CN114229837B - Graphene film and preparation method thereof - Google Patents
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- CN114229837B CN114229837B CN202111537990.9A CN202111537990A CN114229837B CN 114229837 B CN114229837 B CN 114229837B CN 202111537990 A CN202111537990 A CN 202111537990A CN 114229837 B CN114229837 B CN 114229837B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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- 238000000034 method Methods 0.000 claims abstract description 24
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- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
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- 238000003825 pressing Methods 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims description 34
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- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 238000001237 Raman spectrum Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
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- 238000010438 heat treatment Methods 0.000 claims description 6
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- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
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- 238000005087 graphitization Methods 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
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- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
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- 229910002804 graphite Inorganic materials 0.000 description 7
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- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
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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
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- 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
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of new materials and application thereof, in particular to a graphene film and a preparation method thereof. The three-dimensional communicated porous metal with high porosity and high density is used as a template, and a graphene layer is catalytically grown on the surface of the metal template under the proper temperature and atmosphere conditions by utilizing a chemical vapor deposition process. And removing the metal substrate to obtain the three-dimensional communicated porous graphene skeleton. And pressing the three-dimensional graphene skeleton into a flexible film by applying pressure. The preparation parameters are regulated and controlled, and the thickness, the pores and the like of the graphene film can be regulated and controlled. The invention has simple process and low production cost. The prepared graphene film has high crystallization quality and flexibility, and has excellent heat conduction and electric conduction performances in the in-plane and vertical plane directions. The graphene film is of a full-carbon structure with high crystallization quality, can be stably used in an air environment below 800 ℃, and has great application potential in the fields of heat conduction, electric conduction, electromagnetic shielding and the like.
Description
Technical Field
The invention relates to the technical field of new materials and application thereof, in particular to a graphene film and a preparation method thereof.
Background
Graphene as a new material has excellent electric conductivity and heat conductivity, and the electron mobility of the graphene can reach 200000cm 2 V -1 s -1 Can realize the highest current transmission density at room temperature, and the heat conductivity coefficient is as high as 5300 and 5300W m -1 K -1 Much higher than carbon nanotubes and diamond. In addition, graphene is a honeycomb perfect lattice formed by single-layer carbon atoms, and has high structural stability and chemical stability. Therefore, the graphene has great application potential in the fields of heat conduction, electric conduction, electromagnetic shielding and the like.
With miniaturization and integration of electronic devices, power density of the electronic devices is rapidly increased, and heat dissipation of the electronic devices is becoming a bottleneck restricting performance improvement. The heat dissipation film material is widely applied to various electronic devices, especially mobile phones, flat plates, notebooks and other portable devices. Because the graphite/graphene material has a heat conduction property far higher than that of a metal material and has good flexibility, the current commercial heat dissipation film mainly comprises a graphite film prepared by taking polyimide (the raw material requirement is strict, the main Japanese production exists the neck risk) as a precursor and a graphene film prepared by taking graphene oxide as a raw material. The polyimide precursor film is mainly produced by foreign enterprises such as Japan, and the risk of neck clamping exists. The preparation process of the graphene oxide generally relates to dangerous chemicals such as potassium permanganate, concentrated sulfuric acid and the like, the preparation process is complex, chemical impurities and products are difficult to separate after being mixed, and the difficulty in removing the impurities is high. Meanwhile, due to the existence of a large number of defects such as surface functional groups, the heat conduction and electric conduction performances of the alloy are still not ideal even though the alloy is subjected to a subsequent complex reduction process. In particular, the thermal conductivity of reduced graphene oxide is two to three orders of magnitude lower than that of eigenstate graphene due to the destruction of the crystal lattice. Meanwhile, both types of thin film preparation processes require a slow temperature rise carbonization process for up to ten or more hours and a subsequent ultra-high temperature graphitization process for more than eight hours (the temperature is generally up to 2800 ℃ or more, which is very energy-consuming).
In addition, there is a very important but yet unsolvable problem in the field of thermal management, namely, a high-temperature and high-performance resistant thermal interface material. Traditional metal materials and ceramic materials have higher heat conduction performance, but cannot be directly applied as a thermal interface material due to higher hardness. The polymer-based thermal interface material, while providing good interface contact, has poor thermal conductivity, typically a thermal conductivity of 10W m -1 K -1 Below, while the temperature resistance is generally below 150 ℃ due to the presence of the polymer matrix material; however, the conventional graphite/graphene film material has good flexibility and high temperature resistance, but is characterized by highly directional (along the plane direction) structure and heat conduction anisotropy. The thermal conductivity of the thermal interface material is much lower than 10W m in the vertical plane direction required for the thermal interface material -1 K -1 Generally at 5W m -1 K -1 In the following, the application requirements cannot be satisfied at all.
