CN115466457A - Graphene modified heat conduction material and preparation method and application thereof - Google Patents
Graphene modified heat conduction material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 194
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- 239000000463 material Substances 0.000 title claims abstract description 39
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention provides a graphene modified heat conduction material and a preparation method and application thereof, and belongs to the technical field of composite materials. Mixing and calcining urea and ammonium chloride to obtain porous C 3 N 4 Heating and mixing with graphene oxide solution to prepare porous C 3 N 4 Graphene oxide, modified by silane coupling agent, and mixed with acid-treated single-walled carbon nanotube to obtain porous C 3 N 4 Graphene oxide/carbon nanotubes prepared byPreparing porous C by over-reduction 3 N 4 The graphene/carbon nano tube is mixed with PP resin by stirring and hot pressing to prepare the graphene modified heat conduction material. Porous C prepared by the invention 3 N 4 The graphene/carbon nano tube has excellent heat conduction and heat dissipation performance, and the graphene modified heat conduction material prepared by adding the graphene/carbon nano tube into PP resin for mixing can be widely used for preparing heat dissipation components of electronic materials, has excellent heat dissipation effect and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a graphene modified heat conduction material and a preparation method and application thereof.
Background
With the rapid development of 5G technology and light, thin, highly integrated and multifunctional electronic products, the development of high thermal conductivity materials is an important approach to solve the problem of the reduction of the operating life and reliability of electronic devices caused by heat accumulation. The polymer-based composite material has high-efficiency heat transfer performance and strong mechanical property, and becomes the best choice of heat management materials in electronic components. The regulation and control of the interface thermal resistance and the construction of a heat transfer path in the composite material are effective ways for improving the thermal conductivity of the polymer-based composite material.
The modification of the heat-conducting filler is an effective means for regulating and controlling the interfacial thermal resistance between the fillers. Although covalent modification can form a heat transfer path between fillers through chemical bonds to reduce the interface thermal resistance, the damage of the inherent structure of the filler affects the thermal conductivity to some extent. On the basis of ensuring the heat conduction performance of the filler, the non-covalent modification effectively reduces the interfacial thermal resistance between the fillers through modes such as hydrogen bond interaction, electrostatic interaction, pi-pi interaction and the like, so that the non-covalent modification becomes the mainstream mode of the current filler modification. Recently, a novel non-covalent bond, cation-pi interaction, has been studied intensively because it can build the strongest interaction in the filler to effectively alleviate the interfacial thermal resistance. However, the modification effect of the cationized small molecules on the heat-conducting filler is limited by the modification efficiency and the relatively weak acting force. Meanwhile, most of the modified micromolecules are non-heat-conducting materials, and the improvement of the interface heat conduction performance between the fillers is also restricted. However, polymer surface modification, which modifies the surface structure of the fillers and also interconnects between fillers to promote efficient phonon transfer or lattice vibration, would be an effective way to solve the above problems.
Graphene is a graphene having sp 2 The carbon-containing six-membered ring structure of the hybrid structure has very stable physical and chemical properties. Compared with the traditional metal materials such as copper, aluminum and the like, the graphene has higher in-plane thermal conductivity coefficient. Due to the special structure, the graphene has lower density, good thermal stability, ultrahigh conductivity, excellent transmittance and better mechanical property.
Disclosure of Invention
The invention aims to provide a graphene modified heat conduction material and a preparation method and application thereof, and the porous C prepared by the invention 3 N 4 Graphene/carbon nano tube material has excellent heat conduction and heat dissipation performance, and stone prepared by adding the graphene/carbon nano tube material into PP resin for mixingThe graphene modified heat conduction material can be widely used for preparing heat dissipation components of electronic materials, has a good heat dissipation effect, and has a wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a graphene modified heat conduction material, which is characterized in that urea and ammonium chloride are mixed and calcined to obtain porous C 3 N 4 Heating and mixing with graphene oxide solution to prepare porous C 3 N 4 Graphene oxide, modified by silane coupling agent, and mixed with acid-treated single-walled carbon nanotube to obtain porous C 3 N 4 Reducing graphene oxide/carbon nanotubes to obtain porous C 3 N 4 The graphene/carbon nano tube is mixed with PP resin by stirring and hot-pressed to prepare the graphene modified heat conduction material.
