CN113604100B - Graphene/copper/micron particle composite material, preparation method thereof, graphene high-temperature heating ink and application - Google Patents
Graphene/copper/micron particle composite material, preparation method thereof, graphene high-temperature heating ink and application Download PDFInfo
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Abstract
The invention provides a graphene/copper/micron particle composite material, a preparation method thereof, graphene high-temperature heating ink and application, wherein the graphene/copper/micron particle composite material comprises micron particles, a copper simple substance and graphene, the copper simple substance covers part or all of the surface of the micron particles, and the graphene covers the outer surface of the copper simple substance and/or the surface of the micron particles; the coverage thickness of the copper simple substance is 2-5 μm, and the coverage thickness of the graphene is 1-3 layers; according to the invention, graphene grows on the surface of copper/micron particles by using a CVD method, so that the obtained graphene/copper/micron particle composite material is coated on the surface of copper to prevent the graphene monomer from agglomerating, the resistivity of the prepared graphene high-temperature heating ink in a test can reach 0.001 omega cm, and the graphene high-temperature heating ink has the advantages of good electrical conductivity, easiness in dispersion, high addition and the like, can resist the temperature of 500-700 ℃, has good thermal conductivity and high-temperature stability, and can be used under the high-temperature condition for a long time.
Description
Technical Field
The invention belongs to the field of electric heating materials, particularly relates to graphene high-temperature heating ink, and particularly relates to a graphene/copper/micron particle composite material and a preparation method thereof, and graphene high-temperature heating ink and application thereof.
Background
The graphene is formed by carbon atoms sp 2 The two-dimensional crystal material with a honeycomb structure formed by covalent bond connection in a hybrid mode has the advantages of large specific surface area, excellent mechanical property, high electrical conductivity, high thermal conductivity coefficient and the like, and the graphene is used as a cleaning ringThe green energy source is kept, the mainstream of energy conservation and environmental protection in the world is met, and the research on the fact that the graphene heating ink becomes a hot topic in the field of electric heating materials is carried out.
After the graphene is electrified, under the action of an electric field, carbon molecular groups in the graphene generate Brownian motion, violent friction and impact are generated among carbon molecules, and the generated heat energy is transferred outwards in the modes of far infrared radiation, convection and the like by virtue of the efficient heat transfer characteristic of the graphene, so that heat conduction is realized. The existing graphene heating ink mainly has two types of high temperature and low temperature, and the graphene high-temperature heating ink is generally applied to the aspects of electronics, electric appliances, military affairs and the like. The pi-pi bond bonding force of graphene is strong, dispersed single graphene is easy to agglomerate under the action of pi-pi bonds, graphene in the graphene high-temperature heating coating prepared in the prior art is easy to agglomerate, different dispersing agents are generally added or oxide or metal particles are generally added in order to block agglomeration among the graphene, although the agglomeration of the graphene is relieved to a certain extent, the obtained graphene high-temperature heating ink is low in electric conductivity and thermal conductivity, poor in high-temperature stability and easy to generate the power attenuation problem after long-term use.
Disclosure of Invention
The invention provides a graphene/copper/micron particle composite material, a preparation method thereof, graphene high-temperature heating ink and application, and aims to solve the problems that the existing graphene high-temperature heating ink is low in electric conductivity and thermal conductivity, poor in high-temperature stability and easy to generate power attenuation after being used for a long time.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a graphene/copper/microparticle composite material, which comprises microparticles, a copper simple substance and graphene, wherein the copper simple substance covers part or all of the surface of the microparticles, and the graphene covers the outer surface of the copper simple substance.
Optionally, the coverage thickness of the copper simple substance is 2-5 μm, and the coverage thickness of the graphene is 1-3 layers.
Optionally, the micro-particles include micro-tablets and/or microspheres, the particle size of the microspheres is 1-50 μm, the long diameter of the micro-tablets is 20-50 μm, and the short diameter of the micro-tablets is 1-20 μm.
Optionally, the microparticles are selected from one or more of alumina, silica, boron nitride and silicon carbide.
On the other hand, the invention provides a preparation method of a graphene/copper/micron particle composite material, which comprises the following steps:
(1) Obtaining a copper sulfate solution; uniformly dispersing the micron particles into a copper sulfate solution;
(2) Taking out, drying and heating the micron particles with the surface adsorbed with the solid copper sulfate to obtain micron particles with the surface adsorbed with copper oxide;
(3) Heating the micron particles with the surfaces adsorbing the copper oxide in a reducing gas atmosphere to obtain micron particles with surfaces adsorbing copper simple substances;
(4) Heating the micron particles with the surface adsorbed with the copper simple substance in a reducing gas atmosphere and/or a protective gas atmosphere, then introducing a carbon source gas, and generating graphene on the surface to obtain the graphene/copper/micron particle composite material.
Optionally, in the step (1), the mass fraction of the copper sulfate solution is 1-30%;
optionally, in the step (2), the heating temperature is 650-800 ℃, and the heat preservation time is 30-40min;
optionally, in the step (3), the heating temperature is 200-220 ℃, and the heating time is 1-2h;
optionally, in the step (4), the micrometer particles with the surface adsorbed with the copper simple substance are heated in a reducing gas atmosphere and/or a protective gas atmosphere, the heating temperature is 1050 ℃, and the heat preservation time is 15-20min.
Optionally, the reducing gas comprises hydrogen; the flow rate of the reducing gas flow is 100-400sccm;
optionally, the carbon source gas comprises methane; the flow rate of the carbon source gas flow is 100-800sccm;
optionally, the protective gas comprises argon.
