CN114014308A - Preparation method of graphene composite material and graphene composite material - Google Patents

Preparation method of graphene composite material and graphene composite material Download PDF

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CN114014308A
CN114014308A CN202111519364.7A CN202111519364A CN114014308A CN 114014308 A CN114014308 A CN 114014308A CN 202111519364 A CN202111519364 A CN 202111519364A CN 114014308 A CN114014308 A CN 114014308A
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周建
丁古巧
张新强
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Jiangsu Yueda Investment Ltd By Share Ltd
Zhongke Yueda Shanghai Material Technology Co ltd
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Zhongke Yueda Shanghai Material Technology Co ltd
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Abstract

The invention discloses a preparation method of a graphene composite material, which comprises the following steps: (1) preparing aqueous suspension of a dispersing agent and a nano inorganic material, adding layered graphite into the aqueous suspension to prepare layered graphite suspension, shearing and dispersing, and homogenizing and impacting by adopting high-pressure micro-jet to prepare aqueous dispersion of the nano inorganic material and graphene; (2) and (3) carrying out spray drying or centrifugal drying on the nano inorganic material and the graphene aqueous dispersion liquid, and calcining at 300-800 ℃ to obtain the graphene composite material. The graphene composite material prepared by the method has few layers of graphene and concentrated layer distribution. The scanning electron microscope random test shows that the graphene is basically within 10 layers, the method is short in production time and high in graphene yield, response can be performed quickly according to application requirements, and interference on application effects caused by different processes and different manufacturers is reduced.

Description

Preparation method of graphene composite material and graphene composite material
Technical Field
The invention belongs to the field of graphene materials, and particularly relates to a preparation method of a graphene composite material and the graphene composite material prepared by the method.
Background
Graphene is a carbonaceous material with a single-atom two-dimensional honeycomb lattice structure formed by tightly packing carbon atoms, and has become the hottest nano-material due to the ultrathin and two-dimensional (2D) properties and unprecedented performances. The specific surface area of the graphene is ultrahigh (the theoretical calculation of the specific surface area of the single-layer graphene is 2620 m)2G), excellent electron mobility (200000 cm)2V · s), high thermal conductivity (thermal conductivity up to 5300W/m · k), superior mechanical properties and good biocompatibility.
The preparation method of the graphene mainly comprises a mechanical stripping method, a chemical oxidation method, a crystal epitaxial growth method, a chemical vapor deposition method, an organic synthesis method, a carbon nanotube stripping method and the like. The liquid phase stripping method in the mechanical stripping mode can prepare the dispersion liquid of the two-dimensional material nanosheets in a large scale, the two-dimensional material nanosheets prepared by stripping have the advantages of high purity, good crystal quality and simplicity and easiness in obtaining, but the size is not easy to control in the stripping process, the repeatability is poor, the time is long, a solvent with strong toxicity is sometimes adopted, and the yield of the prepared graphene is extremely low.
In the prior art, composite materials formed by graphene and inorganic materials (such as metals and metal oxides) are widely applied to various fields, such as heat and electricity conduction, super capacitors, lithium batteries, electrocatalysis, fuel cells and the like. Graphene composite materials are an important field in graphene application research.
At present, the main preparation method of the graphene composite material is to disperse the purchased graphene in the solution, disperse inorganic salt in the solution, perform in-situ reduction or hydrolysis in the solution to form oxidation, perform water washing treatment on impurities and high-temperature treatment to obtain the final product. The existing method for preparing the composite material of the graphene and the inorganic material has higher reaction requirement and is not easy to form large-scale preparation. And secondly, the graphene obtaining channels are different, so that the thickness of the graphene is uneven, and the application of the graphene composite material is greatly influenced. The number of layers of commercially available graphene is generally large, about 15-30 layers, and the performances of electric conduction, heat conduction, catalysis and the like of real graphene cannot be embodied, and researches of Partoens and the like (2006) find that when the number of layers of graphite layers is less than 10, an electronic structure different from that of common three-dimensional graphite is embodied, so that the fewer the number of layers of graphene is, the more concentrated the number distribution of the layers is, the better the performances of the graphene can be embodied. [ Partoens B, Peeters F M.from graphene to graphite: electronic structural around the K point. Phys Rew B,2006,74:075404-
In the prior art, various problems exist in the preparation of the composite material of graphene and inorganic materials, including the problems of more layers of graphene, non-centralized layer distribution, complex preparation method, more introduced impurities in the product and the like. Therefore, a great deal of problems and challenges still face to truly realize large-scale synthesis and industrial application of graphene composite materials.