As a further improvement of the invention, the method comprises the following steps:
s1. Porous C 3 N 4 The preparation of (1): uniformly mixing urea and ammonium chloride solids, calcining and cooling to prepare the porous C 3 N 4 ；
S2. Porous C 3 N 4 Preparation of graphene oxide: adding the porous C prepared in the step S1 into the graphene oxide solution 3 N 4 Ultrasonic treatment, heating reaction and drying to obtain the porous C 3 N 4 Graphene oxide;
s3. Porous C 3 N 4 Preparation of graphene oxide/carbon nanotubes: putting the single-walled carbon nanotube into acid liquor for heating treatment, filtering, washing, adding water, and adding the porous C prepared in the step S2 3 N 4 Heating graphene oxide and silane coupling agent for reaction, filtering, washing and drying to obtain porous C 3 N 4 Graphene oxide/carbon nanotubes;
s4. Porous C 3 N 4 Preparation of graphene/carbon nanotubes: the porous C prepared in the step S3 3 N 4 Adding graphene oxide/carbon nano tube into water, dispersing uniformly by ultrasonic, adding ammonia water and hydrazine hydrate, and heating for reaction to obtain porous C 3 N 4 Graphene/carbon nanotubes;
s5, preparing a graphene modified heat conduction material: adding PP resin into a mixing roll, and adding the porous C prepared in the step S4 3 N 4 Mixing and stirring graphene/carbon nano tubes, and hot-pressing to obtain the graphene modified heat conduction material.
As a further improvement of the invention, the mass ratio of the urea to the ammonium chloride in the step S1 is 3-7; the calcining temperature is 500-600 ℃, and the time is 2-4h.
As a further improvement of the invention, the graphene oxide and the porous C in the step S2 3 N 4 The mass ratio of (A) to (B) is 2-4:10; the ultrasonic power is 1000-2000W, and the processing time is 1-3h; the heating is carried out until the temperature is 180-200 ℃, and the reaction time is 15-20h.
As a further improvement of the invention, in the step S3, the acid solution is concentrated sulfuric acid and concentrated nitric acid, the mass of which is 1-3; the heating treatment is carried out for 12-15h until the temperature is 60-80 ℃, and the single-walled carbon nanotube and the porous C are formed 3 N 4 The mass ratio of the graphene oxide to the silane coupling agent is 3-5; the heating reaction is carried out at the temperature of 70-90 ℃ for 1-3h; the silane coupling agent is at least one selected from KH550, KH560, KH570, KH580, KH590, KH602 and KH 792.
As a further improvement of the invention, the silane coupling agent is a compound mixture of KH590 and KH792, and the mass ratio is 3-7.
As a further development of the invention, the hole C is provided in step S4 3 N 4 The mass ratio of graphene oxide/carbon nano tube, ammonia water and hydrazine hydrate is 12-15: 1-2; the concentration of the ammonia water is 27-32wt%; the heating reaction is carried out at the temperature of 90-100 ℃ for 1-3h.
As a further improvement of the invention, the PP resin and the porous C in the step S5 3 N 4 The mass ratio of graphene/carbon nanotube is 10:1-2; the stirring and mixing temperature is 190-200 ℃, the time is 10-15min, and the rotating speed is 50-100r/min; the hot pressing temperature is 190-200 ℃, the pressing time is 3-5min, the pressure is released for 30-40s, and the steps are repeated for 3 times.
The invention further protects the graphene modified heat conduction material prepared by the preparation method.
The invention further protects the application of the graphene modified heat conduction material in the preparation of heat dissipation components.
