CN112607726A - Graphene composite material, preparation method and application thereof - Google Patents
Graphene composite material, preparation method and application thereof Download PDFInfo
- Publication number
- CN112607726A CN112607726A CN202011497081.2A CN202011497081A CN112607726A CN 112607726 A CN112607726 A CN 112607726A CN 202011497081 A CN202011497081 A CN 202011497081A CN 112607726 A CN112607726 A CN 112607726A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- composite material
- graphene
- nitride
- stirring
- 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.)
- Pending
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 207
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 71
- 238000003756 stirring Methods 0.000 claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 45
- 230000009467 reduction Effects 0.000 claims abstract description 39
- 239000011258 core-shell material Substances 0.000 claims abstract description 30
- 150000004767 nitrides Chemical class 0.000 claims abstract description 24
- 239000007921 spray Substances 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 238000001694 spray drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000009775 high-speed stirring Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 230000017525 heat dissipation Effects 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000010248 power generation Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000006722 reduction reaction Methods 0.000 description 34
- 229910002601 GaN Inorganic materials 0.000 description 16
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 16
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 12
- 229910052733 gallium Inorganic materials 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 231100000331 toxic Toxicity 0.000 description 11
- 230000002588 toxic effect Effects 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000013081 microcrystal Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 229910052582 BN Inorganic materials 0.000 description 8
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- -1 polyoxyethylene octylphenol Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Images
Classifications
-
- 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
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0632—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0648—After-treatment, e.g. grinding, purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
- C01B21/0728—After-treatment, e.g. grinding, purification
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention relates to a graphene composite material, a preparation method and application thereof, which comprises the steps of preparing a graphene oxide dispersion liquid, gradually adding nitride into the graphene oxide dispersion liquid under the stirring state, continuously stirring and adding a dispersion stabilizer to obtain a graphene oxide mixed material, and preparing the nitride and graphene oxide mixed material into a nitride-graphene oxide composite material with a core-shell structure by a spray dryer under the stirring condition; and preparing the prepared nitride-graphene oxide composite material with the core-shell structure into a nitride-graphene composite material in a reduction mode. According to the invention, graphene oxide is uniformly coated on the surface of the nitride material, the obtained core-shell structure composite material can exist stably, the graphene composite material is integrally formed, the production cost is low, and the electric conductivity and the thermal conductivity are obviously improved.
Description
Technical Field
The invention relates to the technical field of heat dissipation and heat conduction, in particular to a graphene composite material, and a preparation method and application thereof.
Background
Graphene (GNPs) is a carbon material having a planar two-dimensional structure, has excellent electrical and thermal conductivity, has a large specific surface area, high transparency and good mechanical properties, and is widely used in the fields of electronic devices, biosensors, transparent conductive films, composite materials and the like.
For example, CN 107869047 a in the prior art discloses a graphene-boron nitride composite material and a preparation method thereof, which utilize the swelling and fusion effect of a graphene oxide coating on the surface of boron nitride to realize the crosslinking of boron nitride fibers. Graphene oxide is used as a sizing agent and a cross-linking agent, and is further reduced by an organic reducing agent to form a graphene layer.
As another example, another application document TW20184076A discloses a semiconductor structure having a graphene layer, wherein the semiconductor may be gallium nitride, grown into graphene on a copper foil by a metal organic chemical vapor deposition method; cleaning the semiconductor substrate, and drying by using nitrogen flow; transferring the graphene onto a semiconductor substrate, etching a copper foil, fixing the graphene layer, and cleaning with acetone; etching the surface of the graphene layer to form holes; and depositing a gallium nitride semiconductor on the surface of the graphene layer.
The composite materials prepared in the prior art have certain problems in stability due to simple coating or mixing. In addition, reducing agents such as hydrogen iodide and hydrazine hydrate involved in the reduction process belong to toxic and harmful chemical reagents, and do not accord with the development concept of green chemistry.
Disclosure of Invention
In order to overcome the technical defects in the prior art, the invention provides a graphene composite material, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the graphene composite material, the preparation method and the application thereof provided by the invention is as follows:
in a first aspect, the embodiment of the invention discloses a preparation method of a graphene composite material, which comprises the following steps:
(1) preparing a graphene oxide dispersion liquid, gradually adding a nitride into the graphene oxide dispersion liquid under a stirring state, continuously stirring and adding a dispersion stabilizer to obtain a graphene oxide mixed material, and preparing the nitride and graphene oxide mixed material into a core-shell nitride-graphene oxide composite material by a spray dryer under the premise of keeping stirring;
(2) and preparing the prepared nitride-graphene oxide composite material with the core-shell structure into a nitride-graphene composite material in a reduction mode.
In any of the above schemes, it is preferable that the graphene oxide dispersion liquid in step (1) is one or more of ultrasonic dispersion, mechanical grinding or high-speed stirring dispersion.
In any of the above embodiments, the concentration of the graphene oxide dispersion liquid in the step (1) is preferably in a range of 3 to 8 mg/ml.
In any of the above embodiments, the rotation speed of the continuous stirring in the step (1) is preferably in the range of 100 to 800 rpm.
In any of the above schemes, preferably, the air inlet temperature range of the spray drying in the step (1) is 20-220 ℃, and the air outlet temperature range is 50-100 ℃.
In any of the above schemes, preferably, the reduction mode in step (2) is one or more of laser reduction, thermal reduction or high pressure reduction.
Compared with the prior art, the preparation method of the graphene composite material has the advantages that the dispersion solvent of the graphene oxide is only aqueous solution, the reduction of the graphene oxide does not relate to toxic and harmful substances, the graphene oxide can be fully reduced by laser, heating or electromagnetism, the reduction effect is better than that of the prior art, and the electric conductivity and the thermal conductivity are obviously improved.
In a second aspect, the graphene composite material is prepared by the preparation method of the graphene composite material.
In any of the above schemes, preferably, the graphene composite material uses a nitride as an inner shell, and graphene is coated on the surface of the nitride to form a core-shell structure of an outer core.
In any of the above embodiments, preferably, the average particle size of the graphene composite material is in a range of 5 to 100 micrometers.
Compared with the prior art, the graphene composite material disclosed by the invention has the advantages that the graphene oxide is uniformly coated on the surface of the nitride material by adopting a spray drying technology, the obtained core-shell structure composite material can stably exist, the operation is simple, the graphene oxide is integrally formed, and the production cost is low.
In a third aspect, the graphene composite material is applied to heat dissipation of electronic devices or photovoltaic power generation.
Compared with the prior art, the graphene composite material disclosed by the invention is applied to heat dissipation of electronic devices or photovoltaic power generation, graphene oxide is uniformly coated on the surface of a nitride material by adopting a spray drying technology, the obtained core-shell structure composite material can stably exist, the operation is simple, the graphene oxide is integrally formed, and the production cost is low.
The dispersion solvent of the graphene oxide is only aqueous solution, the reduction of the graphene oxide does not relate to toxic and harmful substances, the graphene oxide can be fully reduced by laser, heating or electromagnetism, the reduction effect is better than that of the prior art, and the electric conductivity and the thermal conductivity are obviously improved.
Drawings
The drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification.
Fig. 1 is a schematic view of a preparation process of a graphene composite material according to the present invention.
Fig. 2 is a schematic structural diagram of a graphene composite material according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and 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.
In order to achieve the purpose of obviously improving the electric conductivity and the thermal conductivity, the invention provides a graphene composite material, wherein a nitride is used as an inner shell, graphene is coated on the surface of the nitride to form an outer core to form a core-shell structure, and the average particle size of the graphene composite material is 5-100 micrometers.
The invention also provides a preparation method of the graphene composite material, which comprises the following steps: the adopted technical scheme is as follows:
(1) preparing a graphene oxide dispersion liquid by ultrahigh-speed stirring and dispersing, stirring the graphene oxide dispersion liquid to form a central vortex, gradually adding a nitride into the graphene oxide dispersion liquid under a stirring state, and continuously stirring and adding a dispersion stabilizer to obtain a graphene oxide mixed material; preparing the nitride-graphene oxide material with a core-shell structure by using the nitride-graphene oxide mixed material through a spray dryer under the premise of keeping stirring;
(2) and performing reduction reaction on the prepared nitride-graphene oxide material with the core-shell structure to prepare nitride-graphene oxide.
The concentration of the graphene oxide dispersion liquid in the step (1) is 3-8 mg/ml; the graphene oxide dispersion liquid is one or more of ultrasonic dispersion, mechanical grinding or high-speed stirring dispersion.
The concentration range of the graphene oxide dispersion liquid in the step (1) is 3-8 mg/ml; the continuous stirring rotating speed range in the step (1) is 100-800 rpm.
The air inlet temperature range of the spray drying in the step (1) is 20-220 ℃, and the air outlet temperature range is 50-100 ℃.
The reduction mode in the step (2) is one or more of laser reduction, thermal reduction or high-pressure reduction.
The invention also provides an application of the graphene composite material, and the graphene composite material is applied to the fields of electronic product heat dissipation, photovoltaic power generation and the like.
For better understanding of the above technical solutions, the technical solutions of the present invention will be described in detail below with reference to the drawings and the detailed description of the present invention.
Example 1:
as shown in fig. 1 and fig. 2, an embodiment of the present invention discloses a preparation method of a graphene composite material, in which graphene oxide dispersion liquid with a concentration of 5mg/ml is prepared by ultrasonic dispersion, an ultrasonic treatment power is 80W, and a sheet diameter of graphene oxide in the obtained graphene oxide dispersion liquid is 5 micrometers; gradually adding boron nitride powder into the graphene oxide dispersion liquid through mechanical stirring, stirring the graphene oxide dispersion liquid to form a central vortex, adding the boron nitride powder into the center of the vortex, and fully mixing and dispersing at the rotating speed of 600 rpm; on the premise of keeping stirring, preparing the boron nitride-graphene oxide powder material with a core-shell structure from the boron nitride and graphene oxide mixture through a spray dryer, wherein the stirring speed of the spray dryer is 200rpm, the air inlet temperature is 20 ℃, and the air outlet temperature is 90 ℃;
the prepared boron nitride-graphene oxide powder material is prepared into a boron nitride-graphene composite material by a laser reduction method, the laser reduction time is 10s, and the laser power is 5W.
The dispersion solvent of the graphene oxide is only aqueous solution, the reduction of the graphene oxide does not relate to toxic and harmful substances, the graphene oxide can be fully reduced through laser, heating or electromagnetism, the reduction effect is better than that of the prior art, the electric conductivity and the thermal conductivity are obviously improved, the spray drying technology is adopted, the graphene oxide is uniformly coated on the surface of the nitride material, the obtained core-shell structure composite material can stably exist, the operation is simple, the graphene oxide is integrally formed, and the production cost is low.
Example 2:
as shown in fig. 1 and fig. 2, an embodiment of the present invention discloses a preparation method of a graphene composite material, which includes preparing a graphene oxide dispersion liquid with a concentration of 3mg/ml by ultra-high speed stirring and dispersing, wherein a stirring speed is 400krpm, and a sheet diameter of graphene oxide in the obtained graphene oxide dispersion liquid is 30 micrometers; gradually adding the gallium nitride flaky microcrystal into the graphene oxide dispersion liquid through mechanical stirring, stirring the graphene oxide dispersion liquid to form a central vortex, adding the gallium nitride flaky microcrystal into the center of the vortex, and fully mixing and dispersing at the rotating speed of 800rpm of mechanical stirring; stirring was continued and 0.01mg/ml of polyoxyethylene octylphenol ether-10 (OP10), a dispersion stabilizer, was added; preparing the gallium nitride and graphene oxide mixed material into a gallium nitride-graphene oxide flaky material with a core-shell structure by a spray dryer on the premise of keeping stirring; the stirring speed of the spray dryer is 100rpm, the air inlet temperature is 160 ℃, and the air outlet temperature is 70 ℃;
placing the prepared flaky material of gallium nitride-graphene oxide in a hydrogen-argon volume ratio of 1: 3, heating the mixed gas to 400 ℃ for 1h to prepare the gallium nitride-graphene oxide.
The dispersion solvent of the graphene oxide is only aqueous solution, the reduction of the graphene oxide does not relate to toxic and harmful substances, the graphene oxide can be fully reduced through laser, heating or electromagnetism, the reduction effect is better than that of the prior art, the electric conductivity and the thermal conductivity are obviously improved, the spray drying technology is adopted, the graphene oxide is uniformly coated on the surface of the nitride material, the obtained core-shell structure composite material can stably exist, the operation is simple, the graphene oxide is integrally formed, and the production cost is low.