On the other hand, the invention provides graphene high-temperature heating ink which comprises the graphene/copper/micron particle composite material prepared by the preparation method or the graphene/copper/micron particle composite material prepared by the preparation method, and the graphene/copper/micron particle composite material comprises the following components in parts by weight: 2-60 parts of graphene/copper/micron particle composite material, 20-95 parts of organic silicon resin, 10-50 parts of diluent, 0.01-0.1 part of defoaming agent, 0.1-1 part of flatting agent and 0.1-1 part of dispersing agent.
On the other hand, the invention provides an application of the graphene high-temperature heating ink, which comprises the graphene high-temperature heating ink, wherein the graphene high-temperature heating ink is applied to high-temperature heating bodies for electronic cigarette lighters, kettles, baking trays, heaters and electric ceramic furnaces; high-temperature heating plates for industrial ovens and tunnel furnaces, and high-temperature heating bodies for high-temperature heating tubes.
The invention has the beneficial effects that:
1. according to the graphene/copper/micron particle composite material provided by the invention, micron particles capable of resisting a higher-temperature material are introduced as an adhesion matrix of graphene, the graphene/copper/micron particle composite material is not decomposed under a high-temperature condition, the temperature resistance of the prepared graphene high-temperature heating ink can reach 500-700 ℃, and the graphene high-temperature heating ink has good thermal conductivity and high-temperature stability and can be used under the high-temperature condition for a long time.
2. According to the graphene/copper/micron particle composite material provided by the invention, copper/graphene grows on the surface of micron particles, the agglomeration of graphene monomers is prevented, the content of graphene growing on the surface of copper simple substance can be effectively controlled through the content of generated copper simple substance, and the prepared graphene high-temperature heating ink has the advantage of high graphene addition.
3. According to the graphene high-temperature heating ink prepared by the invention, the added graphene/copper/micron particle composite material has no introduction of other impurity particles, the micron particles effectively prevent the graphene in the heating ink from agglomerating, and the resistivity of the prepared graphene high-temperature heating ink in a test can reach 0.001 omega cm, so that the graphene high-temperature heating ink has excellent effects of good conductivity and easiness in dispersion.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a graphene/copper/micron particle composite material, which comprises micron particles, a copper simple substance and graphene; the elementary copper is covered on part or all of the surface of the micron particles, and the graphene is covered on the outer surface of the elementary copper.
In some embodiments, the micron particles capable of resisting a higher temperature material are introduced to serve as an attachment matrix of graphene, the micron particles are not decomposed under a high temperature condition, the micron particles and graphene and copper simple substances act together, and the prepared graphene high-temperature heating ink can resist high temperature. In some embodiments, the prepared graphene high-temperature heating ink is coated on a high-temperature heating plate, and the high-temperature heating plate can be electrified for 3000 hours at 550-600 ℃ without power attenuation. Under the combined action of the introduced micron particles, graphene and copper simple substances, the prepared high-temperature heating ink has the temperature resistance of 500-700 ℃, has good thermal conductivity and high-temperature stability, and can be used under the high-temperature condition for a long time.
In some embodiments, the copper simple substance covers part of or all of the surface of the micrometer particles, the graphene covers the outer surface of the copper simple substance, the agglomeration of the graphene simple substance in the graphene high-temperature heating ink can be effectively prevented, no other impurity particles are introduced, the resistivity of the prepared graphene high-temperature heating ink in a test can reach 0.001 omega cm, and the prepared graphene high-temperature heating ink has the excellent effects of good conductivity and easy dispersion. Graphene is easier to grow on the outer surface of the copper simple substance, the content of graphene growing on the surface of the copper simple substance can be effectively controlled through the content of the generated copper simple substance, and the prepared graphene high-temperature heating ink has the advantage of high addition of graphene.
The copper simple substance covers part or all of the surface of the micron particles, and the covering thickness of the copper simple substance is 2-5 mu m; the graphene covers the outer surface of the copper simple substance, and the covering thickness of the graphene is 1-3 layers.
In some embodiments, the coverage thickness of the copper simple substance is less than 2 microns, the coverage thickness is small, graphene is not easy to grow on the copper simple substance, the content of the graphene is small, and the heat conduction and the electric conduction performance of the graphene high-temperature heating ink are affected. The coverage thickness of the copper simple substance is larger than 5 microns, more graphene grows on the surface of the copper simple substance, and when the produced graphene/copper/micron particle composite material is dispersed into resin, the high-temperature heating ink is easy to have uneven dispersing agent due to more graphene content, so that the characteristic of the high-temperature heating ink is reduced.
In some embodiments, the coverage thickness of the graphene is higher than the above range, the content of the graphene is large, the graphene is not easily dispersed in the resin, the prepared ink is not uniformly dispersed, and the content of the graphene is too large to be easily agglomerated. The coverage thickness of the graphene is lower than the range value, the content of the graphene is less, and the electric conduction and heat conduction performance of the prepared high-temperature heating ink is reduced.
The micrometer particles comprise micro-tablets and/or microspheres, the particle size of the microspheres is 1-50 μm, the long diameter of the micro-tablets is 20-50 μm, and the short diameter of the micro-tablets is 1-20 μm. The microparticles may be selected from the group consisting of microplatelets, microparticles may also be selected from the group consisting of microspheres alone, and microparticles may also be both microplatelets and microspheres.