As described above, two major types of graphite/graphene films currently have problems that are difficult to overcome in terms of preparation process and application performance. Therefore, the bottleneck problem is solved, and the high-temperature-resistant high-performance graphene film material is developed to be applied to the fields of heat dissipation film materials and heat conduction interface materials, so that the high-temperature-resistant high-performance graphene film material has important significance.
Disclosure of Invention
The invention aims to provide a graphene film and a preparation method thereof, wherein the graphene film material has high temperature resistance, has excellent heat conduction performance in a plane and in a direction perpendicular to the plane, solves the problem that the two types of graphite/graphene films are difficult to overcome in preparation process and application performance at present, and can be applied to the fields of heat dissipation film materials and heat conduction interface materials.
The technical scheme of the invention is as follows:
a method for preparing a graphene film, the method comprising the steps of:
(1) Heating the reaction furnace chamber to a set temperature of 600-1200 ℃ under the protection atmosphere of carrier gas;
(2) Placing a three-dimensional communicated porous metal matrix with high porosity and high density into a constant temperature area of a reaction furnace chamber, introducing reducing gas, and preserving heat for 0-60 min;
(3) Introducing a mixed atmosphere of carbon source gas, reducing gas and carrier gas into the reaction chamber, and catalyzing the surface of the porous metal matrix to grow graphene; the flow ratio of the carbon source gas, the reducing gas and the carrier gas in the mixed atmosphere is 1: (0-80): (0 to 100), preferably 1: (1-50): (0-50); the reaction time is 1min to 120min, preferably 20min to 100min;
(4) Cooling the porous metal matrix under the protective atmosphere of carrier gas, and taking out to obtain a three-dimensional communicated high-density graphene skeleton structure growing on the porous metal matrix;
(5) Removing the porous metal matrix by adopting a metal etching solution to obtain three-dimensional porous graphene;
(6) And pressing the obtained three-dimensional porous graphene to form a graphene film.
In the preparation method of the graphene film, in the step (1), the carrier gas protective atmosphere is one or more than two of argon, nitrogen and helium, the set temperature is 900-1100 ℃, and the graphene is grown by the reaction in the step (3) at the set temperature.
The preparation method of the graphene film comprises the following steps of2) Wherein the porous metal matrix is porous alloy formed by one or more than two metals of three-dimensional communicated porous nickel, porous copper, porous iron, porous cobalt, porous silver, porous gold, porous platinum and porous titanium with high porosity and high density, and preferably nickel, copper or nickel-copper alloy; the porosity of the porous metal matrix is distributed between 210 and 4000PPI, and the density is between 0.5 and 6.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the porous metal matrix has a porosity distribution of 500-3000 PPI and an areal density of 1.5-5.5 g/cm 3 。
In the preparation method of the graphene film, in the step (3), the carbon source gas is one or more than two of methane, ethane, ethylene and acetylene, the reducing gas is one or more than two of hydrogen and ammonia, and the carrier gas is one or more than two of argon, nitrogen and helium.
In the preparation method of the graphene film, in the step (4), the carrier gas protective atmosphere is one or more than two of argon, nitrogen and helium.
In the preparation method of the graphene film, in the step (5), the metal etching liquid is one or more than two mixed aqueous solutions of hydrochloric acid, sulfuric acid, nitric acid, ammonium persulfate and ferric chloride.
In the preparation method of the graphene film, in the step (6), the three-dimensional porous graphene is pressed into a film by means of extrusion or rolling, wherein the pressure is 0.2-300 MPa, and preferably 30-270 MPa.
According to the preparation method of the graphene film, the thickness, the pore and the morphology of the prepared porous graphene can be regulated and controlled by selecting different porous metal matrixes and/or regulating and controlling the temperature and the reaction atmosphere growth parameters in the reduction reaction; the thickness range of the prepared graphene film is 10-1000 mu m, and the density is 0.8-2.2 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the thickness of the prepared graphene film ranges from 100 to 500 mu m, and the density is 1.2 to 2.1g/cm 3 。
The graphene film prepared by the method is of a three-dimensional full-communication structure, and has excellent crystallization quality without graphitization treatment due to the catalytic activity of the porous metal matrix: the Raman spectrum of the graphene film is characterized, and the characteristic peak of the graphene is obvious and the defect-free peak (D peak) appears; the X-ray diffraction spectrum of the graphene film is characterized in that the characteristic diffraction peak of the graphene film is obvious, the peak position is 26.5 degrees, the half-width is 0.102 degrees, and the peak position deviation and the impurity peak are avoided.
