CN108658615B - High-thermal-conductivity graphene-based composite film and preparation method thereof - Google Patents
High-thermal-conductivity graphene-based composite film and preparation method thereof Download PDFInfo
- Publication number
- CN108658615B CN108658615B CN201810612571.9A CN201810612571A CN108658615B CN 108658615 B CN108658615 B CN 108658615B CN 201810612571 A CN201810612571 A CN 201810612571A CN 108658615 B CN108658615 B CN 108658615B
- Authority
- CN
- China
- Prior art keywords
- based composite
- composite film
- graphene
- graphene oxide
- dispersion liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/522—Graphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/652—Reduction treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Abstract
The invention discloses a high-thermal-conductivity graphene-based composite film and a preparation method thereof. The graphene-based composite film comprises the following raw materials in percentage by mass: 40-70% of graphene oxide, 30-60% of a stabilizer, 1-3% of a surfactant and 1-10% of a reinforcing agent; during preparation, the graphene oxide dispersion liquid, the stabilizer, the surfactant and the enhancer dispersion liquid are mixed, ultrasonically treated and uniformly stirred to obtain the graphene oxide-based composite dispersion liquid, a graphene oxide-based composite film is obtained by using a solution film forming method, and finally the graphene oxide-based composite film is obtained by a secondary hot-pressing reduction process. The thickness of the graphene-based composite film is 10-50 microns and is controllable, and the room-temperature heat conductivity coefficient is 800-‑1k‑1The tensile strength can reach 10-30MPa, and the 180-degree bending is free from damage.
Description
Technical Field
The invention relates to a heat-conducting composite material, in particular to a light, flexible and high-heat-conducting graphene-based composite material and a preparation method thereof, which are used in the fields of high-power and high-heat-flow-density electronic industry and heat dissipation of electronic devices of intelligent equipment.
Background
With the increasing miniaturization of electronic devices and the increasing power density of components, the interest in advanced materials with fast and high thermal conductivity has increased tremendously. Although the traditional metal material has good flexibility, the traditional metal material has high density and low thermal conductivity, and can not meet the requirements of people. Therefore, non-metallic materials have become a focus of research. Although the thermal conductivity coefficient of the high-quality graphite and diamond film can reach 2000W m-1k-1However, the severe production conditions and high production costs limit their large-scale application. Furthermore, raw graphite blocks cannot be used directly in the electronics industry due to their low thermal conductivity, fragility and tendency to dusting.
Graphene, a novel two-dimensional material, with good thermal conductivity and mechanical propertiesExcellent mechanical performance, acid and alkali resistance and other excellent performances. The thermal conductivity of the suspended single-layer graphene at room temperature is as high as 5300W m-1k-1Far exceeds graphite and diamond, and is the material with the highest heat conductivity coefficient known at present. The direct application of graphene is often used as an additive to enhance the properties of a substrate material, such as thermal conductivity, electrical conductivity, mechanical properties, and the like, which cannot fully exert the excellent properties of graphene. A graphene thin film, which is one of macroscopic materials of graphene, is receiving wide attention by virtue of high thermal conductivity, electrical conductivity, and mechanical properties. The current preparation method of graphene-based film material generally comprises the steps of firstly forming a film from graphene oxide (or graphene nanosheet), then carrying out high-temperature (2000->800Wm-1k-1) And a film material with certain mechanical properties. The process has obvious defects, such as high energy consumption and incompatibility with the trend of energy conservation and emission reduction; the operation conditions are harsh, and the realization difficulty of the ultrahigh temperature and the ultrahigh pressure is high; high production cost, low economic benefit of the product and the like. Therefore, it is a development trend to research and develop a production process for preparing graphene-based thin film materials with high thermal conductivity and good mechanical properties under low temperature and low pressure conditions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a heat conduction coefficient of 800-1600W m at room temperature- 1k-1The high-thermal-conductivity graphene-based composite film with tensile strength of 10-30MPa and no damage after 180-degree bending and the preparation method thereof have a series of advantages of low preparation process temperature, low pressure, simple operation, low energy consumption, low cost and the like.
The purpose of the invention is realized by the following technical scheme:
the utility model provides a high heat conduction graphite alkene base composite film which characterized in that: the graphene-based composite film comprises the following raw materials in percentage by mass: 40-70% of graphene oxide, 30-60% of a stabilizer, 1-3% of a surfactant and 1-10% of a reinforcing agent; the mass ratio of the solid raw material to the liquid dispersant is 1-10: 1000;
adding the graphene oxide into the graphene oxide dispersion liquid;
the stabilizer is one or a mixture of more of nano cellulose, xylitol, glucose and sorbitol;
the surfactant is one or the mixture of two of dodecyl benzene sulfonic acid and dodecyl glucoside;
the reinforcing agent is added in the form of carbon nano tube and/or carbon fiber dispersion liquid;
the thickness of the graphene-based composite film is 10-50 microns and is controllable, and the room-temperature heat conductivity coefficient is 800-1600Wm-1k-1The tensile strength is 10-30MPa, and the 180-degree bending is not damaged.