In some embodiments, the microspheres provided by the present invention have a particle size of 1-50 μm, the long diameter of the micro-slabs is 20-50 μm, and the short diameter of the micro-slabs is 1-20 μm. If the particle size of the microspheres is less than 1 mu m or the size of the micro-tablets is less than the range, the particle size or the length and the length are small, and the microspheres are easy to agglomerate; if the particle size is larger than 50 micrometers or the size of the micro-sheet is larger than the range, the particle size or the length-diameter and the short-diameter are too large, the prepared graphene/copper/micrometer particle composite material is not easy to be uniformly dispersed into resin, and the conductivity of the ink is reduced.
The micron particles provided by the invention are selected from one or more of alumina, silicon dioxide, boron nitride and silicon carbide, and the micron particles are required to be micro-sheets and micro-spheres with high-temperature resistance. In some embodiments, the micro-pieces and microspheres provided by the present invention include alumina micro-pieces and microspheres, silica micro-pieces and microspheres, boron nitride micro-pieces and microspheres, and silicon carbide micro-pieces and microspheres, which are high temperature resistant, but are not limited to the above micro-pieces and microspheres. According to the invention, graphene is produced on the high-temperature resistant microchip and microsphere to prepare the graphene/copper/micron particle composite material, so that the graphene monomer can be prevented from agglomerating, the graphene is more easily dispersed into resin, no other impurities are introduced, the resistivity of the prepared graphene high-temperature heating ink can reach 0.001 omega cm at the lowest, and the prepared graphene high-temperature heating ink has excellent conductivity.
The invention provides a preparation method of a graphene/copper/micron particle composite material, which comprises the following steps:
(1) Obtaining a copper sulfate solution; dispersing the micron particles into a copper sulfate solution;
(2) Taking out the micro-particles, and drying the copper sulfate solution on the surface to obtain the micro-particles with solid copper sulfate adsorbed on the surface; heating the micron particles with the surface adsorbed with the solid copper sulfate at 650-800 ℃, and keeping the temperature for 30-40min to obtain the micron particles with the surface adsorbed with the copper oxide;
(3) Heating the micron particles with the surface adsorbed with the copper oxide in a reducing gas atmosphere at the temperature of 200-220 ℃, preferably 205-215 ℃ for 1-2h; micron particles with copper simple substances adsorbed on the surfaces are obtained. The reducing gas is preferably hydrogen gas, wherein the flow rate of the hydrogen gas is 100-400sccm.
(4) The micron particles with the surface adsorbed with the copper simple substance are placed into a CVD tubular furnace and heated in a reducing gas atmosphere and/or a protective gas atmosphere, wherein the preferable reducing gas is hydrogen, and the protective gas is argon; heating in hydrogen or argon environment, wherein the flow rate of hydrogen is 100-400sccm, the temperature rise rate is 10-30 ℃/min, the temperature is raised to 1050 ℃, and the temperature is kept for 15-20min; and then introducing a carbon source gas, preferably selecting the carbon source gas as methane gas, keeping the methane flow rate at 100-800sccm for 30min, cooling to room temperature at the cooling speed of 20-30 ℃/min, and generating graphene on the surface to obtain the graphene/copper/micron particle composite material.
In some embodiments, in step (1), the copper sulfate solution has a mass fraction of 1% to 30%.
If the mass fraction of the copper sulfate solution is higher than 30 percent, the content of copper sulfate is too large, the solution becomes anhydrous copper sulfate, and the copper sulfate can not be better adsorbed on the surfaces of the micro-tablets and the micro-spheres; if the mass fraction of the copper sulfate solution is lower than 1%, the content of copper sulfate in the copper sulfate solution is too low, copper sulfate adsorbed on the surfaces of the micro-sheet and the micro-sphere is reduced, copper simple substances generated by copper sulfate cannot be formed to be better and completely coated on the surfaces of the micro-sheet and the micro-sphere, the proportion of generated graphene is reduced, and the electrical conductivity and the thermal conductivity of the prepared graphene high-temperature heating ink are reduced.
The copper sulfate solution has the mass fraction of 1-30%, copper sulfate is easier to adsorb on the surfaces of the micro-sheets and the microspheres, copper sulfate prepared by the method can better and completely coat the micro-sheets and the microspheres, graphene with a proper proportion can be better grown on the surface of the copper simple substance, the copper sulfate solution with the mass fraction can generate graphene with a higher content, the graphene addition amount in the prepared graphene high-temperature heating ink is high, and the improvement of the electrical conductivity and the thermal conductivity of the graphene high-temperature heating ink is more facilitated.
In some embodiments, in the steps (3) and (4), the flow rate of the hydrogen gas is 200-300sccm; in the step (4), the flow rate of the methane is 400-600sccm.
The flow rate of hydrogen is 200-300sccm, and the flow rate of methane is 400-600sccm; the flow rates of hydrogen and methane gas are in the range, the hydrogen is sufficient, the production of the copper simple substance can be more facilitated, and the flow rate of the methane gas is in the range, so that the condition of generating sufficient graphene can be achieved. When the hydrogen flow rate is more than 400sccm, the copper simple substance generated by the copper oxide reaction does not increase with the increase of the hydrogen flow rate; when the flow rate of the methane is more than 800sccm, the content of the generated graphene is not increased any more; the method controls the flow rates of the hydrogen and the methane within a certain range, so that the content of the generated graphene can be achieved, and the cost can be saved.
In some embodiments, the microparticles are selected from one or more of alumina, silica, boron nitride, and silicon carbide; the micrometer particles comprise microspheres and/or micro-tablets, the particle size of the microspheres is 1-50 μm, the long diameter of the micro-tablets is 20-50 μm, and the short diameter of the micro-tablets is 1-20 μm.