The graphene film has controllable morphology, and has excellent heat conduction and electric conduction performances in the in-plane and vertical plane directions due to excellent crystallization quality and three-dimensional full-communication structural characteristics: the in-plane thermal conductivity is 400-1500W/mK, the vertical plane thermal conductivity is 10-180W/mK, and the electrical conductivity is 1500-20000S/cm; preferably, the in-plane thermal conductivity is 800 to 1450W/mK, the vertical plane thermal conductivity is 30 to 150W/mK, and the electrical conductivity is 3000 to 18000S/cm.
The design mechanism of the invention is as follows:
according to the invention, three-dimensional communicated porous metal with high porosity and high density is used as a template, and a graphene layer is catalytically grown on the surface of the metal template under the proper temperature and atmosphere conditions by utilizing a chemical vapor deposition process. And removing the metal substrate to obtain the three-dimensional communicated porous graphene skeleton. And pressing the three-dimensional graphene skeleton into a flexible film by applying pressure. The preparation parameters are regulated and controlled, and the thickness, the pores and the like of the graphene film can be regulated and controlled. The invention has simple process and low production cost. The prepared graphene film has high crystallization quality and flexibility, and has excellent heat conduction and electric conduction performances in the in-plane and vertical plane directions. The graphene film is of a full carbon structure with high crystallization quality, so that the graphene film can be stably used in an air environment below 800 ℃.
The invention has the following advantages and beneficial effects:
1. according to the invention, three-dimensional communicated height is used as a substrate template to catalyze and grow graphene. The morphology and thickness of the prepared graphene can be regulated and controlled by regulating and controlling the types and the growth parameters, so that different application requirements can be met.
2. All reactants and reaction liquid except inert carrier gas can be recycled, and harmful waste gas and waste liquid are not generated in the whole process, so that the preparation method is low-carbon and environment-friendly.
3. Due to the higher reaction temperature and the catalytic activity of the transition metal matrix, the graphene film prepared by the method has the crystallization quality comparable to that of mechanically stripped eigenstate graphene. Raman spectra characterize graphene with distinct and defect-free peaks (D peaks) present. As can be seen from XRD results, the graphene film has obvious graphene characteristic diffraction peak, 26.5 degrees peak position and 0.102 degree half-width, and no peak position shift and impurity peak. Therefore, the graphene film has excellent electric conductivity and heat conductivity.
4. The thermal weight loss result shows that the temperature of the graphene film can be tolerated to 800 ℃ in the air. Therefore, the material is different from the traditional heat conduction interface material (the heat conductivity is generally below 10W/mK, the temperature resistance is generally below 150 ℃), and the material can be used as a high-performance high-temperature-resistant (the heat conductivity is above 10W/mK, and the temperature resistance is above 800 ℃) heat interface material.
5. The heat conductivity of the traditional heat dissipation film material in the vertical plane direction is very low and is far lower than 10W m -1 K -1 Generally at 5Wm -1 K -1 In the following, the temperature difference gradient is obvious in the direction perpendicular to the plane of the heat dissipation film, the heat is difficult to effectively transfer in the whole heat dissipation film material, and the heat dissipation performance of the material is seriously affected. The heat dissipation film material prepared by the invention has heat conductivity of more than 10W/mK in the vertical plane direction, and has better heat dissipation performance compared with the traditional heat dissipation film material.
6. The invention has simple process, easy mass production, no need of carbonization and graphitization processes (the carbonization process generally needs to be slowly heated up to more than ten hours, the temperature of the subsequent graphitization process is more than 2800 ℃ and the time is more than eight hours), and low production cost.
7. The graphene film material disclosed by the invention does not appear in the prior art, has positive technical effects and application, and has great application potential in the fields of heat conduction, electric conduction, electromagnetic shielding and the like.
Drawings
Fig. 1 is a macroscopic photograph of a graphene film.
Fig. 2 is a microscopic photograph (surface) of a graphene film.
Fig. 3 is a microscopic photograph (side) of a graphene film.
Fig. 4 is a raman spectrum of a graphene film.
Fig. 5 is an XRD characteristic peak of the graphene film. In the figure, the abscissa 2θ represents the diffraction angle (degree), and the ordinate Intensity represents the relative Intensity (a.u.).