In order to further achieve the object of the present invention, preferably, the graphene oxide dispersion liquid uses water as a solvent, and the concentration of the graphene oxide dispersion liquid is 1.0-8.0mg ml-1The product is stably stored for more than 6 months without sediment; the carbon nano tube and/or carbon fiber dispersion liquid takes absolute ethyl alcohol as a solvent, and the concentration is 0.5-1.5mg ml-1。
Preferably, the graphene oxide dispersion is prepared by a modified Hummers method, comprising the steps of:
1) pre-oxidation: dispersing graphite powder, potassium persulfate and phosphorus pentoxide in concentrated sulfuric acid, carrying out condensation reflux reaction for 5-8 hours in a water bath at 75-85 ℃, cooling to room temperature, adding deionized water for dilution, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and drying to obtain pre-oxidized graphite;
2) reoxidation: mixing the pre-oxidized graphite and concentrated sulfuric acid, slowly adding potassium permanganate under the conditions of ice water bath and stirring, ensuring that the temperature of the mixture is not more than 20 ℃, then heating to 30-40 ℃ for reaction for 1-4 hours, adding deionized water for dilution, stirring at room temperature for 1-2 hours, and then dropwise adding hydrogen peroxide to remove residual potassium permanganate to obtain the bright yellow oxidized graphite suspension.
3) Washing and dispersing: standing and layering the graphite oxide suspension, pouring out supernatant, and dropwise adding dilute hydrochloric acid into the graphite oxide precipitate; and standing, layering, pouring out supernatant, adding dilute hydrochloric acid into the precipitate, repeatedly washing, adding deionized water into the last graphite oxide precipitate, centrifuging, pouring out centrifugal supernatant, adding deionized water into the rest graphite oxide precipitate, ultrasonically dispersing for 2-4 hours, then filling into a dialysis bag, and dialyzing for several days in deionized water until sulfate ions are not detected in the dialyzed deionized water and the pH value is 6.5-7.0 to obtain the graphene oxide dispersion liquid.
Preferably, the mass ratio of the graphite powder to the potassium persulfate to the phosphorus pentoxide is 1:0.5-0.7: 0.5-0.7; the mass ratio of the pre-oxidized graphite to the concentrated sulfuric acid to the potassium permanganate is 1:55-73: 3-5.
Preferably, the molar concentration of the concentrated sulfuric acid is 15-18mol L-1The molar concentration of the dilute hydrochloric acid is 2.5-3.0mol L-1。
Preferably, the drying temperature is 100-110 ℃; the repeated washing times are 4-6 times; the rotation speed of the centrifugal treatment is 4000-6000rpm, and the time is 15-30 minutes.
Preferably, the carbon nano tube is a high-thermal-conductivity multi-wall carbon nano tube with the outer diameter of less than 10 nanometers, the length of 5-15 micrometers and the purity of more than 97 percent; the carbon fiber is carbon fiber powder with the carbon content of more than 95 percent, the mesh number of 300-200 and the maximum length of 50-74 microns.
The preparation method of the high-thermal-conductivity graphene-based composite film comprises the following steps: mixing the graphene oxide dispersion liquid, the stabilizer, the surfactant and the reinforcing agent dispersion liquid, performing ultrasonic treatment and stirring uniformly to obtain a graphene oxide-based composite dispersion liquid, obtaining a graphene oxide-based composite film by using a solution film-forming method, and finally obtaining the graphene-based composite film by a secondary hot-pressing reduction process; the secondary hot-pressing reduction process comprises the following two steps:
1) placing the graphene oxide-based composite film in a high-temperature-resistant graphite mold, applying a pressure of 1-3MPa, heating to 250-300 ℃ in an inert atmosphere, preserving the temperature for 30-60 minutes, and then gradually cooling to room temperature to obtain a primarily-reduced graphene oxide-based composite film;
2) and applying the pressure of 10-12MPa to the primarily reduced graphene oxide-based composite film, heating to 700-800 ℃ in an inert atmosphere, preserving the temperature for 60-120 minutes, and cooling to room temperature to obtain the graphene-based composite film.
Preferably, the step 1) and the step 2) are performed in a high-temperature tube furnace in an inert gas atmosphere in an inert atmosphere; the inert gas comprises argon or nitrogen.
Preferably, the solution film forming method is a vacuum filtration method, a film coating method or an evaporation solution method.
The graphene oxide-based composite film is prepared by an improved Hummers method, a certain amount of stabilizer, surfactant and enhancer dispersion liquid is added, the mixture is ultrasonically stirred and uniformly mixed to obtain graphene oxide-based composite dispersion liquid, the graphene oxide-based composite dispersion liquid is prepared by film forming means such as a vacuum filtration method, a coating method or an evaporation solution method, and the like, and finally the graphene oxide-based composite film is obtained by a secondary hot-pressing reduction process, wherein the thickness of the graphene oxide-based composite film is 10-50 microns and is controllable, and the room-temperature heat conductivity coefficient is 800-1600 Wm--1k-1The tensile strength is 10-30MPa, the sheet is not damaged when bent at 180 degrees, and the sheet has good heat transfer performance, mechanical performance and light weight, and has great practical application value.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the improved Hummers method used in the invention does not need to use harmful nitrates (such as sodium nitrate and the like) to prepare the graphene oxide dispersion liquid; the graphite powder can be fully oxidized at a lower reaction temperature (30-40 ℃) in the reoxidation process through preoxidation; the prepared graphene oxide dispersion liquid can be stably stored for more than 6 months without precipitation, and sufficient raw material guarantee is provided for the subsequent preparation of the graphene-based composite film.
(2) The thickness of the graphene-based composite film prepared by the method is 10-50 microns and is controllable, and the heat conduction coefficient is 800-1600W m at room temperature-1k-1The tensile strength is 10-30MPa, the sheet is not damaged when bent at 180 degrees, and the sheet does not drop powder obviously, and has good heat transfer performance, mechanical performance and light weight.
(3) The secondary hot-pressing reduction process adopted by the invention can remove most of oxygen-containing groups in the graphene-based composite film under the conditions of low temperature (250-. Compared with the prior art, the method for preparing the commercial graphite film or the graphene film under the high temperature (2000-.