In another embodiment of the invention, the graphene high-temperature heating ink provided by the invention comprises the following components in parts by weight: 2-60 parts of graphene/copper/micron particle composite material, 20-95 parts of organic silicon resin, 10-50 parts of diluent, 0.01-0.1 part of defoaming agent, 0.1-1 part of flatting agent and 0.1-1 part of dispersing agent.
In some embodiments, the silicone resin comprises one or more of methyl silicone, methyl phenyl silicone, phenyl silicone; the defoaming agent comprises one or more of mineral oil, organic silicon and polyether; the diluent comprises one or more of dimethylbenzene, methylbenzene, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, acetone, n-butanol, methyl isobutyl ketone, absolute ethyl alcohol, ethyl acetate, butyl acetate, chlorobenzene, dichlorobenzene, dichloromethane, acetonitrile, pyridine, phenol and the like; the flatting agent comprises one or more of acrylic acid, organic silicon and fluorocarbon; the dispersant comprises one or more of fatty acids, fatty amides, esters, paraffin and metal soaps.
The resin is selected from organic silicon resin, the organic silicon resin is a framework formed by alternately connecting silicon atomic nucleus oxygen atoms, contains organic groups and inorganic groups, and can better bond inorganic substances and organic substances together, so that the graphene/copper/micron particle composite material can be more easily and uniformly dispersed in the organic silicon resin, more stable and uniform graphene high-temperature heating ink is formed, and the bonding force between the ink and a base material is enhanced. The diluent is mainly used for adjusting the viscosity of the ink and adjusting the high-temperature heating ink of the graphene to be favorable for coating the ink on the surface of the base material. The dispersing agent mainly has the effects of reducing the content of the graphene/copper/micron particle composite material, better dispersing the graphene/copper/micron particle composite material into mixed solution such as resin and the like, enhancing the stability of the ink and reducing the precipitation. The defoaming agent is mainly used for inhibiting the generation of bubbles, accelerating the breaking of the generated bubbles, eliminating the bubbles generated in the stirring process of the graphene high-temperature heating ink and realizing the beautiful coating effect; the leveling agent is mainly used for eliminating the defects of shrinkage cavity and the like of an ink coating, so that the coating is smooth and flat, the coating effect is attractive, and the coating characteristic is enhanced.
In another embodiment of the present invention, the present invention provides a method for preparing graphene high-temperature heating ink, including the following steps:
a) Weighing 2-60 parts of graphene/copper/micron particle composite material and 10-50 parts of diluent, adding into a high-speed dispersion machine, adjusting the rotating speed to 800-1200r/min, and dispersing for 20-30min to obtain dispersion A;
b) Weighing 0.1-1 part of flatting agent, 0.01-0.1 part of defoaming agent and 0.1-1 part of dispersing agent, sequentially adding the flatting agent, the defoaming agent and the dispersing agent into the dispersion liquid A prepared in the step a), and adjusting the rotating speed to be 600-800r/min and the dispersing time to be 20-30min to obtain a dispersion liquid B;
c) Weighing 20-95 parts of organic silicon resin, adding into the dispersion liquid B prepared in the step B), adjusting the rotating speed to 300-500r/min, and dispersing for 30-40min to prepare the graphene high-temperature ink.
In some embodiments, according to the preparation method of the graphene high-temperature heating ink provided by the invention, the graphene/copper/micron particle composite material and the diluent are added into a high-speed dispersion machine for high-speed dispersion, and mainly because the graphene completely grows on the surfaces of copper/micron particle microspheres and micro-sheets and covers the surfaces of the copper/micron particle microspheres and the micro-sheets, the diluent is added for dilution, so that the graphene/copper/micron particle composite material containing high-content graphene can be prevented from being agglomerated; the setting range of the dispersion rotating speed is 800-1200r/min, so that the graphene/copper/micron particle composite material can be better dispersed into a diluent, and the graphene can be well adsorbed on the surfaces of copper/micron particle microspheres and micro-sheets. If the dispersion rotating speed is higher than a set range value, the graphene is easy to desorb; if the dispersion rotating speed is lower than the set range value, the graphene aggregation phenomenon is easy to occur due to the high graphene content on the surfaces of the copper/micron particle microspheres and the micro-sheets.
In another embodiment of the invention, the invention provides an application of the graphene high-temperature heating ink, which comprises the graphene high-temperature heating ink obtained by the preparation method, and the graphene high-temperature heating ink is applied to high-temperature heating bodies for electronic cigarette lighters, kettles, baking trays, heaters and electric ceramic furnaces and appliances; high-temperature heating plates for industrial ovens and tunnel furnaces, and high-temperature heating bodies for high-temperature heating tubes.
Through a large number of experiments, the inventor finds that graphene in the graphene high-temperature heating ink in the prior art is easy to agglomerate, in order to prevent the graphene from agglomerating, the inventor finds that graphene growing on a micron particle can prevent the graphene from agglomerating, and because the graphene can grow on a copper simple substance, the inventor provides a graphene/copper/micron particle composite material which can prevent the graphene from agglomerating and can also grow enough graphene on the surface of the copper simple substance, the addition amount of the graphene in the prepared graphene high-temperature heating ink can be adjusted according to actual requirements, and the method is simple and easy to realize. According to the preparation method of the graphene/copper/micron particle composite material, the graphene is grown on the surfaces of copper/micron particle micro-sheets and micro-spheres by using a CVD method, so that the obtained graphene/copper/micron particle composite material is coated on the surface of copper/oxide, the agglomeration of graphene monomers is hindered, other impurity particles are not introduced, and the prepared graphene high-temperature heating ink has the advantages of low resistivity, good conductivity, easiness in dispersion, high addition and the like, and the resistivity can reach 0.001 omega cm; the microchip and the microsphere which can resist higher temperature are introduced, the decomposition is avoided under the high-temperature condition, the temperature resistance of the prepared graphene high-temperature heating ink can reach 500-700 ℃, the graphene high-temperature heating ink has good thermal conductivity and high-temperature stability, and the graphene high-temperature heating ink can be used under the high-temperature condition for a long time. When the working temperature of the graphene high-temperature heating plate coated with the graphene high-temperature heating ink prepared by the invention is 550-600 ℃, continuous power-on test is carried out for 3000 hours, and the power of the heating plate is not attenuated.