Fig. 6 is a thermal weight loss curve of a graphene film.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples. The thermal conductivity of the prepared graphene film was tested by using LFA 467 flash thermal conductivity meter (the meter is widely used in domestic electronic product manufacturers and scientific research units at present, and the test execution ASTM E1461 standard) of NETZSCH corporation in germany.
Example 1:
in this example, the reaction chamber was heated to 1000℃under a nitrogen atmosphere, and a constant temperature zone of 500PPI with a porosity of 2.5g/cm was added to the reaction chamber 3 The three-dimensional communicated high-porosity high-density porous nickel is filled with hydrogen, the temperature is kept for 10min, the flow of the hydrogen is 600sccm, and the effect of firstly filling the hydrogen is that: removing the oxide layer on the surface of the matrix; continuously introducing a mixed gas of ethylene and hydrogen, wherein the flow rate of the mixed gas is 620sccm, and the flow rate ratio of the ethylene to the hydrogen in the mixed gas is 1:30, the reaction time is 30min, and graphene is catalytically grown on the surface of the three-dimensional communicated high-porosity high-density porous nickel matrix.
Taking out the three-dimensional communicated high-density graphene skeleton growing on the porous metal matrix under the protection of nitrogen, putting the graphene skeleton into a hydrochloric acid aqueous solution (etching solution) with the concentration of 3mol/L, preserving the temperature for 60min at the temperature of 80 ℃, completely removing nickel in the graphene skeleton, taking out, cleaning and drying the graphene skeleton, and obtaining the three-dimensional communicated hollow graphene skeleton structure. And placing the graphene framework in a die of a tablet press, and applying pressure of 30MPa to obtain the graphene film.
As shown in fig. 1, the macro structure of the graphene film is shown in fig. 2 and 3, which are respectively microscopic morphology photographs of the surface and the side surface, and it can be seen from the figure that the graphene film has a three-dimensional communicated microstructure.
As shown in fig. 4, from the raman spectrum of the obtained sample, the graphene prepared by the method has high crystallization quality due to the higher reaction temperature and the catalytic activity of the metal matrix. Raman spectra characterize graphene with distinct and defect-free peaks (D peaks) present.
As shown in fig. 5, XRD results can show that the graphene film has obvious graphene characteristic diffraction peak, 26.5 degrees peak position and 0.102 degree half-width, and no peak position shift and impurity peak.
As shown in fig. 6, the thermal weight loss result shows that the temperature can be tolerated in the air to 800 ℃, so that the electric conduction and heat conduction properties are excellent. The thickness of the prepared graphene film is 100 mu m, and the density is 1.5g/cm 3 The in-plane thermal conductivity was 910W/mK, the vertical plane thermal conductivity was 42W/mK, and the electrical conductivity was 4250S/cm.
Because the hollow graphite film morphology after etching the metal substrate in the embodiment described below is basically the same as that in embodiment 1 in raman spectrum, XRD and thermogravimetric results, and no further description is given.
Example 2:
heating the reaction furnace chamber to 1000 ℃ under the protection of argon, adding 800PPI of porosity and 3.5g/cm of surface density into the constant temperature area of the reaction furnace chamber 3 The three-dimensional communicated high-porosity high-density porous copper is filled with hydrogen, the flow rate of the hydrogen is 500sccm, and the effect of firstly filling the hydrogen is as follows: removing the oxide layer on the surface of the matrix; continuously introducing a mixed gas of methane and hydrogen, wherein the flow rate of the mixed gas is 510sccm, and the flow rate ratio of methane to hydrogen in the mixed gas is 1:50, the reaction time is 50min, and graphene is catalytically grown on the surface of the three-dimensional communicated high-porosity high-density porous copper matrix.
Taking out the three-dimensional communicated high-density graphene skeleton growing on the porous metal matrix under the protection of nitrogen, putting the graphene skeleton into 2mol/L sulfuric acid aqueous solution (etching solution), preserving the temperature for 120min at 80 ℃, completely removing copper in the graphene skeleton, taking out, cleaning and drying the graphene skeleton, and obtaining the three-dimensional communicated hollow graphene skeleton structure. And placing the graphene framework in a die of a tablet press, and applying pressure of 40MPa to obtain the graphene film. The prepared graphiteThe alkene film thickness is 120 mu m, and the density is 1.8g/cm 3 The in-plane thermal conductivity was 830W/mK, the vertical plane thermal conductivity was 60W/mK, and the electrical conductivity was 3520S/cm.