Example 3:
as shown in fig. 1 and fig. 2, an embodiment of the present invention discloses a preparation method of a graphene composite material, in which graphene oxide dispersion liquid with a concentration of 8mg/ml is prepared by ultra-high speed stirring and dispersion, and the sheet diameter of graphene oxide in the obtained graphene oxide dispersion liquid is 70 μm; gradually adding aluminum nitride into the dispersion liquid through mechanical stirring, stirring the graphene oxide dispersion liquid to form a central vortex, adding the gallium nitride flaky microcrystal into the center of the vortex, fully mixing, and further grinding in a colloid mill; adding 0.01mg/ml of dispersion stabilizer OP10 during grinding; preparing the aluminum nitride and graphene oxide mixed material into a core-shell aluminum nitride-graphene oxide flaky material by a spray dryer on the premise of keeping stirring; the stirring speed of the spray dryer is 500rpm, the air inlet temperature is 100 ℃, and the air outlet temperature is 50 ℃;
and (3) placing the prepared aluminum nitride-graphene oxide material in a microwave oven for 1000W for 1-2S to prepare the aluminum nitride-graphene oxide material.
The dispersion solvent of the graphene oxide is only aqueous solution, the reduction of the graphene oxide does not relate to toxic and harmful substances, the graphene oxide can be fully reduced through laser, heating or electromagnetism, the reduction effect is better than that of the prior art, the electric conductivity and the thermal conductivity are obviously improved, the spray drying technology is adopted, the graphene oxide is uniformly coated on the surface of the nitride material, the obtained core-shell structure composite material can stably exist, the operation is simple, the graphene oxide is integrally formed, and the production cost is low.
Example 4:
as shown in fig. 1 and fig. 2, an embodiment of the present invention discloses a preparation method of a graphene composite material, which includes preparing a graphene oxide dispersion liquid with a concentration of 5mg/ml by ultra-high speed stirring and dispersing, wherein a stirring speed is 350krpm, and a sheet diameter of graphene oxide in the obtained graphene oxide dispersion liquid is 100 micrometers; gradually adding the gallium nitride flaky microcrystal into the dispersion liquid through mechanical stirring, stirring the graphene oxide dispersion liquid to form a central vortex, adding the gallium nitride flaky microcrystal into the center of the vortex, and fully mixing and dispersing at the rotating speed of 800rpm of mechanical stirring; preparing the gallium nitride and graphene oxide mixed material into a gallium nitride-graphene oxide flaky material with a core-shell structure by a spray dryer on the premise of keeping stirring; the stirring speed of the spray dryer is 200rpm, the air inlet temperature is 220 ℃, and the air outlet temperature is 100 ℃;
adding water into a high-pressure stirring container, putting the prepared gallium nitride-graphene oxide material into the high-pressure stirring container, sealing the stirring container, injecting hydrogen into the water, pressurizing to 350MPa, stirring at the rotating speed of 400rpm, and keeping stirring for 2 hours under the pressure to prepare the gallium nitride-graphene oxide.
The dispersion solvent of the graphene oxide is only aqueous solution, the reduction of the graphene oxide does not relate to toxic and harmful substances, the graphene oxide can be fully reduced through laser, heating or electromagnetism, the reduction effect is better than that of the prior art, the electric conductivity and the thermal conductivity are obviously improved, the spray drying technology is adopted, the graphene oxide is uniformly coated on the surface of the nitride material, the obtained core-shell structure composite material can stably exist, the operation is simple, the graphene oxide is integrally formed, and the production cost is low.
Example 5:
as shown in fig. 1 and fig. 2, an embodiment of the invention discloses a preparation method of a graphene composite material, which comprises the steps of preparing a graphene oxide dispersion liquid with a concentration of 4mg/ml by ultrasonic dispersion, wherein the ultrasonic treatment power is 90W, and the sheet diameter of graphene oxide in the obtained graphene oxide dispersion liquid is 50 micrometers; gradually adding boron nitride powder into the graphene oxide dispersion liquid through mechanical stirring, stirring the graphene oxide dispersion liquid to form a central vortex, adding the boron nitride powder into the center of the vortex, and fully mixing and dispersing at the rotating speed of 500 rpm; on the premise of keeping stirring, preparing the boron nitride-graphene oxide powder material with a core-shell structure by using a spray dryer, wherein the stirring speed of the spray dryer is 200rpm, the air inlet temperature is 50 ℃, and the air outlet temperature is 100 ℃;
the prepared boron nitride-graphene oxide powder material is prepared into a boron nitride-graphene composite material by a laser reduction method, the laser reduction treatment time is 8s, and the laser power is 4W.
The dispersion solvent of the graphene oxide is only aqueous solution, the reduction of the graphene oxide does not relate to toxic and harmful substances, the graphene oxide can be fully reduced through laser, heating or electromagnetism, the reduction effect is better than that of the prior art, the electric conductivity and the thermal conductivity are obviously improved, the spray drying technology is adopted, the graphene oxide is uniformly coated on the surface of the nitride material, the obtained core-shell structure composite material can stably exist, the operation is simple, the graphene oxide is integrally formed, and the production cost is low.
Example 6:
as shown in fig. 1 and fig. 2, an embodiment of the present invention discloses a preparation method of a graphene composite material, which includes preparing a graphene oxide dispersion liquid with a concentration of 5mg/ml by ultra-high speed stirring and dispersing, wherein a stirring speed is 600krpm, and a sheet diameter of graphene oxide in the obtained graphene oxide dispersion liquid is 60 micrometers; gradually adding the gallium nitride flaky microcrystal into the graphene oxide dispersion liquid through mechanical stirring, stirring the graphene oxide dispersion liquid to form a central vortex, adding the gallium nitride flaky microcrystal into the center of the vortex, and fully mixing and dispersing at the rotating speed of 800rpm of mechanical stirring; stirring was continued and 0.01mg/ml of polyoxyethylene octylphenol ether-10 (OP10), a dispersion stabilizer, was added; preparing the gallium nitride and graphene oxide mixed material into a gallium nitride-graphene oxide flaky material with a core-shell structure by a spray dryer on the premise of keeping stirring; the stirring speed of the spray dryer is 100rpm, the air inlet temperature is 200 ℃, and the air outlet temperature is 80 ℃;
placing the prepared flaky material of gallium nitride-graphene oxide in a hydrogen-argon volume ratio of 1: 3, heating the mixed gas to 400 ℃ for 1h to prepare the gallium nitride-graphene oxide.
The dispersion solvent of the graphene oxide is only aqueous solution, the reduction of the graphene oxide does not relate to toxic and harmful substances, the graphene oxide can be fully reduced through laser, heating or electromagnetism, the reduction effect is better than that of the prior art, the electric conductivity and the thermal conductivity are obviously improved, the spray drying technology is adopted, the graphene oxide is uniformly coated on the surface of the nitride material, the obtained core-shell structure composite material can stably exist, the operation is simple, the graphene oxide is integrally formed, and the production cost is low.
Example 7:
as shown in fig. 1 and fig. 2, an embodiment of the present invention discloses a preparation method of a graphene composite material, in which a graphene oxide dispersion liquid with a concentration of 7mg/ml is prepared by ultra-high speed stirring and dispersion, and the sheet diameter of graphene oxide in the obtained graphene oxide dispersion liquid is 60 micrometers; gradually adding aluminum nitride into the dispersion liquid through mechanical stirring, stirring the graphene oxide dispersion liquid to form a central vortex, adding the gallium nitride flaky microcrystal into the center of the vortex, fully mixing, and further grinding in a colloid mill; adding 0.01mg/ml of dispersion stabilizer OP10 during grinding; preparing the aluminum nitride and graphene oxide mixed material into a core-shell aluminum nitride-graphene oxide flaky material by a spray dryer on the premise of keeping stirring; the stirring speed of the spray dryer is 500rpm, the air inlet temperature is 220 ℃, and the air outlet temperature is 100 ℃;
and (3) placing the prepared aluminum nitride-graphene oxide material in a microwave oven for 1000W for 1-2S to prepare the aluminum nitride-graphene oxide material.
The dispersion solvent of the graphene oxide is only aqueous solution, the reduction of the graphene oxide does not relate to toxic and harmful substances, the graphene oxide can be fully reduced through laser, heating or electromagnetism, the reduction effect is better than that of the prior art, the electric conductivity and the thermal conductivity are obviously improved, the spray drying technology is adopted, the graphene oxide is uniformly coated on the surface of the nitride material, the obtained core-shell structure composite material can stably exist, the operation is simple, the graphene oxide is integrally formed, and the production cost is low.
Example 8:
as shown in fig. 1 and fig. 2, an embodiment of the present invention discloses a preparation method of a graphene composite material, which includes preparing a graphene oxide dispersion liquid with a concentration of 4mg/ml by ultra-high speed stirring and dispersing, wherein a stirring speed is 500krpm, and a sheet diameter of graphene oxide in the obtained graphene oxide dispersion liquid is 100 micrometers; gradually adding the gallium nitride flaky microcrystal into the dispersion liquid through mechanical stirring, stirring the graphene oxide dispersion liquid to form a central vortex, adding the gallium nitride flaky microcrystal into the center of the vortex, and fully mixing and dispersing at the rotating speed of 800rpm of mechanical stirring; preparing the gallium nitride and graphene oxide mixed material into a gallium nitride-graphene oxide flaky material with a core-shell structure by a spray dryer on the premise of keeping stirring; the stirring speed of the spray dryer is 200rpm, the air inlet temperature is 210 ℃, and the air outlet temperature is 90 ℃;
adding water into a high-pressure stirring container, putting the prepared gallium nitride-graphene oxide material into the high-pressure stirring container, sealing the stirring container, injecting hydrogen into the water, pressurizing to 350MPa, stirring at the rotating speed of 400rpm, and keeping stirring for 2 hours under the pressure to prepare the gallium nitride-graphene oxide.
The dispersion solvent of the graphene oxide is only aqueous solution, the reduction of the graphene oxide does not relate to toxic and harmful substances, the graphene oxide can be fully reduced through laser, heating or electromagnetism, the reduction effect is better than that of the prior art, the electric conductivity and the thermal conductivity are obviously improved, the spray drying technology is adopted, the graphene oxide is uniformly coated on the surface of the nitride material, the obtained core-shell structure composite material can stably exist, the operation is simple, the graphene oxide is integrally formed, and the production cost is low.
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a graphene composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a graphene oxide dispersion liquid, gradually adding a nitride into the graphene oxide dispersion liquid under a stirring state, continuously stirring and adding a dispersion stabilizer to obtain a graphene oxide mixed material, and preparing the nitride and graphene oxide mixed material into a core-shell nitride-graphene oxide composite material by a spray dryer under the premise of keeping stirring;
(2) and preparing the prepared nitride-graphene oxide composite material with the core-shell structure into a nitride-graphene composite material in a reduction mode.
2. The method for preparing the graphene composite material according to claim 1, wherein: the graphene oxide dispersion liquid in the step (1) is one or more of ultrasonic dispersion, mechanical grinding or high-speed stirring dispersion.
3. The method for preparing the graphene composite material according to claim 2, wherein: the concentration range of the graphene oxide dispersion liquid in the step (1) is 3-8 mg/ml.
4. The method for preparing a graphene composite material according to claim 3, wherein: the rotating speed range of the continuous stirring in the step (1) is 100-800 rpm.
5. The method for preparing the graphene composite material according to claim 4: the method is characterized in that: the air inlet temperature range of the spray drying in the step (1) is 20-220 ℃, and the air outlet temperature range is 50-100 ℃.
6. The method for preparing the graphene composite material according to claim 5: the method is characterized in that: the reduction mode in the step (2) is one or more of laser reduction, thermal reduction or high-pressure reduction.
7. A graphene composite material, characterized in that: prepared by the preparation method of the graphene composite material according to any one of claims 1 to 6.
8. The graphene composite material according to claim 7, wherein: the graphene composite material takes nitride as an inner shell, and graphene is coated on the surface of the nitride to form a core-shell structure of an outer core.
9. The graphene composite material according to claim 8, wherein: the average particle size range of the graphene composite material is 5-100 micrometers.