The present invention will be further described below with reference to the following examples.
Example 1 preparation of graphene/copper/microparticle composites
(1) Obtaining a copper sulfate solution with the mass fraction of 5%; uniformly dispersing 10-micron-size alumina microspheres, 20-micron-size alumina micro-tablets, 15-micron-size silicon dioxide microspheres, 10-micron-size boron nitride microspheres and 10-micron-size silicon carbide microspheres into a copper sulfate solution with the mass fraction of 5%.
(2) Taking out alumina microspheres with the particle size of 10 microns, alumina micro-tablets with the long diameter of 20 microns and the short diameter of 5 microns, silica micro-microspheres with the particle size of 15 microns, boron nitride micro-microspheres with the particle size of 10 microns and silicon carbide micro-microspheres with the particle size of 10 microns, and drying copper sulfate solution on the surface to obtain alumina micro-tablets, alumina micro-microspheres, silica micro-microspheres, boron nitride micro-microspheres and silicon carbide micro-microspheres with the surfaces adsorbing solid copper sulfate; and heating the alumina micro-tablets, the micro-spheres, the silica micro-spheres, the boron nitride micro-spheres and the silicon carbide micro-spheres with the surfaces adsorbing the solid copper sulfate at 650 ℃, and keeping the temperature for 30min to obtain the alumina micro-tablets, the micro-spheres, the silica micro-spheres, the boron nitride micro-spheres and the silicon carbide micro-spheres with the surfaces adsorbing the copper oxide.
(3) And heating the surface-adsorbed alumina micro-tablets, micro-spheres, silicon dioxide micro-spheres, boron nitride micro-spheres and silicon carbide micro-spheres to 200 ℃ in a hydrogen atmosphere for 1h, wherein the flow rate of hydrogen is 150sccm, so as to obtain the alumina micro-tablets, micro-spheres, silicon dioxide micro-spheres, boron nitride micro-spheres and silicon carbide micro-spheres with the surface-adsorbed copper simple substance.
(4) Putting an alumina microchip, a microsphere, a silicon dioxide microsphere, a boron nitride microsphere and a silicon carbide microsphere with surfaces adsorbing copper simple substances into a CVD (chemical vapor deposition) tube furnace, heating in a hydrogen environment, wherein the flow rate of hydrogen is 150sccm, the temperature rise rate is 10 ℃/min, the temperature is increased to 1050 ℃, the temperature is kept for 15min, then introducing methane gas, the flow rate of methane is 200sccm, the temperature is kept for 30min, then cooling, the temperature reduction rate is 20 ℃/min, cooling to room temperature, and generating graphene on the surfaces to obtain the graphene/copper/micron particle composite material.
Example 2 preparation of graphene/copper/microparticle composites
(1) Obtaining a copper sulfate solution with the mass fraction of 28%; alumina microspheres with the grain size of 10 microns, alumina micro-tablets with the long diameter of 20 microns and the short diameter of 5 microns, silicon dioxide microspheres with the grain size of 15 microns and boron nitride microspheres with the grain size of 10 microns are uniformly dispersed into copper sulfate solution with the mass fraction of 28%.
(2) Taking out alumina microspheres with the particle size of 10 microns, alumina micro-tablets with the long diameter of 20 microns and the short diameter of 5 microns, silica micro-microspheres with the particle size of 15 microns and boron nitride microspheres with the particle size of 10 microns, and drying copper sulfate solution on the surface to obtain alumina micro-tablets, alumina micro-microspheres, silica micro-microspheres, boron nitride micro-microspheres and silicon carbide micro-microspheres with solid copper sulfate adsorbed on the surface; and heating the alumina micro-tablets and micro-spheres, the silicon dioxide micro-spheres, the boron nitride micro-spheres and the silicon carbide micro-spheres with the surfaces adsorbing the solid copper sulfate at the heating temperature of 750 ℃, and keeping the temperature for 40min to obtain the alumina micro-tablets and micro-spheres, the silicon dioxide micro-spheres, the boron nitride micro-spheres and the silicon carbide micro-spheres with the surfaces adsorbing the copper oxide.
(3) And heating the aluminum oxide micro-sheets, the micro-spheres, the silicon dioxide micro-spheres, the boron nitride micro-spheres and the silicon carbide micro-spheres with the surfaces adsorbing copper oxide to 210 ℃ in a hydrogen atmosphere for 1.5h, wherein the flow rate of hydrogen is 300sccm, so as to obtain the aluminum oxide micro-sheets, the micro-spheres, the silicon dioxide micro-spheres, the boron nitride micro-spheres and the silicon carbide micro-spheres with the surfaces adsorbing copper simple substances.