(4) According to the invention, the stabilizing agent and the reinforcing agent are added into the graphene oxide dispersion liquid, so that the graphene nanosheet structure can be effectively repaired and the air gap in the composite film can be filled in the hot-pressing reduction process, a more complete lamellar structure is obtained, a smoother heat conduction channel is formed, and the heat conduction performance and the mechanical performance of the film are improved.
Detailed Description
The present invention is further described with reference to the following examples, which should not be construed as limiting the scope of the present invention, but rather as providing those skilled in the art with insubstantial changes and modifications from the invention.
The thermal conductivity of the prepared film sample was calculated by the formula λ α · ρ · Cp, where λ is the thermal conductivity of the sample (W m)-1k-1) And α is the thermal diffusivity (mm) of the sample2s-1) And ρ is the density of the sample (g cm)-3) Cp is the specific heat capacity of the sample (J g)-1K-1) (ii) a Furthermore, the sample is measured by adopting a laser flash method with rapid and accurate characteristics facing to the thermal diffusion coefficient, the used instrument is a flash method thermal conductivity instrument (NETZSCH LFA 447NanoFlas), and the measurement temperature is room temperature; the density of the sample is calculated by the mass and the volume of the sample; the specific heat capacity of the sample was measured by a dynamic flow differential scanning calorimeter (DSC, NETZSCH DSC 204F1) at a test temperature of 25 ℃. Film samples were oriented to specific test procedure references for thermal conductivity (Kong, Qing-Qiang, Liu Z, Gao, Jian-Guo, et al. Hierarchical Graphere-Carbonfiber Composite Paper as a Flexible Heat radiator [ J. As].AdvancedFunctional Materials,2014,24(27) 4222 and 4228; preparation of Song-Ning-Jing-graphene-based thin film and mechanical and thermal property research [ D]University of chinese academy of sciences, 2016).
The tensile strength refers to the resistance of the maximum uniform plastic deformation which can be borne by the material, and is used for judging the mechanical property of the material. The tensile strength of the sample was determined by dynamic thermomechanical analysis (TA DMA Q800), 0.01N pre-stress, 0.05% min tensile rate-1。
And (3) bending test, namely directly bending the film sample by 180 degrees under the unsupported condition, wherein the minimum curvature radius can reach 3.5 mm, and no damage occurs.
Example 1
A high-thermal-conductivity graphene-based composite film and a preparation method thereof comprise the following specific steps:
(1) preparation of graphene oxide dispersions by an improved Hummers method
Pre-oxidation: 0.7 g of potassium persulfate and 0.7 g of phosphorus pentoxide were uniformly dispersed in 6 ml of 18mol L-1Adding 1 g of graphite powder into the concentrated sulfuric acid, uniformly shaking, carrying out condensation reflux reaction in a water bath at the temperature of 80 ℃ for 6 hours, cooling to room temperature, diluting into 150 ml of deionized water, carrying out vacuum filtration, washing with the deionized water and ethanol for several times until the deionized water and ethanol are neutral, and drying the solid at the temperature of 105 ℃ for 4 hours to obtain pre-oxidized graphite;
reoxidation: 1 g of pre-oxidized graphite and 40 ml of 18mol L-1The concentrated sulfuric acid is mixed in an ice water bath and stirred, 5 g of potassium permanganate is slowly added under the condition that the temperature of the mixture is not more than 20 ℃, then the mixture is heated to about 35 ℃ for reaction for 2 hours, 200 ml of deionized water is slowly added for dilution after the reaction is finished (the temperature of the solution is kept to be not higher than 50 ℃), and 8 ml of hydrogen peroxide is dropwise added after the mixture is stirred for 2 hours at room temperature to remove residual potassium permanganate, so that the graphene oxide suspension liquid with bright yellow solution is obtained;
washing and dispersing: standing and layering the obtained graphene oxide suspension, carefully pouring out supernatant, and dropwise adding 150 ml of 3mol L into the precipitate-1Then standing the diluted hydrochloric acid for layering, pouring out supernatant, and adding 150 ml of 3mol L-1Is repeated 6 times, and 100 mm of the final graphite oxide precipitate is addedAnd (3) raising the deionized water, centrifuging at 6000rpm for 20 minutes, pouring out the supernatant, adding 200 ml of deionized water into the rest graphite oxide precipitate, ultrasonically dispersing for 3 hours, then filling into a dialysis bag, and dialyzing in deionized water for 7 days until sulfate ions cannot be detected in the dialyzed deionized water and the pH value is 7.0 to obtain the graphene oxide dispersion liquid.