10. Use of the graphene composite material of any one of claims 7 to 9 in electronic device heat dissipation or photovoltaic power generation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011497081.2A CN112607726A (en) | 2020-12-17 | 2020-12-17 | Graphene composite material, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011497081.2A CN112607726A (en) | 2020-12-17 | 2020-12-17 | Graphene composite material, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112607726A true CN112607726A (en) | 2021-04-06 |
Family
ID=75240927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011497081.2A Pending CN112607726A (en) | 2020-12-17 | 2020-12-17 | Graphene composite material, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112607726A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11932581B1 (en) * | 2023-08-23 | 2024-03-19 | The Florida International University Board Of Trustees | Foams of nanomaterials and fabrication methods thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074619A (en) * | 2013-02-06 | 2013-05-01 | 上海应用技术学院 | Graphene oxide-silver compound particle and preparation method thereof |
| CN105949512A (en) * | 2016-05-12 | 2016-09-21 | 上海大学 | Intercalation assembly based boron nitride-graphene composite material as well as application and preparation method thereof |
| CN107746052A (en) * | 2017-10-31 | 2018-03-02 | 电子科技大学 | A kind of preparation method of the graphene aerogel of N doping |
| CN108565435A (en) * | 2018-05-09 | 2018-09-21 | 东南大学 | A kind of preparation method of graphene porous particle |
-
2020
- 2020-12-17 CN CN202011497081.2A patent/CN112607726A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074619A (en) * | 2013-02-06 | 2013-05-01 | 上海应用技术学院 | Graphene oxide-silver compound particle and preparation method thereof |
| CN105949512A (en) * | 2016-05-12 | 2016-09-21 | 上海大学 | Intercalation assembly based boron nitride-graphene composite material as well as application and preparation method thereof |
| CN107746052A (en) * | 2017-10-31 | 2018-03-02 | 电子科技大学 | A kind of preparation method of the graphene aerogel of N doping |
| CN108565435A (en) * | 2018-05-09 | 2018-09-21 | 东南大学 | A kind of preparation method of graphene porous particle |
Non-Patent Citations (2)
| Title |
|---|
| 董丽娜等: "导热石墨烯/聚合物纳米复合材料研究进展", 《现代塑料加工应用》 * |
| 黄金田 潘艳飞等: "《磁性棒状中空复合材料研究》", 31 December 2019, 吉林大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11932581B1 (en) * | 2023-08-23 | 2024-03-19 | The Florida International University Board Of Trustees | Foams of nanomaterials and fabrication methods thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107159068A (en) | A kind of preparation method of graphene composite aerogel | |
| CN112280312B (en) | Heat-conducting and wave-absorbing integrated graphene thermal interface material and preparation method thereof | |
| CN104108700B (en) | A kind of grapheme material powder and preparation method | |
| CN112210120A (en) | Heat-conducting filler and preparation method thereof, and polyarylethersulfone heat-conducting composite material and preparation method thereof | |
| CN106495133A (en) | High heat conduction Flexible graphene method for manufacturing thin film | |
| CN111629575A (en) | MXene-based nano composite wave-absorbing material and preparation method thereof | |
| CN111925630B (en) | High-strength electromagnetic shielding and heat conducting PBT/PET nano composite material and preparation method thereof | |
| CN110760189A (en) | Different layer type Ti3C2Filled high-thermal-conductivity silicone grease thermal interface material and preparation method thereof | |
| CN112607726A (en) | Graphene composite material, preparation method and application thereof | |
| CN111410190B (en) | Graphene-boron nitride composite film with insulating and heat-conducting properties and preparation method thereof | |
| CN111393856B (en) | Graphene-based high-thermal-conductivity low-thermal-resistance thermal conductive paste and preparation method thereof | |
| KR20100004399A (en) | High conducting film using low-dimensional materials | |
| Yu et al. | Fabrication of multi-nanocavity and multi-reflection interface in rGO for enhanced EMI absorption and reduced EMI reflection | |
| CN108529609A (en) | A kind of graphene aqueous solution and preparation method thereof | |
| CN110204214A (en) | A kind of preparation method of graphene-based film | |
| Huang et al. | Highly enhanced thermal conductivity from boron nitride nanosheets and MXene phonon resonance in 3D PMMA spheres composites | |
| CN106847364A (en) | A kind of preparation method and application of the laminated film of copper-zinc-tin-sulfur and three-dimensional grapheme | |
| CN111117155A (en) | Preparation method of graphene/epoxy resin composite material | |
| CN109988360B (en) | Graphene heat-conducting polymer material and preparation method thereof | |
| CN116535748A (en) | Thermal-conductivity-enhanced elastic thermal interface composite material and preparation method thereof | |
| CN103599806A (en) | Photocatalyst used for synthesis of aromatic aldehyde chemical and preparation method thereof | |
| CN110371935A (en) | A kind of preparation method and nanometer sheet of New Two Dimensional ternary compound | |
| CN106219532A (en) | A kind of nanometer carbon pipe array/graphite composite heat conduction film and preparation method thereof | |
| CN106219531A (en) | A kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film | |
| CN113265143B (en) | Preparation method of nano titanium dioxide/graphene aerogel/resin-based 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210406 |
|
| RJ01 | Rejection of invention patent application after publication |