The invention has the following beneficial effects: the invention takes urea as raw material and ammonium chloride as dynamic gas template agent, and adopts a thermal polycondensation method to prepare the porous C 3 N 4 Is an atomic crystal material with excellent heat conductivity, and N atom sp 2 Hybridization, namely connecting the carbon atoms with 3C atoms on an approximate plane, facilitating heat dissipation and vibration, simultaneously enabling the N atoms to easily form hydrogen bonds with oxygen-containing parts of graphene oxide for stable compounding, and further compounding with single-walled carbon nanotubes with multiple hydrogen formed after surface acidification to prepare the porous C 3 N 4 Graphene oxide/carbon nanotubes, further reduced to obtain porous C 3 N 4 The graphene/carbon nano tube composite material has excellent heat conduction and heat dissipation performance, and the graphene modified heat conduction material prepared by adding the graphene/carbon nano tube composite material into PP resin for mixing can be widely used for preparing heat dissipation components of electronic materials, has excellent heat dissipation effect and has wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an SEM image of the graphene-modified thermal conductive material prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Preparing graphene oxide by an improved Hummers method:
step one, weighing 10G of natural graphite powder (G), 4G of potassium persulfate and 10G of phosphorus pentoxide, adding the natural graphite powder (G), the potassium persulfate and the phosphorus pentoxide into a three-neck flask filled with 24 mL of sulfuric acid under the condition of stirring, firstly reacting for 3h in a constant-temperature water bath at 60 ℃, then moving the three-neck flask into a constant-temperature water bath at 25 ℃ for reacting for 5h, performing suction filtration, washing the three-neck flask to be neutral by using ionized water, and drying the three-neck flask in the air to obtain pre-oxidized graphite (P-G);
step two, weighing l g of pre-oxidized graphite, adding the pre-oxidized graphite into a three-neck flask filled with 25 mL of sulfuric acid under the condition of stirring, putting the three-neck flask into an ice water bath, adding 3 g of potassium permanganate after the pre-oxidized graphite is completely dissolved, reacting for 2 hours, moving the three-neck flask into a constant-temperature water bath at 35 ℃ for reacting for 40 minutes, finally adding deionized water, continuing to react for 1 hour at 35 ℃, and finally dropwise adding 30% of H 2 O 2 So that the solution turned bright yellow until no more gas was formed. The mixture was filtered by centrifugation while hot and washed to neutrality with a large amount of 5% hydrochloric acid and deionized water. And (3) after the final precipitate is subjected to ultrasonic oscillation for l h, pouring the precipitate into a culture dish, and drying the precipitate for 24 h at 90 ℃ to obtain flaky Graphite Oxide (GO).
The single-walled carbon nanotube has the purity of more than 90 percent, the outer diameter of 1-2nm, the inner diameter of 0.8-1.6nm and the length of 1-2 mu m, and is purchased from Suzhou Cifeng graphene science and technology Co., ltd; hydrazine hydrate, the main content is more than 80.11 percent, the pH is =11, and the hydrazine hydrate is purchased from Wuhan Chu Jianghuaoyu chemical engineering development limited company; PP resin, with a content of more than 56%, was purchased from Rui-Tech Co., ltd.
Example 1
The embodiment provides a preparation method of a graphene modified heat conduction material, which comprises the following steps:
s1. Porous C 3 N 4 The preparation of (1): uniformly mixing 3 parts by weight of urea and 1 part by weight of ammonium chloride solid, calcining at 500 ℃ for 2h, and cooling to obtain the porous C 3 N 4 ；
S2. Porous C 3 N 4 Preparation of graphene oxide: adding 10 parts by weight of the graphene oxide-containing aqueous solution prepared in the step S1 into 2 parts by weight of the graphene oxide-containing aqueous solutionPorous C 3 N 4 Ultrasonic treatment at 1000W for 1h, heating at 180 ℃ for 15h, and drying to obtain porous C 3 N 4 Graphene oxide;
s3. Porous C 3 N 4 Preparation of graphene oxide/carbon nanotubes: and (2) placing 3 parts by weight of single-walled carbon nanotubes in acid liquor for heating treatment, wherein the acid liquor is concentrated sulfuric acid and concentrated nitric acid, the mass of the acid liquor is 1, the heating treatment is carried out until the temperature is 60 ℃, the treatment time is 12 hours, filtering, washing and adding into water are carried out, and 10 parts by weight of the porous C prepared in the step (S2) are added into the water 3 N 4 Graphene oxide and 0.1 part by weight of silane coupling agent, heating for reaction, filtering, washing and drying to obtain porous C 3 N 4 Graphene oxide/carbon nanotubes;
the silane coupling agent is a compound mixture of KH590 and KH792, and the mass ratio of the silane coupling agent to the KH792 is 3;
s4. Porous C 3 N 4 Preparation of graphene/carbon nanotubes: 12 parts by weight of the porous C obtained in step S3 3 N 4 Adding graphene oxide/carbon nano tube into water, uniformly dispersing by ultrasonic, adding 3 parts by weight of 27wt% ammonia water and 1 part by weight of hydrazine hydrate, heating to 90 ℃, and reacting for 1h to obtain porous C 3 N 4 Graphene/carbon nanotubes;
s5, preparing a graphene modified heat conduction material: adding 10 parts by weight of PP resin into a mixing roll, and adding 1 part by weight of the porous C prepared in the step S4 3 N 4 And/graphene/carbon nano tube, stirring and mixing at 190 ℃ for 10min at a rotation speed of 50r/min, hot-pressing at 190 ℃ for 3min, and decompressing for 30s, wherein the steps are repeated for 3 times to obtain the graphene modified heat conduction material. Fig. 1 is an SEM image of the prepared graphene modified thermal conductive material.