(2) Dispersing 10 mg of carbon nano tube in 10 ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 2 hours to obtain the concentration of 1.0mgml-1The carbon nanotube dispersion liquid of (1); 10 mg of carbon fiber was dispersed in 10 ml of absolute ethanol and sonicated for 2 hours to give a concentration of 1.0mg ml-1The carbon fiber dispersion of (4); the concentration of 6 ml is 4.2mg ml-1The graphene oxide dispersion was mixed with 15 mg of glucose, 0.5 mg of dodecylbenzenesulfonic acid, and 1.5 ml of 1.0 mg/ml-1And 1 ml of 1.0mg ml of the carbon nanotube dispersion-1Mixing the carbon fiber dispersion liquid, performing ultrasonic treatment for 20 minutes, and stirring for 5 minutes to obtain a uniformly mixed graphene oxide-based composite dispersion liquid;
(3) vacuum filtering the uniformly mixed graphene oxide-based composite dispersion solution on a mixed cellulose filter membrane (Jinteng, water system filter membrane) with the diameter of 50 mm and the pore diameter of 45 microns for 4 hours by adopting a vacuum filtration method, taking the filter membrane, putting the filter membrane in a 50 ℃ vacuum drying oven for drying for 2 hours, and tearing off the mixed cellulose filter membrane to obtain the graphene oxide-based composite film;
(4) placing the graphene oxide-based composite film in a graphite mold, applying a pressure of 3MPa, heating to 300 ℃ in a high-temperature tube furnace protected by argon atmosphere, preserving heat for 60 minutes, and gradually cooling to room temperature to obtain a primarily reduced graphene oxide-based composite film;
(5) and applying a pressure of 12MPa to the primarily reduced graphene oxide-based composite film, putting the film into a high-temperature tube furnace in an argon atmosphere, heating to 800 ℃, keeping the temperature for 120 minutes, and cooling to room temperature to obtain the graphene-based composite film.
Through the steps, the thickness of the graphene-based composite film is 12 microns, and the facing thermal conductivity is 1580W m-1k-1The tensile strength is 20MPa, and the 180-degree bending is not damaged.
Example 2:
(1) preparation of graphene oxide dispersions by an improved Hummers method
Pre-oxidation: 0.5 g of potassium persulfate and 0.6 g of phosphorus pentoxide were uniformly dispersed in 5 ml of 18mol L-1Adding 1 g of graphite powder into the concentrated sulfuric acid, uniformly shaking, carrying out condensation reflux reaction in a water bath at 83 ℃ for 5 hours, cooling to room temperature, diluting into 120 ml of deionized water, carrying out vacuum filtration, washing with deionized water and ethanol for several times until the deionized water is neutral, and drying the solid at 100 ℃ for 5 hours to obtain pre-oxidized graphite;
reoxidation: 1 g of pre-oxidized graphite and 30 ml of 18mol L-1Mixing concentrated sulfuric acid, slowly adding 3 g of potassium permanganate under the conditions of ice water bath and stirring, ensuring that the temperature of the mixture is not more than 20 ℃, then heating to 38 ℃ for reaction for 3 hours, slowly adding 180 ml of deionized water for dilution (keeping the temperature of the solution not higher than 50 ℃) after the reaction is finished, stirring at room temperature for 1.5 hours, and then dropwise adding 6 ml of hydrogen peroxide to remove residual potassium permanganate to obtain a graphene oxide suspension liquid with bright yellow solution;
washing and dispersing: standing and layering the obtained graphene oxide suspension, carefully pouring out supernatant, and dropwise adding 180 ml of 2.6mol L into the precipitate-1Then standing the diluted hydrochloric acid for layering, pouring out supernatant, and adding 180 ml of 2.6mol L-1The diluted hydrochloric acid is repeated for 5 times, 120 ml of deionized water is added into the last graphite oxide precipitate, the graphite oxide precipitate is centrifuged for 25 minutes at 5000rpm, the supernatant fluid is poured off, 220 ml of deionized water is added into the rest graphite oxide precipitate, ultrasonic dispersion is carried out for 2.5 hours, then the graphite oxide precipitate is filled into a dialysis bag and placed into deionized water for dialysis for 7 days until sulfate ions can not be detected by the dialyzed deionized water and the pH value is 6.7, and the graphene oxide dispersion liquid is obtained.
(2) Dispersing 10 mg of carbon nano tube in 10 ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 2 hours to obtain the concentration of 1.0mgml-1The carbon nanotube dispersion liquid of (1); 5mg of carbon fiber was dispersed in 5 ml of absolute ethanol and sonicated for 2 hours to give a concentration of 1.0mg ml-1The carbon fiber dispersion of (4); the concentration of 10 ml is 4.0mg ml-1The graphene oxide dispersion liquid is mixed with 25 mg of xylitol, 1 mg of dodecyl glucoside and 2 ml of 1.0mg ml-1And 0.5 ml of 1.0mg ml-1Mixing the carbon fiber dispersion liquid, performing ultrasonic treatment for 15 minutes, and stirring for 5 minutes to obtain a uniformly mixed graphene oxide-based composite dispersion liquid;
(3) vacuum filtering the uniformly mixed graphene oxide-based composite dispersion solution on a mixed cellulose filter membrane (Jinteng, water system filter membrane) with the diameter of 50 mm and the pore diameter of 45 microns for 6 hours by adopting a vacuum filtration method, taking the filter membrane, putting the filter membrane in a 50 ℃ vacuum drying oven for drying for 2 hours, and tearing off the mixed cellulose filter membrane to obtain the graphene oxide-based composite film;
(4) placing the graphene oxide-based composite film in a graphite mold, applying 2MPa pressure, heating to 280 ℃ in a high-temperature tube furnace protected by argon atmosphere, preserving heat for 40 minutes, and then gradually cooling to room temperature to obtain a primarily-reduced graphene oxide-based composite film;
(5) and applying 10MPa pressure to the primarily reduced graphene oxide-based composite film, putting the film into a high-temperature tube furnace in an argon atmosphere, heating to 750 ℃, keeping the temperature for 100 minutes, and cooling to room temperature to obtain the graphene-based composite film.
Through the steps, the thickness of the graphene-based composite film is 20 microns, and the facing thermal conductivity is 1300W m-1k-1The tensile strength is 12MPa, and the 180-degree bending is not damaged.