Therefore, a preparation method capable of preparing a graphene composite material with a small number of layers and a concentrated distribution of the number of layers is needed, and the method is simple and low in cost.
Disclosure of Invention
Aiming at the defects of the preparation method of the graphene composite material in the prior art, the invention aims to provide the preparation method of the graphene composite material, the preparation method is simple and mild in steps, and the prepared product is few in graphene layers and concentrated in layer distribution.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a graphene composite material comprises the following steps:
(1) preparing aqueous suspension of a dispersing agent and a nano inorganic material, adding layered graphite into the aqueous suspension to prepare layered graphite suspension, shearing and dispersing, and homogenizing and impacting by adopting high-pressure micro-jet to prepare aqueous dispersion of the nano inorganic material and graphene;
(2) and (3) carrying out spray drying or centrifugal drying on the nano inorganic material and the graphene aqueous dispersion liquid, and calcining at 300-800 ℃ to obtain the graphene composite material.
Preferably, the layered graphite is selected from one or more of natural crystalline flake graphite, synthetic graphite, expandable graphite, expanded graphite, intercalated graphite, graphite nanosheets, electrochemically pretreated graphite, colloidal graphite and highly oriented thermally cracked graphite powder.
Preferably, the nano inorganic material is selected from one or more of nano zinc oxide, nano titanium dioxide, nano silicon dioxide, nano aluminum oxide, nano silver and nano carbon.
Preferably, the weight ratio of the graphene to the nano inorganic material is 1: 20-1: 1.
More preferably, the weight ratio of the graphene to the nano inorganic material is 1:15 to 1: 5.
Preferably, the particle size of the nano inorganic material is 5 to 100 nm.
Preferably, the dispersant can be substantially decomposed by high-temperature calcination in the range of 300-800 ℃.
Preferably, the dispersant is one or more selected from riboflavin sodium phosphate, protein colloid, sodium cholate and polyvinylpyrrolidone.
Preferably, the weight ratio of the dispersant to the graphene is 1: 20-1: 1.
More preferably, the weight ratio of the dispersant to the graphene is 1:15 to 1: 5.
Preferably, the temperature for mechanically processing the layered graphite suspension after shear dispersion in the step (2) is 10-80 ℃.
Preferably, the calcination in step (3) is in an oxygen-free condition or in an inert gas atmosphere.
The graphene composite material prepared by the preparation method is provided on the other hand, wherein the number of graphene layers is 2-10, and the number of 30% of graphene layers is 7. When the composite material is applied to engineering plastics, the composite material has good physical properties and heat conductivity.
According to the preparation method of the graphene composite material, in the graphene production stage, the characteristics of the nano-size effect, the hydrophilic property, the surface group and the like of the nano inorganic material and the dispersing agent are jointly acted on the surface of graphite, the high-pressure homogenization is utilized, the graphite stripping dispersion is promoted, the interaction of graphene sheet layers is reduced, a stable solution containing the dispersing agent, the nano inorganic material and the graphene solution is formed, and finally the uniform inorganic nanoparticle modified graphene sheet is obtained. And (3) carrying out centrifugation or spray drying on a dispersion liquid mixed by the dispersing agent, the nano inorganic material and the graphene, calcining at high temperature, and removing the dispersing agent to obtain the inorganic nano material and graphene composite material.
According to the preparation method of the graphene composite material, the graphene can be quickly and efficiently stripped under the assistance of the nano inorganic material and the dispersing agent, and the inorganic nano material and graphene composite material with good performance can be obtained. The scanning electron microscope random test shows that the graphene is basically within 10 layers, the method is short in production time and pollution-free, can quickly respond according to application requirements, and does not need to worry about interference on application effects caused by uneven graphene layers.
The graphene nano inorganic composite material prepared by the invention not only can simultaneously keep the inherent characteristics of graphene and inorganic nano particles, but also is convenient for the graphene to play the greatest advantage together with the composite material in practical application, generates a novel synergistic effect, and reduces the interference of different graphene layers produced by different manufacturers and different processes on the application effect.
In the graphene composite material, the number of layers of graphene in the composite of graphene and nano inorganic material is small, and the layers are mainly distributed and concentrated, so that the graphene composite material has a very good application prospect in the fields of antibiosis, heat conduction, static resistance, catalysis and the like.
Drawings
Fig. 1 and 2 are scanning electron micrographs of the dispersant, the nano-inorganic material, and the graphene dispersion prepared in example 1 of the present invention.
Fig. 3 and 4 are scanning electron microscope images of the dispersant, the nano inorganic material and the graphene prepared in comparative example 1 of the present invention.
FIG. 5 shows the transmission electron microscopy analysis results of the dispersion containing nano-titania powder and graphene obtained in example 1.
Fig. 6 is a transmission electron microscopy analysis of the number of layers of the randomly selected 100 graphene sheets in the suspension before filtering and drying of comparative example 2.
Detailed Description
In view of the disadvantages of the graphene composite material (i.e., the composite material formed by graphene and inorganic material (e.g., metal oxide)) and the graphene composite material finally obtained in the prior art, the inventors of the present invention have conducted extensive studies to find that the inorganic material and graphene are pre-mixed and then physically dispersed and exfoliated, and that the obtained product has a small number of layers and a concentrated number of layers, thereby completing the present invention.
In the description of the present invention, the graphene composite material is a composite material formed by graphene and a nano inorganic material, such as nano metal and nano metal oxide. The nano metal includes but is not limited to iron, copper, silver particles, and the nano metal oxide includes but is not limited to nano titanium dioxide, nano silicon dioxide, nano aluminum oxide, nano silver and nano carbon. The graphene composite material formed by the nano inorganic materials and the graphene has the performances of heat conduction, electric conduction, catalysis and the like. Has wide application, such as heat conducting and electric conducting material, super capacitor material, lithium battery material, electric catalytic material, fuel cell material, etc. Nano titanium dioxide means that the diameter of its particles is in the nanometer range. Other nanomaterials are similarly defined.
In the description of the present invention, the nano inorganic material means an inorganic material having a size (e.g., diameter) of 100nm or less.
The present invention is further described below in conjunction with specific embodiments, it being understood that the following examples are intended only to provide further details of the best modes of practicing the invention and should not be interpreted as limiting the scope of the invention. Experimental procedures in the following examples, where specific conditions are not specified, are generally in accordance with conventional procedures and conditions, or with conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by weight. The instruments used for the scanning electron microscopy analysis in the following examples are: the manufacturer: TESCAN CHINA, type: RISE Microscope), the instruments used for transmission electron microscopy analysis are: (FET-Tencnai G2F 20S-7 WIN)
Example 1
1.1 preparation of graphene composite titanium dioxide aqueous dispersion:
(1) adopting expanded graphite powder (Qingdatianda graphite Co., Ltd., model: 80 mesh) as stripping raw materials, firstly preparing riboflavin sodium phosphate and 25mg/ml nano titanium dioxide aqueous solution (the particle size of the nano titanium dioxide is 5-30nm, Anhui Xuancheng crystal Rui new material Co., Ltd.) with the concentrations of which are respectively 5mg/ml, and then adding the expanded graphite powder into the aqueous solution, wherein the weight ratio of the expanded graphite powder, the nano titanium dioxide, the riboflavin sodium phosphate and the water is 5:2.5: 0.5: and 92, shearing and dispersing the mixed solution for 15 minutes by using colloid mill equipment, rotating at the speed of 5000r/min to obtain an expanded graphite dispersion liquid, then sending the expanded graphite dispersion liquid into a high-pressure microjet homogenizer for impacting for 30 minutes, under the pressure of 280MPa and at the temperature of 35 ℃ to obtain a graphene composite dispersion liquid of 80mg/ml, analyzing the graphene composite titanium dioxide by using a transmission electron microscope to obtain images shown in figures 1 and 2, randomly testing the highest number of layers to be 9 layers (figure 1) and the lowest number of layers to be 2 layers (figure 2), obviously compounding nano titanium dioxide powder and graphene, randomly selecting 100 graphene by using a projection electron microscope, classifying and counting, wherein in figure 5, the graphene is basically in 10 layers. The number of layers of about 30% of the graphene in the product was 7.
1.2 preparation of graphene composite nano titanium dioxide material:
and (3) directly spray-drying the aqueous graphene dispersion liquid prepared in the step (1.1) to obtain graphene powder with less than 10 layers, and calcining the powder in nitrogen in a muffle furnace at 500 ℃ for 1h to obtain the graphene composite inorganic nano-material powder.
Example 2
2.1 preparation of graphene composite zinc oxide aqueous dispersion:
the method comprises the steps of using electrochemically treated graphite powder (refer to Chinese patent CN 107235487A, the name of the invention is graphene preparation method, Dingguqiao and the like, published: prepared by the content recorded in 2017, 10 and 10) as stripping raw materials, firstly preparing polyvinylpyrrolidone and nano zinc oxide aqueous solution (the particle size of nano zinc oxide is 15nm, Darcy concentrated nanotechnology (Changzhou) Co., Ltd.) with the concentrations of 5mg/ml and 20mg/ml respectively, and then adding the electrochemically stripped graphite into the aqueous solution, wherein the weight ratio of the electrochemically stripped graphite powder, the nano zinc oxide, the polyvinylpyrrolidone and the water is 5:2: 0.5: and 92.5, shearing and dispersing the mixed solution for 15 minutes by adopting colloid mill equipment at the rotating speed of 5000r/min, shearing and dispersing the mixed solution for 15 minutes to obtain an electrochemical stripping graphite dispersion solution, and then sending the electrochemical stripping graphite dispersion solution into a high-pressure micro-jet homogenizer for impacting for 30 minutes at the pressure of 250MPa and the temperature of 30 ℃ to obtain a 75mg/ml graphene composite zinc oxide dispersion solution. Transmission electron microscope analysis is carried out on the graphene composite zinc oxide, and the fact that the nano zinc oxide and the graphene are compounded together is obviously seen. And (3) adopting a projection electron microscope, randomly selecting 100 pieces of graphene, and classifying and counting, wherein the graphene is basically in 10 layers. The number of layers of about 50% of graphene in the product is 7-8.
2.2 preparation of graphene composite nano zinc oxide material:
and (3) directly spray-drying the aqueous graphene composite zinc oxide dispersion liquid prepared in the step (2.1) to obtain graphene composite zinc oxide powder with less than 10 layers, and calcining the powder in nitrogen in a muffle furnace at 550 ℃ for 1h to obtain the graphene composite nano zinc oxide material powder.
Example 3
3.1 preparation of graphene composite nano-alumina aqueous dispersion:
the method comprises the steps of adopting crystalline flake graphite powder (Qingdatianda graphite Co., Ltd., model number: 300 meshes) as a stripping raw material, firstly preparing aqueous solutions of 8mg/ml sodium cholate and 40mg/ml nano alumina (the particle size of the nano alumina is 20nm, Wingdegaseitai Co., Ltd.), and then adding the crystalline flake graphite powder into the aqueous solutions, wherein the weight ratio of the crystalline flake graphite powder to the sodium cholate to the nano alumina to the water is 8:0.8: 4: 81.2, shearing and dispersing the mixed solution for 15 minutes by using colloid mill equipment at the rotating speed of 5000r/min, shearing and dispersing the mixed solution for 15 minutes to obtain crystalline flake graphite dispersion liquid, and then homogenizing for 2 hours by using a high-pressure homogenizer at the pressure of 180MPa and the temperature of 25 ℃ to obtain 120mg/ml graphene composite nano-alumina aqueous dispersion liquid. Transmission electron microscope analysis is carried out on the graphene composite aluminum oxide, and the nano aluminum oxide and the graphene are obviously compounded together. And (3) adopting a projection electron microscope, randomly selecting 100 pieces of graphene, and classifying and counting, wherein the graphene is basically in 10 layers. The number of layers of about 55% of graphene in the product is 7-8.
3.2 preparation of graphene composite nano alumina powder:
and (3) directly spray-drying the aqueous graphene composite alumina dispersion liquid prepared in the step (3.1) to obtain graphene composite alumina powder with less than 10 layers, and calcining the powder in nitrogen in a muffle furnace at 450 ℃ for 1h to obtain the graphene composite nano alumina material powder.
Example 4
4.1 preparation of graphene composite nano-silica aqueous dispersion:
(1) taking a nano graphite sheet (Qingdatianda graphite Co., Ltd., model: 10000 meshes) as a stripping raw material, firstly preparing water solution of water-soluble collagen (molecular weight of 500-2000 Dalton) with the concentration of 6mg/ml and nano silicon dioxide (the particle size of the nano silicon dioxide is 20nm, winning Degussa Co., Ltd.) with the concentration of 5mg/ml, and then adding the nano graphite sheet into the water solution, wherein the weight ratio of the nano graphite sheet, the water-soluble collagen, the nano silicon dioxide and the water is 6:0.6: 0.5: and 92.9, shearing and dispersing the mixed solution for 15 minutes by adopting colloid mill equipment at the rotating speed of 5000r/min, shearing and dispersing the mixed solution for 15 minutes to obtain nano graphite sheet dispersion liquid, shearing and dispersing the mixed solution for 15 minutes to obtain nano graphite dispersion liquid, and then homogenizing for 2 hours by adopting a high-pressure homogenizer at the pressure of 280MPa and the temperature of 35 ℃ to obtain 65mg/ml graphene composite nano silicon dioxide aqueous dispersion liquid. Transmission electron microscope analysis is carried out on the graphene composite silicon dioxide, and the nano silicon dioxide and the graphene are obviously compounded together. And (3) adopting a projection electron microscope, randomly selecting 100 pieces of graphene, and classifying and counting, wherein the graphene is basically in 10 layers. The number of layers of about 65% of graphene in the product is 6-8.
4.2 preparation of graphene composite nano-silica:
and (3) directly spray-drying the aqueous graphene composite silicon dioxide dispersion liquid prepared in the step (4.1) to obtain graphene composite silicon dioxide powder with less than 10 layers, and calcining the powder in nitrogen in a muffle furnace at 450 ℃ for 1h to obtain graphene composite nano silicon dioxide material powder.
Comparative example 1
(1) Expanded graphite powder (Qingdatianda graphite Co., Ltd., model: 80 mesh) is used as a stripping raw material, riboflavin sodium phosphate with the concentration of 5mg/ml is prepared firstly, and then the expanded graphite powder is added into the water solution, wherein the weight ratio of the expanded graphite powder to the riboflavin sodium phosphate to the water is 5: 0.5: and 94.5, shearing and dispersing the mixed solution for 15 minutes by adopting colloid mill equipment at the rotating speed of 5000r/min to obtain expanded graphite dispersion liquid, and then sending the expanded graphite dispersion liquid into a high-pressure micro-jet homogenizer for impacting for 30 minutes at the pressure of 280MPa and the temperature of 35 ℃ to obtain 50mg/ml graphene composite dispersion liquid. Transmission electron microscopy analysis was performed on the graphene composite dispersion to obtain images shown in fig. 3 and 4, in which the highest number of layers was 35 (fig. 3) and the lowest number of layers was 6 (fig. 4) in random tests.
Comparative example 2
Preparing 10mg/mL graphene (the graphene is a mixture of products purchased from three different companies) aqueous solution, recording the solution as A, measuring 50mL absolute ethanol solution, slowly adding 15mL butyl titanate in the stirring state, violently stirring for 1h to prepare butyl titanate alcoholic solution B, then slowly dropwise adding the solution B into the solution A in the violently stirring state, continuously stirring for 2h at the speed of 300r/min, filtering, drying, and calcining for 1h at 50 ℃. Grinding and sieving the product (200 meshes) to obtain TiO2A graphene composite material. Randomly selecting 100 pieces of graphene in the suspension before filtering and drying,and (3) classifying and counting the number of layers after electron microscope analysis, as shown in fig. 6, wherein the number of layers of the graphene is randomly distributed in 2-30 layers.
The number of layers of commercially available graphene is large, the distribution of the number of layers is relatively dispersed, the number of layers is mostly 15-30, and the performances of electric conduction, heat conduction, catalysis and the like of the graphene are inferior to those of the graphene with the number of layers distributed in a concentrated manner of 2-10.
