 ℃ at a speed of 20 ℃/min under the protection of nitrogen, preserving the temperature for 1.5h, and then keeping the furnace temperature to be reduced at a speed of 4 ℃/min until the temperature reaches the room temperature.
And 5, deposition of carbon nano-particles: connecting the graphene oxide-substrate composite film serving as an anode with a power supply of an electrophoresis apparatus, and performing second electrophoretic deposition by using a carbon nanotube solution as an electrolyte, wherein the second electrophoretic deposition process comprises the following steps: the deposition voltage is 40V, the deposition time is 20min, and the relative distance between the electrodes is 30cm, so that a layer of black colloidal substances is formed on the surface of the anode.
And 6, performing secondary drying and annealing treatment, and putting the substrate into a vacuum drying oven for drying, so as to obtain the graphene oxide/carbon nanotube-substrate composite film. The second drying and annealing treatment comprises the following steps: keeping the air pressure in the atmosphere furnace at normal pressure in the nitrogen protective atmosphere, heating to 120 ℃, preserving the heat for 30min, and then naturally cooling to room temperature.
Example 4
The amount of carbon nanotubes adsorbed by the acetylene black solution was examined in addition to example 1, and was different from example 1 in that: in a further embodiment, after step 3, a 2.4g/L acetylene black solution is sprayed on the surface of the dark brown gum, and then step 4 is performed. The rest of the procedure and materials were the same as in example 1.
Example 5
The amount of carbon nanotubes adsorbed by the acetylene black solution was examined in addition to example 1, and was different from example 1 in that: in a further embodiment, after step 3, a 1.5g/L acetylene black solution is sprayed on the surface of the dark brown gum, and then step 4 is performed. The rest of the procedure and materials were the same as in example 1.
Example 6
The amount of carbon nanotubes adsorbed by the acetylene black solution was examined in addition to example 1, and was different from example 1 in that: in a further embodiment, after step 3, a 3.5g/L acetylene black solution is sprayed on the surface of the dark brown gum, and then step 4 is performed. The rest of the procedure and materials were the same as in example 1.
Example 7
The amount of carbon nanotubes adsorbed by the acetylene black solution was examined in addition to example 1, and was different from example 1 in that: obtaining a model diagram of an electronic component to be processed through simulation software ANSYS, and calculating and simulating a temperature step distribution diagram of the electronic component, as shown in FIG. 3, and spraying acetylene black solution with a predetermined amount of substance on a predetermined area of the surface of the dark brown colloidal substance after the step 3 based on the temperature step distribution diagram; wherein the spraying amount of the acetylene black at different areas of the substrate is proportional to the temperature of the electronic component at the area. Step 4 is then performed. The remaining steps and materials were the same as in example 1.
Example 8
On the basis of the embodiment 1, only the previous steps 1 to 4 are performed to obtain the graphene oxide-substrate composite film, and the rest steps and materials are the same as the embodiment 1.
Example of detection
The relevant parameters of the composite film obtained in the above example are detected, and the specific experimental data are as follows:
from the above table, it can be seen that the thermal conductivity of the graphene oxide/carbon nanotube-substrate composite films in embodiments 1 to 4 is improved by one step compared to that of a single silicon substrate, and the graphene oxide/carbon nanotube-substrate composite films also have a certain improvement compared to that of the graphene oxide-substrate composite films, and have stronger mechanical strength.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (10)
1. The preparation method of the graphene heat dissipation film with uniform heat dissipation is characterized by comprising the following steps:
step 1, preparing electrolyte: adding graphene oxide into deionized water, and uniformly dispersing under the action of ultrasonic waves to obtain a graphene oxide suspension liquid with the concentration of 0.25-2 g/L;
preparing a carbon nanotube solution, namely adding a carbon nanotube into a mixed solution of sodium carboxymethyl cellulose and absolute ethyl alcohol for ultrasonic dispersion to obtain the carbon nanotube solution with the concentration of 1.5-4.5 g/L;
step 2, cleaning the base material: cutting a non-metal substrate into a preset size, and then removing oil by using a cleaning agent and treating by using a roughening liquid to remove oxides and impurities on the surface of the substrate;
and 3, depositing a graphene oxide film: connecting the substrate serving as an anode with an electrophoresis apparatus power supply, and performing second electrophoretic deposition by using the graphene oxide suspension as electrolyte to form a layer of dark brown colloidal substance on the surface of the anode;
and 4, spraying acetylene black: spraying acetylene black solution with a predetermined amount of substance on a predetermined area of the surface of the dark brown colloidal substance;
step 5, primary drying and annealing treatment: putting the base material into a vacuum drying oven for drying, thereby obtaining a graphene oxide-base material composite film;
step 6, deposition of carbon nano-particles: connecting the graphene oxide-substrate composite film serving as an anode with an electrophoresis apparatus power supply, and performing second electrophoretic deposition by using a carbon nanotube solution as an electrolyte to form a layer of black colloidal substance on the surface of the anode;
step 7, primary drying and annealing treatment: and (3) putting the base material into a vacuum drying oven for drying, thereby obtaining the graphene oxide/carbon nanotube-base material composite film.
2. The preparation method of the graphene heat dissipation film with uniform heat dissipation according to claim 1, wherein the graphene oxide needs to be pretreated, and the treatment method comprises the following steps: adding 1g of natural flaky graphite powder into a mixed solution containing 0.5-1 g of concentrated sodium nitrate and 45-50 ml of concentrated sulfuric acid, then adding 6-9 g of potassium permanganate, fully stirring, then gradually adding a hydrogen peroxide solution to remove residual potassium permanganate, diluting, centrifuging, washing the obtained graphene oxide with a hydrochloric acid solution and deionized water, and placing the graphene oxide into an atmosphere furnace for vacuum drying.
3. The method for preparing the graphene heat dissipation film with uniform heat dissipation according to claim 1, wherein the base material is one of a sapphire substrate, a glass substrate, a silicon carbide substrate and a silicon/silicon dioxide substrate.
4. The preparation method of the graphene heat dissipation film with uniform heat dissipation according to claim 3, wherein the roughening solution treatment process comprises the following steps: one side of the non-metal substrate is sealed by adopting a corrosion-resistant sealant, then the non-metal substrate is cleaned by using a hydrofluoric acid solution, and the non-metal substrate is soaked in a chromic anhydride coarsening solution for 24～And (3) after 48 hours, baking the substrate in a vacuum oven at 105-130 ℃ for 30-60 min until the surface turns yellow, then cleaning the substrate by deionized water to remove oxides and impurities on the surface of the substrate, and finally storing the substrate in a benzotriazole water solution in a liquid seal manner.
5. The method for preparing the graphene heat dissipation film with uniform heat dissipation according to claim 4, wherein the chromic anhydride roughening solution comprises: the chromic anhydride coarsening liquid comprises: 5-10% of zinc powder, 4-8% of chromic anhydride, 2-4% of potassium ferricyanide, 0.5-2% of phosphoric acid, 1-2% of sodium fluoride, 0.5-1% of surfactant and the balance of water.
6. The method for preparing the graphene heat dissipation film with uniform heat dissipation according to claim 1, wherein the first electrophoretic deposition process comprises: the deposition voltage is 40-80V, the deposition time is 10-15 min, and the relative distance between the electrodes is 10-30 cm;
the second electrophoretic deposition process comprises the following steps: the deposition voltage is 20-40V, the deposition time is 20-30 min, and the relative distance between the electrodes is 10-30 cm.
7. The method for preparing a graphene heat dissipation film with uniform heat dissipation according to claim 1, wherein in the spraying process of the acetylene black, the spraying amount of the acetylene black in different areas is directly proportional to the heat accumulation amount of the electronic component in the area.
8. The method for preparing the graphene heat dissipation film with uniform heat dissipation according to claim 1, wherein the carbon nanotubes are carboxylated multiwalled carbon nanotubes.
9. The substrate-graphene oxide composite thin film material is obtained based on the preparation method of the graphene heat dissipation film with uniform heat dissipation as defined in any one of claims 1-8.
10. The application of the substrate-graphene oxide composite film material as a substrate in preparing an electrical element is characterized in that the electrical element is prepared on the other side of the substrate-graphene oxide composite film material through gluing and etching.
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| CN113437033B (en) * | 2021-06-28 | 2022-07-15 | 珠海格力电器股份有限公司 | Packaging structure, preparation method thereof and electronic device |
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