Example 3:
(1) preparation of graphene oxide dispersions by an improved Hummers method
Pre-oxidation: 0.7 g of potassium persulfate and 0.5 g of phosphorus pentoxide were uniformly dispersed in 6 ml of 18mol L-1Adding 1 g of graphite powder into the concentrated sulfuric acid, uniformly shaking, carrying out condensation reflux reaction in a water bath at 78 ℃ for 7 hours, cooling to room temperature, diluting into 130 ml of deionized water, carrying out vacuum filtration, using deionized water ethanol and washing for several times until the solution is neutral, and drying the solid at 110 ℃ for 4 hours to obtain pre-oxidized graphite;
reoxidation: 1 g of pre-oxidized graphite and 35 ml of 16mol L-1Mixed with concentrated sulfuric acid in iceSlowly adding 4 g of potassium permanganate in a water bath and under stirring conditions, ensuring that the temperature of the mixture is not more than 20 ℃, then heating to 40 ℃ for reaction for 2.5 hours, slowly adding 160 ml of deionized water for dilution (keeping the temperature of the solution not higher than 50 ℃) after the reaction is finished, stirring at room temperature for 1.5 hours, and then dropwise adding 7 ml of hydrogen peroxide to remove residual potassium permanganate to obtain a graphene oxide suspension liquid with bright yellow solution;
washing and dispersing: standing and layering the obtained graphene oxide suspension, carefully pouring out supernatant, and dropwise adding 140 ml of 2.8mol L into the precipitate-1Then standing the mixture for layering, pouring out supernatant, and adding 140 ml of 2.8mol L-1The diluted hydrochloric acid is repeated for 5 times, 140 ml of deionized water is added into the last graphite oxide precipitate, the graphite oxide precipitate is centrifuged for 15 minutes at 5500rpm, the supernatant fluid is poured off, 200 ml of deionized water is added into the rest graphite oxide precipitate, ultrasonic dispersion is carried out for 3 hours, then the graphite oxide precipitate is filled into a dialysis bag and placed into deionized water for dialysis for 7 days until sulfate ions can not be detected by the dialyzed deionized water and the pH value is 6.5, and the graphene oxide dispersion liquid is obtained.
(2) 10 mg of carbon fiber was dispersed in 10 ml of absolute ethanol and sonicated for 2 hours to give a concentration of 1.0mg ml-1The carbon fiber dispersion of (4); 40 ml of the solution with the concentration of 3.0mg ml-1The graphene oxide dispersion liquid is mixed with 60 mg of nano-cellulose, 2mg of dodecyl glucoside, 2mg of dodecyl benzene sulfonic acid and 5 ml of 1.0mg ml-1Mixing the carbon fiber dispersion liquid, performing ultrasonic treatment for 25 minutes, and stirring for 5 minutes to obtain a uniformly mixed graphene oxide-based composite dispersion liquid;
(3) and pouring the uniformly mixed graphene oxide-based composite dispersion liquid into a circular flat-bottom glass dish with the diameter of 50 mm by adopting an evaporation solution method, putting the flat-bottom glass dish into a 55-DEG C forced-air electric heating drying oven to evaporate the solvent for 6 hours, and carefully tearing the film from the glass dish to obtain the graphene oxide-based composite film.
(4) Placing the graphene oxide-based composite film in a graphite mold, applying 1MPa pressure, heating to 250 ℃ in a high-temperature tube furnace protected by argon atmosphere, preserving heat for 30 minutes, and then gradually cooling to room temperature to obtain a primarily reduced graphene oxide-based composite film;
(5) and applying a pressure of 12MPa to the primarily reduced graphene oxide-based composite film, putting the film into a high-temperature tube furnace in an argon atmosphere, heating to 700 ℃, keeping the temperature for 90 minutes, and cooling to room temperature to obtain the graphene-based composite film.
Through the steps, the thickness of the graphene-based composite film is 42 microns, and the facing thermal conductivity is 900W m-1k-1The tensile strength is 25MPa, and the 180-degree bending is not damaged.
Example 4:
(1) preparation of graphene oxide dispersions by an improved Hummers method
Pre-oxidation: 0.6 g of potassium persulfate and 0.6 g of phosphorus pentoxide were uniformly dispersed in 5 ml of 18mol L-1Adding 1 g of graphite powder into the concentrated sulfuric acid, uniformly shaking, carrying out condensation reflux reaction in a water bath at 85 ℃ for 5.5 hours, cooling to room temperature, diluting to 160 ml of deionized water, carrying out vacuum filtration, washing with deionized water and ethanol for several times until the deionized water is neutral, and drying the solid at 108 ℃ for 3.5 hours to obtain pre-oxidized graphite;
reoxidation: 1 g of pre-oxidized graphite and 38 ml of 18mol L-1Slowly adding 3.5 g of potassium permanganate into the mixed concentrated sulfuric acid in an ice-water bath under stirring conditions, ensuring that the temperature of the mixture is not more than 20 ℃, then heating to 36 ℃ for reaction for 3.5 hours, slowly adding 170 ml of deionized water for dilution (keeping the temperature of the solution not higher than 50 ℃) after the reaction is finished, stirring at room temperature for 2 hours, and then dropwise adding 7 ml of hydrogen peroxide to remove residual potassium permanganate to obtain a graphene oxide suspension liquid with bright yellow solution;
washing and dispersing: standing and layering the obtained graphene oxide suspension, carefully pouring out supernatant, and dropwise adding 180 ml of 3mol L into the precipitate-1Then standing the diluted hydrochloric acid for layering, pouring out supernatant, and adding 180 ml of 3mol L-1Repeating the reaction for 4 times, adding 120 ml of deionized water into the last graphite oxide precipitate, centrifuging at 4500rpm for 20 min, pouring off the supernatant, adding 180 ml of deionized water into the rest graphite oxide precipitate, ultrasonically dispersing for 2.5 hr, loading into dialysis bag, and placing into deionized water bagDialyzing in water for 7 days until sulfate ions can not be detected by the dialyzed deionized water and the pH value is 6.8 to obtain the graphene oxide dispersion liquid.