Example 2
The embodiment provides a preparation method of a graphene modified heat conduction material, which comprises the following steps:
s1. Porous C 3 N 4 The preparation of (1): uniformly mixing 7 parts by weight of urea and 1 part by weight of ammonium chloride solid, calcining at 600 ℃ for 4h, and cooling to obtain the porous C 3 N 4 ；
S2. Porous C 3 N 4 Preparation of graphene oxide: adding 10 parts by weight of the porous C prepared in the step S1 into an aqueous solution containing 4 parts by weight of graphene oxide 3 N 4 Ultrasonic treating at 2000W for 3h, heating at 200 deg.C for 20h, drying to obtain porous C 3 N 4 Graphene oxide;
s3. Porous C 3 N 4 Preparation of graphene oxide/carbon nanotubes: and (2) placing 5 parts by weight of single-walled carbon nanotubes in acid liquor for heating treatment, wherein the acid liquor is concentrated sulfuric acid and concentrated nitric acid, the mass of the acid liquor is 3, the heating treatment is carried out until the temperature is 80 ℃, the treatment time is 15 hours, filtering, washing and adding into water are carried out, and 10 parts by weight of the porous C prepared in the step (S2) are added into the water 3 N 4 Graphene oxide and 0.2 part by weight of silane coupling agent, heating for reaction, filtering, washing and drying to obtain porous C 3 N 4 Graphene oxide/carbon nanotubes;
the silane coupling agent is a compound mixture of KH590 and KH792, and the mass ratio is 7;
s4. Porous C 3 N 4 Preparation of graphene/carbon nanotubes: 14 parts by weight of the porous C obtained in step S3 3 N 4 Adding graphene oxide/carbon nano tube into water, uniformly dispersing by ultrasonic, adding 5 parts by weight of 32wt% ammonia water and 2 parts by weight of hydrazine hydrate, heating to 100 ℃, and reacting for 3 hours to obtain porous C 3 N 4 Graphene/carbon nanotubes;
s5, preparing a graphene modified heat conduction material: adding 10 parts by weight of PP resin into a mixing roll, and adding 2 parts by weight of the porous C prepared in the step S4 3 N 4 And/graphene/carbon nano tube, stirring and mixing at 200 ℃ for 15min at a rotation speed of 100r/min, hot-pressing at 200 ℃ for 5min, and releasing pressure for 40s, wherein the steps are repeated for 3 times to obtain the graphene modified heat conduction material.
Example 3
The embodiment provides a preparation method of a graphene modified heat conduction material, which comprises the following steps:
s1. Porous C 3 N 4 The preparation of (1): uniformly mixing 5 parts by weight of urea and 1 part by weight of ammonium chloride solid, calcining at 550 ℃ for 3 hours, cooling, and preparingGet porous C 3 N 4 ；
S2. Porous C 3 N 4 Preparation of graphene oxide: adding 10 parts by weight of porous C prepared in the step S1 into an aqueous solution containing 3 parts by weight of graphene oxide 3 N 4 Ultrasonic treatment at 1500W for 2h, heating reaction at 190 deg.C for 17h, and drying to obtain porous C 3 N 4 Graphene oxide;
s3. Porous C 3 N 4 Preparation of graphene oxide/carbon nanotubes: and (2) placing 4 parts by weight of single-walled carbon nanotubes in an acid solution for heating treatment, wherein the acid solution is concentrated sulfuric acid and concentrated nitric acid, the mass of the acid solution is 2 3 N 4 Graphene oxide and 0.15 part by weight of silane coupling agent, heating for reaction, filtering, washing and drying to obtain porous C 3 N 4 Graphene oxide/carbon nanotubes;
the silane coupling agent is a compound mixture of KH590 and KH792, and the mass ratio is 5;
s4. Porous C 3 N 4 Preparation of graphene/carbon nanotubes: 13 parts by weight of the porous C obtained in step S3 3 N 4 Adding graphene oxide/carbon nano tube into water, uniformly dispersing by ultrasonic, adding 4 parts by weight of 30wt% ammonia water and 1.5 parts by weight of hydrazine hydrate, heating to 95 ℃, and reacting for 2 hours to obtain porous C 3 N 4 Graphene/carbon nanotubes;
s5, preparing a graphene modified heat conduction material: adding 10 parts by weight of PP resin into a mixing roll, and adding 1.5 parts by weight of the porous C prepared in the step S4 3 N 4 And/graphene/carbon nano tube, stirring and mixing at 195 ℃ for 12min at a rotation speed of 70r/min, hot pressing at 195 ℃ for 4min, and releasing pressure for 35s, and repeating for 3 times to obtain the graphene modified heat conduction material.
Example 4
Compared with example 3, the silane coupling agent is single KH590, and other conditions are not changed.
Example 5
Compared with example 3, the silane coupling agent is single KH792, and other conditions are not changed.
Comparative example 1
Compared with example 3, steps S1 and S2 were not performed, and other conditions were not changed.
The method comprises the following steps:
s1, preparing graphene oxide/carbon nano tubes: placing 4 parts by weight of single-walled carbon nanotubes in acid liquor for heating treatment, wherein the acid liquor is concentrated sulfuric acid and concentrated nitric acid, the mass of the acid liquor is 2;
the silane coupling agent is a compound mixture of KH590 and KH792, and the mass ratio is 5;
s2, preparing the graphene/carbon nano tube: 13 parts by weight of the porous C obtained in step S3 3 N 4 Adding graphene oxide/carbon nano tube into water, uniformly dispersing by ultrasonic, adding 4 parts by weight of 30wt% ammonia water and 1.5 parts by weight of hydrazine hydrate, heating to 95 ℃, and reacting for 2 hours to obtain graphene/carbon nano tube;
s3, preparing the graphene modified heat conduction material: adding 10 parts by weight of PP resin into a mixing roll, adding 1.5 parts by weight of the graphene/carbon nano tube prepared in the step S2, stirring and mixing at 195 ℃ for 12min at a rotating speed of 70r/min, hot-pressing at 195 ℃ for 4min, releasing pressure for 35S, and repeating for 3 times to obtain the graphene modified heat conduction material.
Comparative example 2
Step S3 was not performed, and other conditions were not changed, as compared with example 3.
The method comprises the following steps:
s1. Porous C 3 N 4 The preparation of (1): uniformly mixing 5 parts by weight of urea and 1 part by weight of ammonium chloride solid, calcining at 550 ℃ for 3 hours, and cooling to obtain the porous C 3 N 4 ；
S2. Porous C 3 N 4 Preparation of graphene oxide: dissolving graphene oxide in water containing 3 parts by weightAdding 10 parts by weight of the porous C prepared in the step S1 into the solution 3 N 4 Ultrasonic treatment at 1500W for 2h, heating reaction at 190 deg.C for 17h, and drying to obtain porous C 3 N 4 Graphene oxide;
s3. Porous C 3 N 4 Preparation of graphene: 13 parts by weight of the porous C obtained in step S2 3 N 4 Adding graphene oxide into water, uniformly dispersing by ultrasonic, adding 4 parts by weight of 30wt% ammonia water and 1.5 parts by weight of hydrazine hydrate, heating to 95 ℃, and reacting for 2 hours to obtain porous C 3 N 4 (ii)/graphene;
s4, preparing the graphene modified heat conduction material: 10 parts by weight of PP resin was charged into a mixer, and 1.5 parts by weight of the cell C obtained in step S3 was added 3 N 4 Graphene, stirring and mixing at 195 ℃ for 12min at a rotation speed of 70r/min, hot pressing at 195 ℃ for 4min, and releasing pressure for 35s, and repeating for 3 times to obtain the graphene modified heat conduction material.
Test example 1
The graphene modified heat conduction materials prepared in examples 1 to 5 of the present invention and comparative examples 1 to 2 were subjected to performance tests, and the results are shown in table 1.
The heat conductivity is tested by a DRX-3A heat conductivity coefficient tester;
the tensile strength is detected according to a method of a standard GB/T1040.4;
the modulus of elasticity is measured according to the method of standard GB/T14694.