Example 3:
heating the reaction furnace chamber to 1100 ℃ under the protection of argon, and adding 1100PPI of porosity and 5.1g/cm of surface density into the constant temperature area of the reaction furnace chamber 3 The three-dimensional communicated high-porosity high-density porous nickel is filled with hydrogen, the flow rate of the hydrogen is 500sccm, and the effect of firstly filling the hydrogen is as follows: removing the oxide layer on the surface of the matrix; continuously introducing a mixed gas of methane, hydrogen and argon, wherein the flow rate of the mixed gas is 1010sccm, and the flow rate ratio of methane to hydrogen in the mixed gas is 1:50, the reaction time is 70min, and graphene is catalytically grown on the surface of a three-dimensional communicated high-porosity high-density porous nickel matrix.
Taking out the three-dimensional communicated high-density graphene skeleton growing on the porous metal matrix under the protection of nitrogen, putting the graphene skeleton into a hydrochloric acid aqueous solution (etching solution) with the concentration of 3mol/L, preserving the temperature for 90 minutes at the temperature of 80 ℃, completely removing nickel in the graphene skeleton, taking out, cleaning and drying the graphene skeleton, and obtaining the three-dimensional communicated hollow graphene skeleton structure. And placing the graphene framework in a die of a tablet press, and applying 80MPa pressure to obtain the graphene film. The thickness of the prepared graphene film is 155 mu m, and the density is 1.95g/cm 3 The in-plane thermal conductivity was 1030W/mK, the vertical plane thermal conductivity was 30W/mK, and the electrical conductivity was 6575S/cm.
Example 4:
heating the reaction furnace chamber to 1100 ℃ under the protection of argon, and adding 1550PPI with the porosity and 5.3g/cm surface density into a constant temperature zone of the reaction furnace chamber 3 The three-dimensional communicated high-porosity high-density porous nickel-copper alloy is filled with hydrogen, the flow rate of the hydrogen is 500sccm, and the effect of firstly filling the hydrogen is as follows: removing the oxide layer on the surface of the matrix; continuously introducing a mixed gas of methane, hydrogen and argon, wherein the flow rate of the mixed gas is 1010sccm, and the flow rate ratio of methane to hydrogen in the mixed gas is 1:50, the reaction time is 80min, and graphite is catalytically grown on the surface of a three-dimensional communicated high-porosity high-density porous nickel-copper alloy matrixAn alkene.
Taking out the three-dimensional communicated high-density graphene skeleton growing on the porous metal matrix under the protection of nitrogen, putting the graphene skeleton into a hydrochloric acid aqueous solution (etching solution) with the concentration of 3mol/L, preserving the temperature for 110min at the temperature of 80 ℃, completely removing nickel-copper alloy in the graphene skeleton, taking out, cleaning and drying the graphene skeleton, and obtaining the three-dimensional communicated hollow graphene skeleton structure. And placing the graphene framework in a die of a tablet press, and applying 180MPa pressure to obtain the graphene film. The thickness of the prepared graphene film is 105 mu m, and the density is 2.1g/cm 3 The in-plane thermal conductivity was 1248W/mK, the vertical in-plane thermal conductivity was 35W/mK, and the electrical conductivity was 9600S/cm.
Example 5:
heating the reaction chamber to 1050 ℃ under nitrogen protection, adding 950PPI with porosity of 4.2g/cm and surface density into the constant temperature zone of the reaction chamber 3 The three-dimensional communicated high-porosity high-density porous cobalt is filled with hydrogen, the flow rate of the hydrogen is 500sccm, and the effect of firstly filling the hydrogen is that: removing the oxide layer on the surface of the matrix; continuously introducing a mixed gas of methane, hydrogen and argon, wherein the flow rate of the mixed gas is 1010sccm, and the flow rate ratio of methane to hydrogen in the mixed gas is 1:50, the reaction time is 60min, and graphene is catalytically grown on the surface of a three-dimensional communicated high-porosity high-density porous cobalt matrix.
Taking out the three-dimensional communicated high-density graphene skeleton growing on the porous metal matrix under the protection of nitrogen, putting the graphene skeleton into a hydrochloric acid aqueous solution (etching solution) with the concentration of 3mol/L, preserving the temperature for 110min at the temperature of 80 ℃, completely removing cobalt in the graphene skeleton, taking out, cleaning and drying the graphene skeleton, and obtaining the three-dimensional communicated hollow graphene skeleton structure. And placing the graphene framework in a die of a tablet press, and applying 90MPa pressure to obtain the graphene film. The thickness of the prepared graphene film is 115 mu m, and the density is 1.74g/cm 3 The in-plane thermal conductivity was 945W/mK, the vertical plane thermal conductivity was 48W/mK, and the electrical conductivity was 5880S/cm.