(2) 10 mg of carbon fiber was dispersed in 10 ml of absolute ethanol and sonicated for 2 hours to give a concentration of 1.0mg ml-1The carbon fiber dispersion of (4); the concentration of 10 ml is 5.0mg ml-1The graphene oxide dispersion was mixed with 10 mg of glucose, 50 mg of sorbitol, 1.5mg of dodecylbenzenesulfonic acid, and 1.2 ml of 1.0 mg/ml-1Mixing the carbon fiber dispersion liquid, performing ultrasonic treatment for 25 minutes, and stirring for 5 minutes to obtain a uniformly mixed graphene oxide-based composite dispersion liquid;
(3) uniformly coating the uniformly mixed graphene oxide-based composite dispersion liquid on a glass substrate for multiple times by using a coating method and a coater, drying the glass substrate in a 55 ℃ drying oven for 2 hours, and carefully tearing off the film from the glass substrate to obtain a graphene oxide-based composite film;
(4) placing the graphene oxide-based composite film in a graphite mold, applying 3MPa pressure, heating to 280 ℃ in a high-temperature tube furnace protected by argon atmosphere, preserving heat for 40 minutes, and then gradually cooling to room temperature to obtain a primarily-reduced graphene oxide-based composite film;
(5) and applying 11MPa pressure to the primarily reduced graphene oxide-based composite film, putting the film into a high-temperature tube furnace in an argon atmosphere, heating to 750 ℃, keeping the temperature for 60 minutes, and cooling to room temperature to obtain the graphene-based composite film.
Through the steps, the thickness of the graphene-based composite film is 26 microns, and the facing thermal conductivity is 1100W m-1k-1The tensile strength is 16MPa, and the 180-degree bending is not damaged.
The existing graphene membrane and composite membrane are prepared by adopting high temperature (2000-. The preparation process has the characteristics of low temperature, low pressure and low energy consumption. The low temperature is that the used thermal reduction temperature is 700-800 ℃, compared with the prior art that the process temperature is 2000-3000 ℃, the temperature is obviously lower, the energy consumption required by the lower temperature is less, and the energy consumption is less; the low pressure is 1-3MPa and 10-12MPa, compared with the prior art that the process pressure is 200-300MPa, the low pressure also has the advantage of obviously lower pressure, the required mechanical energy is smaller, and the energy is saved; the invention has the advantages of low temperature, low pressure and low energy consumption, so that on one hand, the production condition is milder, the harsh condition requirement of the used equipment is less, the safe and reliable performance of the operation is higher, the operation is simpler and more convenient, and the production cost is greatly reduced; on the other hand, the low energy consumption better meets the construction requirements of energy-saving emission-reducing and environment-friendly society, can reduce more discharge amount of greenhouse gases and the like, and obviously reduces the environmental protection cost.
The coefficient of thermal conductivity of the existing graphene film is generally 1000W m-1k-1The thickness of the graphene-based composite film prepared by the invention is 10-50 microns and controllable, and the room temperature-oriented thermal conductivity is 800-1600W m-1k-1The graphene-based composite film has the advantages that the tensile strength can reach 10-30MPa, the film is bent at 180 degrees and is not damaged, the graphene-based composite film has good heat transfer performance, mechanical performance and light weight, compared with the prior art, the graphene-based composite film has excellent comprehensive performance, the heat conductivity coefficient is not lower than that of a graphene film in the prior art, and the graphene-based composite film has a slight advantage, and more importantly, the flexible, light and high-heat-conductivity graphene composite film is prepared under mild process conditions in an energy-saving and low-cost manner; the heat dissipation device has wide application range and has great application prospect in the fields of high-power and high-heat-flux electronic industry and heat dissipation of electronic devices of intelligent equipment.