TABLE 1
| Group of | Thermal conductivity (Wm) -1 K -1 ） | Thermal conductivity enhancement rate (%) | Tensile Strength (MPa) | Modulus of elasticity (MPa) |
| Example 1 | 0.72 | 177 | 34.5 | 625 |
| Example 2 | 0.75 | 188 | 35.2 | 632 |
| Example 3 | 0.78 | 200 | 35.7 | 639 |
| Example 4 | 0.66 | 154 | 32.2 | 575 |
| Example 5 | 0.64 | 146 | 31.7 | 577 |
| Comparative example 1 | 0.45 | 73 | 27.6 | 535 |
| Comparative example 2 | 0.50 | 92 | 28.5 | 552 |
As can be seen from the above table, the graphene modified thermal conductive materials prepared in embodiments 1 to 3 of the present invention have excellent thermal conductive properties and mechanical properties.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the graphene modified heat conduction material is characterized by mixing and calcining urea and ammonium chloride to obtain porous C 3 N 4 Heating and mixing with graphene oxide solution to prepare porous C 3 N 4 Graphene oxide, modified by silane coupling agent, and mixed with acid-treated single-walled carbon nanotubes to obtain porous C 3 N 4 Reducing graphene oxide/carbon nanotubes to obtain porous C 3 N 4 The graphene/carbon nano tube is mixed with PP resin by stirring and hot pressing to prepare the graphene modified heat conduction material.
2. The method of claim 1, comprising the steps of:
s1. Porous C 3 N 4 The preparation of (1): uniformly mixing urea and ammonium chloride solids, calcining and cooling to obtain the porous C 3 N 4 ；
S2. Porous C 3 N 4 Preparation of graphene oxide: adding the graphene oxide solution into the solution prepared in the step S1Hole C 3 N 4 Ultrasonic treatment, heating reaction and drying to obtain porous C 3 N 4 Graphene oxide;
s3. Porous C 3 N 4 Preparation of graphene oxide/carbon nanotubes: putting the single-walled carbon nanotube into acid liquor for heating treatment, filtering, washing, adding water, and adding the porous C prepared in the step S2 3 N 4 Heating graphene oxide and silane coupling agent for reaction, filtering, washing and drying to obtain porous C 3 N 4 Graphene oxide/carbon nanotubes;
s4. Porous C 3 N 4 Preparation of graphene/carbon nanotubes: mixing the porous C prepared in the step S3 3 N 4 Adding graphene oxide/carbon nano tube into water, dispersing uniformly by ultrasonic, adding ammonia water and hydrazine hydrate, and heating for reaction to obtain porous C 3 N 4 Graphene/carbon nanotubes;
s5, preparing the graphene modified heat conduction material: adding PP resin into a mixing roll, and adding the porous C prepared in the step S4 3 N 4 Mixing and stirring the graphene/carbon nano tube, and hot-pressing to obtain the graphene modified heat conduction material.
3. The method according to claim 2, wherein the mass ratio of urea to ammonium chloride in step S1 is 3-7; the calcining temperature is 500-600 ℃, and the time is 2-4h.
4. The method according to claim 2, wherein the graphene oxide and the porous C in step S2 are mixed together 3 N 4 The mass ratio of (A) to (B) is 2-4:10; the ultrasonic power is 1000-2000W, and the processing time is 1-3h; the heating is carried out until the temperature is 180-200 ℃, and the reaction time is 15-20h.
5. The preparation method according to claim 2, wherein the acid solution in step S3 is concentrated sulfuric acid and concentrated nitric acid with a mass of 1-3; the heating treatment is carried out for 12-15h until the temperature is 60-80 ℃, and the single-walled carbon nanotube and the porous C are formed 3 N 4 The mass ratio of the graphene oxide to the silane coupling agent is (3-5); the heating reaction is carried out at the temperature of 70-90 ℃ for 1-3h; the silane coupling agent is at least one selected from KH550, KH560, KH570, KH580, KH590, KH602 and KH 792.
6. The preparation method according to claim 5, characterized in that the silane coupling agent is a compound mixture of KH590 and KH792, and the mass ratio is 3-7.
7. The method of claim 2, wherein the hole C in step S4 3 N 4 The mass ratio of graphene oxide/carbon nano tube, ammonia water and hydrazine hydrate is 12-15: 1-2; the concentration of the ammonia water is 27-32wt%; the heating reaction is carried out at the temperature of 90-100 ℃ for 1-3h.
8. The method according to claim 2, wherein the PP resin, the porous C, and the like in the step S5 are mixed 3 N 4 The mass ratio of graphene/carbon nanotube is 10:1-2; the stirring and mixing temperature is 190-200 ℃, the time is 10-15min, and the rotating speed is 50-100r/min; the hot pressing temperature is 190-200 ℃, the pressurizing time is 3-5min, the pressure is released for 30-40s, and the steps are repeated for 3 times.
9. The graphene modified heat conduction material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the graphene modified thermal conductive material of claim 9 in the preparation of a heat sink.
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