In conclusion, the graphene film disclosed by the invention is controllable in form and thickness, has very high crystallization quality, excellent in electric conduction and heat conduction properties, simple in preparation method and process, and low in preparation cost, and most of raw materials can be recycled. The above examples of the prepared graphene film are only illustrative, and should not be construed as limiting the scope of the present invention, and any method of equivalent substitution or modification according to the technical solution and the inventive concept of the present invention should be covered in the protection scope of the present invention.
Claims (6)
1. The preparation method of the graphene film is characterized by comprising the following steps of:
(1) Heating the reaction furnace chamber to a set temperature of 600-1200 ℃ under the protection atmosphere of carrier gas;
(2) Placing a three-dimensional communicated porous metal matrix with high porosity and high density into a constant temperature area of a reaction furnace chamber, introducing reducing gas, and preserving heat for 10-60 min;
(3) Introducing a mixed atmosphere of carbon source gas and reducing gas into the reaction furnace chamber, and catalyzing the surface of the porous metal matrix to grow graphene; the flow ratio of the carbon source gas to the reducing gas in the mixed atmosphere is 1: (30-80), and the reaction time is 1-120 min;
(4) Cooling the porous metal matrix under the protective atmosphere of carrier gas, and taking out to obtain a three-dimensional communicated high-density graphene skeleton structure growing on the porous metal matrix;
(5) Removing the porous metal matrix by adopting a metal etching solution to obtain three-dimensional porous graphene;
(6) Pressing the obtained three-dimensional porous graphene to form a graphene film;
in the step (2), the porous metal matrix is porous alloy formed by one or more than two metals of three-dimensional communicated porous nickel, porous copper, porous iron, porous cobalt, porous silver, porous gold, porous platinum and porous titanium with high porosity and high density; the porosity of the porous metal matrix is distributed between 210 and 4000PPI, and the density is between 0.5 and 6.5g/cm 3 ；
In the step (3), the carbon source gas is one or more than two of methane, ethane, ethylene and acetylene, and the reducing gas is one or two of hydrogen and ammonia;
the graphene film is of a three-dimensional full-communication structure, and has excellent crystallization quality without graphitization treatment due to the catalytic activity of the porous metal matrix: the Raman spectrum of the graphene film is characterized, and the characteristic peak of the graphene is obvious and the defect-free peak (D peak) appears; the X-ray diffraction spectrum of the graphene film is characterized in that the characteristic diffraction peak of the graphene film is obvious, the peak position is 26.5 degrees, the half-width is 0.102 degrees, and the peak position deviation and the impurity peak are avoided;
the shape of the graphene film is controllable, and the graphene film has excellent heat conduction and electric conduction properties in the in-plane and vertical plane directions due to excellent crystallization quality and three-dimensional full-communication structural characteristics: the in-plane thermal conductivity is 400-1500W/mK, the vertical plane thermal conductivity is 10-180W/mK, and the electrical conductivity is 1500-20000S/cm.
2. The method according to claim 1, wherein in the step (1), the carrier gas atmosphere is one or a mixture of two or more of argon, nitrogen and helium, the set temperature is 900 to 1100 ℃, and the reaction in the step (3) is performed at the set temperature when graphene grows.
3. The method of producing a graphene film according to claim 1, wherein in the step (4), the carrier gas protective atmosphere is one or a mixture of two or more of argon, nitrogen and helium.
4. The method according to claim 1, wherein in the step (5), the metal etching liquid is an aqueous solution of one or more of hydrochloric acid, sulfuric acid, nitric acid, ammonium persulfate, and ferric chloride.
5. The method for preparing a graphene film according to claim 1, wherein in the step (6), the three-dimensional porous graphene is pressed into a film by means of extrusion or rolling, and the pressure is 0.2-300 MPa.
6. The preparation method of the graphene film according to claim 1, wherein the method can regulate the thickness, the pores and the morphology of the prepared porous graphene by selecting different porous metal matrixes and/or regulating the temperature and the reaction atmosphere growth parameters in the reduction reaction; the thickness range of the prepared graphene film is 10-1000 mu m, and the density is 0.8-2.2 g/cm 3 。
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