Claims (9)
1. The utility model provides a high heat conduction graphite alkene base composite film which characterized in that: the graphene-based composite film comprises the following raw materials in percentage by mass: 40-70% of graphene oxide, 30-60% of a stabilizer, 1-3% of a surfactant and 1-10% of a reinforcing agent; the mass ratio of the solid raw material to the liquid dispersant is 1-10: 1000; the sum of the raw material compositions meets 100 percent;
adding the graphene oxide into the graphene oxide dispersion liquid;
the stabilizer is one or a mixture of more of nano cellulose, xylitol, glucose and sorbitol;
the surfactant is one or the mixture of two of dodecyl benzene sulfonic acid and dodecyl glucoside;
the reinforcing agent is added in the form of carbon nano tube and/or carbon fiber dispersion liquid;
the thickness of the graphene-based composite film is 10-50 microns and controllable, and the room-temperature heat conductivity coefficient is 800--1k-1The tensile strength is 10-30MPa, and the 180-degree bending is not damaged;
the preparation method of the graphene-based composite film comprises the steps of mixing graphene oxide dispersion liquid, a stabilizer, a surfactant and an enhancer dispersion liquid, performing ultrasonic treatment and stirring uniformly to obtain graphene oxide-based composite dispersion liquid, obtaining the graphene oxide-based composite film by using a solution film forming method, and finally obtaining the graphene-based composite film by a secondary hot-pressing reduction process; the secondary hot-pressing reduction process comprises the following two steps:
1) placing the graphene oxide-based composite film in a high-temperature-resistant graphite mold, applying a pressure of 1-3MPa, heating to 250-300 ℃ in an inert atmosphere, preserving the temperature for 30-60 minutes, and then gradually cooling to room temperature to obtain a primarily-reduced graphene oxide-based composite film;
2) applying pressure of 10-12MPa to the primarily reduced graphene oxide-based composite film, heating to 700-800 ℃ in an inert atmosphere, preserving the temperature for 60-120 minutes, and cooling to room temperature to obtain the graphene-based composite film;
the graphene oxide dispersion liquid takes water as a solvent, and the concentration of the graphene oxide dispersion liquid is 1.0-8.0mg ml-1The product is stably stored for more than 6 months without sediment; the carbon nano tube and/or carbon fiber dispersion liquid takes absolute ethyl alcohol as a solvent, and the concentration is 0.5-1.5mg ml-1。
2. The graphene-based composite film with high thermal conductivity according to claim 1, wherein: the graphene oxide dispersion liquid is prepared by an improved Hummers method, and comprises the following steps:
1) pre-oxidation: dispersing graphite powder, potassium persulfate and phosphorus pentoxide in concentrated sulfuric acid, carrying out condensation reflux reaction for 5-8 hours in a water bath at 75-85 ℃, cooling to room temperature, adding deionized water for dilution, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and drying to obtain pre-oxidized graphite;
2) reoxidation: mixing the pre-oxidized graphite and concentrated sulfuric acid, slowly adding potassium permanganate under the conditions of ice water bath and stirring, ensuring that the temperature of the mixture is not more than 20 ℃, then heating to 30-40 ℃, reacting for 1-4 hours, adding deionized water for dilution, stirring for 1-2 hours at room temperature, and then dropwise adding hydrogen peroxide to remove residual potassium permanganate to obtain a bright yellow oxidized graphite suspension;
3) washing and dispersing: standing and layering the graphite oxide suspension, pouring out supernatant, and dropwise adding dilute hydrochloric acid into the graphite oxide precipitate; and standing, layering, pouring out supernatant, adding dilute hydrochloric acid into the precipitate, repeatedly washing, adding deionized water into the last graphite oxide precipitate, centrifuging, pouring out centrifugal supernatant, adding deionized water into the rest graphite oxide precipitate, ultrasonically dispersing for 2-4 hours, then filling into a dialysis bag, and dialyzing for several days in deionized water until sulfate ions are not detected in the dialyzed deionized water and the pH value is 6.5-7.0 to obtain the graphene oxide dispersion liquid.
3. The graphene-based composite film with high thermal conductivity according to claim 2, wherein: the mass ratio of the graphite powder to the potassium persulfate to the phosphorus pentoxide is 1:0.5-0.7: 0.5-0.7; the mass ratio of the pre-oxidized graphite to the concentrated sulfuric acid to the potassium permanganate is 1:55-73: 3-5.
4. The graphene-based composite film with high thermal conductivity according to claim 2, wherein: the molar concentration of the concentrated sulfuric acid is 15-18mol L-1The molar concentration of the dilute hydrochloric acid is 2.5-3.0mol L-1。
5. The graphene-based composite film with high thermal conductivity according to claim 2, wherein: the drying temperature is 100-110 ℃; the repeated washing times are 4-6 times; the rotation speed of the centrifugal treatment is 4000-6000rpm, and the time is 15-30 minutes.
6. The graphene-based composite film with high thermal conductivity according to claim 1, wherein: the carbon nano tube is a high-thermal-conductivity multi-wall carbon nano tube with the outer diameter of less than 10 nanometers, the length of 5-15 micrometers and the purity of more than 97 percent; the carbon fiber is carbon fiber powder with the carbon content of more than 95 percent, the mesh number of 300-200 and the maximum length of 74 microns.
7. The method for preparing the graphene-based composite film with high thermal conductivity according to any one of claims 1 to 6, wherein: mixing the graphene oxide dispersion liquid, the stabilizer, the surfactant and the reinforcing agent dispersion liquid, performing ultrasonic treatment and stirring uniformly to obtain a graphene oxide-based composite dispersion liquid, obtaining a graphene oxide-based composite film by using a solution film-forming method, and finally obtaining the graphene-based composite film by a secondary hot-pressing reduction process; the secondary hot-pressing reduction process comprises the following two steps:
1) placing the graphene oxide-based composite film in a high-temperature-resistant graphite mold, applying a pressure of 1-3MPa, heating to 250-300 ℃ in an inert atmosphere, preserving the temperature for 30-60 minutes, and then gradually cooling to room temperature to obtain a primarily-reduced graphene oxide-based composite film;
2) and applying the pressure of 10-12MPa to the primarily reduced graphene oxide-based composite film, heating to 700-800 ℃ in an inert atmosphere, preserving the temperature for 60-120 minutes, and cooling to room temperature to obtain the graphene-based composite film.
8. The preparation method of the graphene-based composite film with high thermal conductivity according to claim 7, wherein the preparation method comprises the following steps: the high-temperature tube furnace in the inert atmosphere in the step 1) and the step 2) is in the inert gas atmosphere; the inert gas comprises argon or nitrogen.