(4) Putting the aluminum oxide micro-sheet, the micro-sphere, the silicon dioxide micro-sphere, the boron nitride micro-sphere and the silicon carbide micro-sphere with the surface adsorbing the copper simple substance into a CVD (chemical vapor deposition) tube furnace, heating in a hydrogen environment, wherein the flow rate of hydrogen is 350sccm, the temperature rise rate is 20 ℃/min, the temperature is increased to 1050 ℃, the temperature is kept for 20min, then introducing methane gas, the flow rate of methane is 600sccm, the temperature is kept for 30min, then cooling is carried out, the temperature reduction rate is 25 ℃/min, the temperature is reduced to room temperature, and graphene is generated on the surfaces of the aluminum oxide micro-sheet, the micro-sphere, the silicon dioxide micro-sphere, the boron nitride micro-sphere and the silicon carbide micro-sphere, so that the graphene/copper/micron particle composite material is obtained.
Example 3 preparation of graphene/copper/microparticle composites
(1) Obtaining a copper sulfate solution with the mass fraction of 28%; uniformly dispersing alumina microspheres with the particle size of 40 microns, silicon dioxide micro-tablets with the long diameter of 45 microns and the short diameter of 15 microns, boron nitride microspheres with the particle size of 40 microns and silicon carbide micro-tablets with the long diameter of 50 microns and the short diameter of 20 microns into a copper sulfate solution with the mass fraction of 28%.
(2) Taking out alumina microspheres with the particle size of 40 microns, silica micro-tablets with the long diameter of 45 microns and the short diameter of 15 microns, boron nitride microspheres with the particle size of 40 microns and silicon carbide micro-tablets with the long diameter of 50 microns and the short diameter of 20 microns, and drying copper sulfate solution on the surface to obtain alumina microspheres, silica micro-tablets, microspheres, boron nitride microspheres and silicon carbide micro-tablets with the surface adsorbing solid copper sulfate; and heating the alumina microspheres, the silica micro-tablets and the microspheres, the boron nitride microspheres and the silicon carbide micro-tablets with the surfaces adsorbing the solid copper sulfate at 800 ℃, and keeping the temperature for 40min to obtain the alumina microspheres, the silica micro-tablets and the microspheres, the boron nitride microspheres and the silicon carbide micro-tablets with the surfaces adsorbing the copper oxide.
(3) And heating the alumina microspheres, the silicon dioxide micro-tablets, the microspheres, the boron nitride microspheres and the silicon carbide micro-tablets with the surfaces adsorbing copper oxide to 200 ℃ in a hydrogen atmosphere for 2h, wherein the flow rate of hydrogen is 400sccm, so as to obtain the alumina microspheres, the silicon dioxide micro-tablets, the microspheres, the boron nitride microspheres and the silicon carbide micro-tablets with the surfaces adsorbing copper simple substances.
(4) Placing the alumina microspheres, the silicon dioxide micro-tablets, the microspheres, the boron nitride microspheres and the silicon carbide micro-tablets with the surfaces adsorbing the copper simple substance into a CVD (chemical vapor deposition) tube furnace, heating in a hydrogen environment, wherein the flow rate of hydrogen is 400sccm, the temperature rise speed is 30 ℃/min, the temperature is raised to 1050 ℃, keeping the temperature for 20min, then introducing methane gas, the flow rate of methane is 800sccm, keeping the temperature for 30min, then cooling, the temperature drop speed is 30 ℃/min, cooling to room temperature, and generating graphene on the surfaces of the alumina microspheres, the silicon dioxide micro-tablets, the microspheres and the boron nitride microspheres and the silicon carbide micro-tablets to obtain the graphene/copper/micron particle composite material.
Example 4 preparation of graphene high-temperature exothermic ink
a) Weighing 20 parts of the graphene/copper/micron particle composite material prepared in the embodiment 1 and 40 parts of diluent xylene, adding the materials into a high-speed dispersion machine, adjusting the rotating speed to be 800r/min, and dispersing for 20min to obtain a dispersion liquid A;
b) Weighing 0.1 part of acrylic flatting agent, 0.05 part of mineral oil defoaming agent and 0.1 part of fatty acid dispersing agent, sequentially adding the components into the dispersion liquid A prepared in the step a), and adjusting the rotating speed to 600r/min and the dispersing time to 20min to obtain a dispersion liquid B;
c) Weighing 39.8 parts of methyl silicone resin, adding into the dispersion liquid B prepared in the step B), adjusting the rotating speed to 300r/min, and dispersing for 30min to prepare the graphene high-temperature ink.
Example 5 preparation of graphene high temperature exothermic ink
a) Weighing 35 parts of the graphene/copper/micron particle composite material prepared in the embodiment 1 and 40 parts of diluent toluene, adding the materials into a high-speed dispersion machine, adjusting the rotating speed to be 800r/min, and dispersing for 20min to obtain a dispersion liquid A;
b) Weighing 0.1 part of acrylic flatting agent, 0.05 part of mineral oil defoaming agent and 0.1 part of paraffin dispersant, sequentially adding the components into the dispersion liquid A prepared in the step a), and adjusting the rotating speed to 600r/min and the dispersion time to 20min to obtain a dispersion liquid B;
c) Weighing 24.8 parts of methyl silicone resin, adding into the dispersion liquid B prepared in the step B), adjusting the rotating speed to 300r/min, and dispersing for 30min to prepare the graphene high-temperature ink.
Example 6 preparation of graphene high temperature exothermic ink
a) Weighing 20 parts of the graphene/copper/micron particle composite material prepared in the embodiment 2 and 40 parts of methyl isobutyl ketone serving as a diluent, adding the materials into a high-speed dispersion machine, and adjusting the rotating speed to 800r/min and the dispersion time to 20min to obtain a dispersion liquid A;
b) Weighing 0.1 part of organic silicon flatting agent, 0.05 part of organic silicon defoaming agent and 0.1 part of fatty acid dispersing agent, sequentially adding the organic silicon flatting agent, the organic silicon defoaming agent and the fatty acid dispersing agent into the dispersion liquid A prepared in the step a), and adjusting the rotating speed to 600r/min and the dispersing time to 20min to obtain a dispersion liquid B;
c) Weighing 39.8 parts of methyl silicone resin, adding the methyl silicone resin into the dispersion liquid B prepared in the step B), and adjusting the rotation speed to 300r/min and the dispersion time to 30min to prepare the graphene high-temperature ink.
Example 7 preparation of graphene high temperature exothermic ink
a) Weighing 20 parts of the graphene/copper/micron particle composite material prepared in the embodiment 2 and 60 parts of diluent ethyl acetate, adding the materials into a high-speed dispersion machine, adjusting the rotating speed to be 800r/min, and dispersing for 20min to obtain a dispersion liquid A;
b) Weighing 0.1 part of acrylic flatting agent, 0.05 part of mineral oil defoaming agent and 0.1 part of ester dispersing agent, sequentially adding the components into the dispersion liquid A prepared in the step a), and adjusting the rotating speed to 600r/min and the dispersing time to 20min to obtain a dispersion liquid B;
c) Weighing 19.8 parts of methyl phenyl silicone resin, adding into the dispersion liquid B prepared in the step B), adjusting the rotating speed to 300r/min, and dispersing for 30min to prepare the graphene high-temperature ink.
Example 8 preparation of graphene high temperature exothermic ink
a) Weighing 20 parts of the graphene/copper/micron particle composite material prepared in the embodiment 3 and 40 parts of diluent 1,4-butanediol diglycidyl ether, adding the materials into a high-speed dispersion machine, adjusting the rotating speed to 800r/min, and dispersing for 20min to obtain dispersion liquid A;
b) Weighing 0.1 part of organic silicon flatting agent, 0.05 part of polyether defoamer and 0.1 part of aliphatic amide dispersant, sequentially adding the materials into the dispersion liquid A prepared in the step a), and adjusting the rotating speed to 600r/min for 20min to obtain a dispersion liquid B;
c) Weighing 39.8 parts of methyl phenyl silicone resin, adding into the dispersion liquid B prepared in the step B), adjusting the rotating speed to 300r/min, and dispersing for 30min to prepare the graphene high-temperature ink.
Example 9 preparation of graphene high temperature exothermic ink
a) Weighing 20 parts of the graphene/copper/micron particle composite material prepared in the embodiment 2 and 20 parts of diluent dichloromethane, adding into a high-speed dispersion machine, adjusting the rotating speed to 800r/min, and dispersing for 20min to obtain a dispersion liquid A;
b) Weighing 0.1 part of organic silicon flatting agent, 0.05 part of polyether defoaming agent and 0.1 part of aliphatic amide dispersing agent, sequentially adding the organic silicon flatting agent, the polyether defoaming agent and the aliphatic amide dispersing agent into the dispersion liquid A prepared in the step a), and adjusting the rotating speed to 600r/min and the dispersing time to 20min to obtain a dispersion liquid B;
c) 59.8 parts of methyl phenyl silicone resin is weighed and added into the dispersion liquid B prepared in the step B), the rotating speed is adjusted to 300r/min, the dispersion time is 30min, and the graphene high-temperature ink is prepared.
Example 10 preparation of graphene high temperature exothermic ink
a) Weighing 40 parts of the graphene/copper/micron particle composite material prepared in the embodiment 3 and 10 parts of butyl acetate serving as a diluent, adding the materials into a high-speed dispersion machine, adjusting the rotating speed to be 800r/min, and dispersing for 20min to obtain a dispersion liquid A;
b) Weighing 0.1 part of fluorocarbon leveling agent, 0.1 part of polyether defoaming agent and 0.1 part of ester dispersing agent, sequentially adding the fluorocarbon leveling agent, the polyether defoaming agent and the ester dispersing agent into the dispersion liquid A prepared in the step a), and adjusting the rotating speed to 600r/min and the dispersing time to 20min to obtain a dispersion liquid B;
c) Weighing 49.7 parts of phenyl silicone resin, adding the phenyl silicone resin into the dispersion liquid B prepared in the step B), adjusting the rotating speed to 300r/min, and dispersing for 30min to prepare the graphene high-temperature ink.
Comparative example 1
Preparation of graphene high-temperature heating ink
a) Weighing 20 parts of graphene and 20 parts of diluent 1,4-butanediol diglycidyl ether, adding into a high-speed dispersion machine, adjusting the rotating speed to 800r/min, and dispersing for 20min to obtain dispersion A;
b) Weighing 0.1 part of organic silicon flatting agent, 0.05 part of polyether defoaming agent and 0.1 part of aliphatic amide dispersing agent, sequentially adding the organic silicon flatting agent, the polyether defoaming agent and the aliphatic amide dispersing agent into the dispersion liquid A prepared in the step a), and adjusting the rotating speed to 600r/min and the dispersing time to 20min to obtain a dispersion liquid B;
c) Weighing 59.8 parts of methyl phenyl silicone resin, adding into the dispersion liquid B prepared in the step B), adjusting the rotating speed to 300r/min, and dispersing for 30min to prepare the graphene high-temperature ink.
Comparative example 2
a) Weighing 20 parts of graphene, 50 parts of alumina and 10 parts of a diluent 1,4-butanediol diglycidyl ether, adding the mixture into a high-speed dispersion machine, adjusting the rotating speed to 800r/min, and dispersing for 20min to obtain a dispersion liquid A;
b) Weighing 0.1 part of organic silicon flatting agent, 0.05 part of polyether defoaming agent and 0.1 part of aliphatic amide dispersing agent, sequentially adding the organic silicon flatting agent, the polyether defoaming agent and the aliphatic amide dispersing agent into the dispersion liquid A prepared in the step a), and adjusting the rotating speed to 600r/min and the dispersing time to 20min to obtain a dispersion liquid B;
c) Weighing 17.8 parts of methyl phenyl silicone resin, adding into the dispersion liquid B prepared in the step B), adjusting the rotating speed to 300r/min, and dispersing for 30min to prepare the graphene high-temperature ink.
Table 1 graphene high temperature heating ink performance test data table
According to the performance test results of the high-temperature heating ink in table 1, it can be seen that in examples 4 to 7, as the content of the graphene/copper/micron particle composite material increases, the resistivity group of the prepared graphene high-temperature heating ink decreases, and the highest use temperature shows a descending trend in a certain range. In examples 6 and 8, the diameter of the micrometer particles or the length and the length of the micrometer particles become larger, and the resistivity of the prepared graphene high-temperature heating ink also tends to be reduced. The resistivity of the high-temperature heat-generating graphene inks prepared in comparative examples 1 and 2 is more than 1.0, the maximum service temperature is 350 ℃ at most, and compared with comparative examples 1 and 2, the resistivity of the high-temperature heat-generating graphene inks prepared in the examples 4 to 10 is reduced by at least 0.8 ohm-cm, and the maximum service temperature is increased by at least 150 ℃. As can be seen from Table 1, compared with comparative examples 1-2, the electric conductivity, the thermal conductivity and the high temperature resistance of the graphene high-temperature heating ink prepared by the invention are greatly improved.
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 (8)
1. The graphene/copper/microparticle composite material is characterized by comprising microparticles, a copper simple substance and graphene, wherein the copper simple substance covers part or all of the surface of the microparticles, and the graphene covers the outer surface of the copper simple substance;
the coverage thickness of the copper simple substance is 2-5 μm, and the coverage thickness of the graphene is 1-3 layers;
the micrometer particles comprise micro-tablets and/or microspheres, the particle size of the microspheres is 1-50 μm, the long diameter of the micro-tablets is 20-50 μm, and the short diameter of the micro-tablets is 1-20 μm;
the preparation method of covering the copper simple substance on the partial or whole surface of the micron particles comprises the following steps:
(1) Obtaining a copper sulfate solution; uniformly dispersing the micron particles into a copper sulfate solution;
(2) Taking out, drying and heating the micron particles with the surface adsorbed with the solid copper sulfate to obtain micron particles with the surface adsorbed with copper oxide;
(3) And heating the micron particles with the surfaces adsorbing the copper oxide in a reducing gas atmosphere to obtain the micron particles with the surfaces adsorbing the copper simple substance.
2. The graphene/copper/microparticle composite material as claimed in claim 1, wherein the microparticles are selected from one or more of alumina, silica, boron nitride and silicon carbide.
3. The method for preparing the graphene/copper/micron particle composite material according to any one of claims 1-2, wherein the method comprises the following steps:
(1) Obtaining a copper sulfate solution; uniformly dispersing the micron particles into a copper sulfate solution;
(2) Taking out, drying and heating the micron particles with the surface adsorbed with the solid copper sulfate to obtain micron particles with the surface adsorbed with copper oxide;
(3) Heating the micron particles with the surfaces adsorbing the copper oxide in a reducing gas atmosphere to obtain micron particles with surfaces adsorbing copper simple substances;
(4) Heating the micron particles with the surface adsorbed with the copper simple substance in a reducing gas atmosphere and/or a protective gas atmosphere, then introducing a carbon source gas, and generating graphene on the surface to obtain the graphene/copper/micron particle composite material.
4. The preparation method of the graphene/copper/micron particle composite material as claimed in claim 3, wherein in the step (1), the mass fraction of the copper sulfate solution is 1% -30%.
5. The preparation method of the graphene/copper/micron particle composite material as claimed in claim 3, wherein in the step (2), the heating temperature is 650-800 ℃, and the holding time is 30-40min; in the step (3), the heating temperature is 200-220 ℃, and the heating time is 1-2h; in the step (4), the micron particles with the surface adsorbed with the copper simple substance are heated in a reducing gas atmosphere and/or a protective gas atmosphere, the heating temperature is 1050 ℃, and the heat preservation time is 15-20min.
6. The method for preparing the graphene/copper/micron particle composite material according to claim 3,
the reducing gas comprises hydrogen; the flow rate of the reducing gas flow is 100-400sccm;
the carbon source gas comprises methane; the flow rate of the carbon source gas flow is 100-800sccm;
the protective gas comprises argon.
7. The graphene high-temperature heating ink is characterized in that: the graphene/copper/micron particle composite material prepared by the preparation method of any one of claims 3 to 6 or the graphene/copper/micron particle composite material of any one of claims 1 to 2 comprises the following components in parts by weight: 2-60 parts of graphene/copper/micron particle composite material, 20-95 parts of organic silicon resin, 10-50 parts of diluent, 0.01-0.1 part of defoaming agent, 0.1-1 part of flatting agent and 0.1-1 part of dispersing agent.
8. The application of the graphene high-temperature heating ink is characterized in that: the graphene high-temperature heating ink is applied to high-temperature heating bodies for electronic cigarette lighters, kettles, baking trays, heaters and electric ceramic furnaces and the like; high-temperature heating plates for industrial ovens and tunnel furnaces, and high-temperature heating bodies for high-temperature heating tubes.
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