The graphene composite titanium dioxide prepared in the embodiment 2 and the comparative example 2 is respectively loaded on the surface of polypropylene fiber to form a photocatalytic net, river water (foul water ditch) is respectively subjected to visible light catalytic treatment, and after 120 days, COD (chemical oxygen demand), dissolved oxygen, ammonia nitrogen and total phosphorus content in two cups of water are tested, and the test result is shown in table 2.
TABLE 1 comparison of Sewage treatment data for example 2 and comparative example 2
COD(mg/L) Dissolved oxygen (mg/L) Ammonia nitrogen (mg/L) Total phosphorus (mg/L)
River water data 37 2.4 1.8 0.35
Example 2 16 8 0.37 0.06
Comparative example 2 22 4.6 0.65 0.11
Example 6
The graphene prepared in the comparative example 1 and alumina are modified by PA6 (recorded as X1), and meanwhile, the graphene composite alumina modified PA6 (recorded as X2) prepared in the example 3 is extruded and granulated at the temperature of 280 ℃ by using a double screw, and the tabletting test is carried out. The test data are shown in table 2, and the tensile strength, the flexural modulus, the thermal conductivity coefficient and the like of the graphene composite alumina are greatly improved.
TABLE 2 comparison of composite Properties
X1 X2
Test results
Tensile strength Mpa 69.92 75.5
Tensile modulus Gpa 6.52 13.16
Elongation at break% 1.07 1.03
Flexural strength Mpa 113.3 126.3
Flexural modulus Gpa 8.64 9.63
Simply supported beam gap KJ/m2 4.06 5
Density g/cm3 1.485 1.502
Thermal conductivity W/m k 2.19 2.6
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Further, it will be appreciated that, after reading the above teachings of the present invention, variations or modifications may be made to the invention by those skilled in the art, which equivalents are also within the scope of the invention as defined by the appended claims.

Claims (10)

1. A preparation method of a graphene composite material is characterized by comprising the following steps:
(1) preparing aqueous suspension of a dispersing agent and a nano inorganic material, adding layered graphite into the aqueous suspension to prepare layered graphite suspension, shearing and dispersing, and homogenizing and impacting by adopting high-pressure micro-jet to prepare aqueous dispersion of the nano inorganic material and graphene;
(2) and (3) carrying out spray drying or centrifugal drying on the nano inorganic material and the graphene aqueous dispersion liquid, and calcining at 300-800 ℃ to obtain the graphene composite material.
2. The method for preparing the graphene composite material according to claim 1, wherein the layered graphite is selected from one or more of natural crystalline flake graphite, synthetic graphite, expandable graphite, expanded graphite, intercalated graphite, graphite nanosheets, electrochemically pretreated graphite, colloidal graphite and highly oriented thermally cracked graphite powder.
3. The method for preparing the graphene composite material according to claim 1, wherein the nano inorganic material is selected from one or more of nano zinc oxide, nano titanium dioxide, nano silicon dioxide, nano aluminum oxide, nano silver and nano carbon.
4. The preparation method of the graphene composite material according to claim 1, wherein the weight ratio of the graphene to the nano inorganic material is 1: 20-1: 1.
5. The method for preparing the graphene composite material according to claim 1, wherein the nano inorganic material has a particle size of 5 to 100 nm.
6. The method for preparing the graphene composite material as claimed in claim 1, wherein the dispersant can be substantially decomposed by high temperature calcination within the range of 300-800 ℃.
7. The method for preparing the graphene composite material according to claim 6, wherein the dispersing agent is one or more selected from riboflavin sodium phosphate, protein colloid, sodium cholate and polyvinylpyrrolidone.
8. The preparation method of the graphene composite material according to claim 1, wherein the weight ratio of the dispersing agent to the graphene is 1: 20-1: 1.
9. The method for preparing the graphene composite material according to claim 1, wherein the temperature of the mechanically treated layered graphite suspension after shear dispersion in the step (2) is 10 to 80 ℃.
10. The graphene composite material prepared by the method according to any one of claims 1 to 9, wherein the number of graphene layers is 2-10 and the distribution of the number of layers is concentrated.
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