9. The preparation method of the graphene-based composite film with high thermal conductivity according to claim 7, wherein the preparation method comprises the following steps: the solution film forming method is a vacuum filtration method, a film coating method or an evaporation solution method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810612571.9A CN108658615B (en) | 2018-06-14 | 2018-06-14 | High-thermal-conductivity graphene-based composite film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810612571.9A CN108658615B (en) | 2018-06-14 | 2018-06-14 | High-thermal-conductivity graphene-based composite film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108658615A CN108658615A (en) | 2018-10-16 |
| CN108658615B true CN108658615B (en) | 2020-04-28 |
Family
ID=63775708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810612571.9A Active CN108658615B (en) | 2018-06-14 | 2018-06-14 | High-thermal-conductivity graphene-based composite film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108658615B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109767992B (en) * | 2019-01-16 | 2020-11-13 | 深圳天元羲王材料科技有限公司 | Preparation method of heat dissipation layer of radiator and radiator |
| CN109824033B (en) * | 2019-03-06 | 2021-01-29 | 华南理工大学 | Method for preparing high-thermal-conductivity graphene film at low cost |
| CN110282974B (en) * | 2019-06-28 | 2020-12-29 | 华南理工大学 | Oriented magnetic carbon fiber graphene composite membrane and preparation method and application thereof |
| CN110342838B (en) * | 2019-07-11 | 2021-08-31 | 济南大学 | High-heat-conductivity cement clinker and preparation method and application of cement product thereof |
| CN110964219B (en) * | 2019-12-12 | 2022-03-25 | 上海大学 | Nano cellulose membrane with high thermal conductivity and preparation method thereof |
| CN111252760B (en) * | 2020-01-22 | 2021-01-05 | 哈尔滨工业大学 | Preparation method of graphene oxide nano roll and composite material thereof |
| CN111518317B (en) * | 2020-05-13 | 2021-12-28 | 上海交通大学 | High-thermal-conductivity and water-transmission composite film material and preparation method and application thereof |
| CN112898953B (en) * | 2021-01-14 | 2021-12-28 | 扬州晟至宝新材料科技有限公司 | Preparation method of graphene heat-conducting film |
| CN112795807B (en) * | 2021-02-26 | 2022-01-25 | 安徽宝德光伏科技有限公司 | Low-cost aluminum substrate photovoltaic solder strip and preparation method thereof |
| CN113717702B (en) * | 2021-08-31 | 2023-09-29 | 中钢天源股份有限公司 | Graphene composite cooling fin and preparation method thereof |
| CN114149619A (en) * | 2021-12-17 | 2022-03-08 | 北京化工大学 | Preparation method of graphene/cellulose composite material |
| CN115232384B (en) * | 2022-08-25 | 2023-02-10 | 青岛优派普环保科技股份有限公司 | Antistatic PE gas pipe and preparation method thereof |
| CN116003148A (en) * | 2022-12-12 | 2023-04-25 | 山东大学 | High-thermal-conductivity graphene composite film and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104627977B (en) * | 2013-11-07 | 2017-02-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide reinforced composite carbon nanopaper and production method thereof |
| CN105038055B (en) * | 2015-08-06 | 2017-09-19 | 中国人民解放军军械工程学院 | A kind of preparation method for carbon fiber and graphite alkenyl shell layered bionic electromagnetic shielding film of classifying |
-
2018
- 2018-06-14 CN CN201810612571.9A patent/CN108658615B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108658615A (en) | 2018-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108658615B (en) | High-thermal-conductivity graphene-based composite film and preparation method thereof | |
| CN109824033B (en) | Method for preparing high-thermal-conductivity graphene film at low cost | |
| CN108251076B (en) | Carbon nanotube-graphene composite heat dissipation film, and preparation method and application thereof | |
| CN104743551B (en) | A kind of preparation method of redox graphene heat conduction thin film | |
| CN105544017B (en) | A kind of highly conductive graphene fiber and preparation method thereof | |
| CN108328635B (en) | Method for preparing alumina aerogel | |
| WO2016011905A1 (en) | Silver-doped graphene composite paper and preparation method therefor | |
| CN103145124B (en) | High-performance graphene paper and preparation method thereof | |
| WO2017186127A1 (en) | Method for preparing graphene-modified polymethyl methacrylate composite material having ultra-high conductivity | |
| CN111394833B (en) | Carbon nano tube/graphene composite fiber and preparation method thereof | |
| CN105254302B (en) | Preparing method for graphene heat conduction sheet | |
| CN103420352A (en) | High-fluoride-content graphite fluoride and preparation method thereof | |
| CN103613093B (en) | A kind of hydrogen reducing prepares the method for Graphene | |
| CN110846529A (en) | Preparation method of graphene reinforced copper composite material | |
| CN111892420B (en) | Method for preparing massive titanium carbide, titanium nitride or titanium carbonitride aerogel | |
| CN109161709B (en) | Preparation method of cracked carbon nanotube reinforced copper-based composite material | |
| CN103951916A (en) | RGO (Reduced Graphene oxide)/ferric oxide-filled polyvinylidene fluoride composite wave-absorbing material and preparation method thereof | |
| CN113716966B (en) | SiCN ceramic aerogel and preparation method and application thereof | |
| CN107814507B (en) | Graphene-based heat-conducting composite material and preparation method and application thereof | |
| CN108899496B (en) | Graphene doped WS2Preparation method and application in lithium/sodium ion battery | |
| WO2021027607A1 (en) | Preparation method for highly conductive graphene copper/aluminium composite wire | |
| CN110835099A (en) | Preparation method of thin-layer boron nitride nanosheet | |
| CN107682944B (en) | Semiconductor electrothermal film and preparation method thereof | |
| WO2022179332A1 (en) | Electric infrared heating film and manufacturing method therefor, and electric infrared heating apparatus | |
| CN110697695A (en) | Preparation method of graphene reinforced metal matrix foam framework structure composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |