CN114261959A - Preparation method of graphene - Google Patents
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Abstract
The invention relates to the technical field of graphene materials, in particular to a preparation method of graphene. The preparation method provided by the invention comprises the following steps: mixing an organic carbon source and a reducing metal, and sequentially performing first calcination and second calcination in a protective atmosphere to obtain the graphene; the temperature of the first calcination is 500-650 ℃; the temperature of the second calcination is 750-1200 ℃. According to the preparation method, the organic carbon source and the reducing metal are directly mixed, conditions are provided for ensuring that the intermediate can be fully contacted with metal powder after the subsequent organic carbon source is converted into the intermediate, meanwhile, no solvent is needed to participate in the reaction in the whole reaction process, the organic carbon source is calcined to generate an amorphous carbon or carbide intermediate through the first calcination, the reducing metal is reacted with the intermediate through the second calcination, the impurity elements in the intermediate are removed to be changed into metal salts, and the intermediate is graphitized to be changed into the high-crystalline graphene.
Description
Technical Field
The invention relates to the technical field of graphene materials, in particular to a preparation method of graphene.
Background
Since the discovery of graphene materials in 2004, graphene has been extensively studied for its atomic-scale thickness, unique electrical properties, high mechanical strength, high thermal conductivity, and high specific surface area. Based on these advantages, graphene materials are commercially used in the energy field, the electronic device field, the conductive thin film and the composite material in the form of graphene, graphene oxide, reduced graphene oxide, CVD-grown thin films and other products. However, due to the limitation of graphene yield and product quality, large-scale industrial production and application are not yet realized.
Disclosure of Invention
The invention aims to provide a preparation method of graphene, which is simple and can realize industrial production.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of graphene, which comprises the following steps:
mixing an organic carbon source and a reducing metal, and sequentially performing first calcination and second calcination in a protective atmosphere to obtain the graphene;
the temperature of the first calcination is 500-650 ℃;
the temperature of the second calcination is 700-1200 ℃.
Preferably, the organic carbon source comprises one or more of melamine, dicyandiamide, glucose, polyimide and polyvinyl chloride.
Preferably, the reducing metal comprises one or more of magnesium, aluminum and zinc.
Preferably, the mass ratio of the organic carbon source to the reducing metal is (1-3): 1.
preferably, the heating rate of heating to the first calcination temperature is 5-55 ℃/min.
Preferably, the time of the first calcination is 60 to 180 min.
Preferably, the temperature of the second calcination is obtained by heating with the temperature of the first calcination as the starting temperature;
the heating rate of the heating is 5-20 ℃/min.
Preferably, the time of the second calcination is 20-60 min.
Preferably, after the second calcination is completed, the method further comprises the steps of first cleaning, suction filtration, second cleaning and drying which are sequentially performed.
Preferably, the first cleaning mode is ultrasonic cleaning, and the cleaning agent adopted by the first cleaning is hydrochloric acid;
and the second cleaning comprises sequentially cleaning with water and ethanol.
The invention provides a preparation method of graphene, which comprises the following steps: mixing an organic carbon source and a reducing metal, and sequentially performing first calcination and second calcination in a protective atmosphere to obtain the graphene; the temperature of the first calcination is 500-650 ℃; the temperature of the second calcination is 700-1200 ℃. According to the preparation method, the organic carbon source and the reducing metal are directly mixed, conditions are provided for ensuring that the intermediate can be fully contacted with the reducing metal powder after the subsequent organic carbon source is converted into the amorphous carbon or carbide intermediate, meanwhile, no solvent is needed to participate in the reaction in the whole reaction process, the organic carbon source is calcined to generate the amorphous carbon or carbide intermediate through first calcination, the reducing metal is reacted with the intermediate through second calcination, the impurity elements in the intermediate are removed to be changed into metal salts, and the intermediate is subjected to graphitization reaction to be changed into the high-crystalline graphene.
Drawings
Fig. 1 is an XRD pattern of graphene prepared in example 1;
fig. 2 is an XPS chart of the total spectrum of graphene prepared in example 1;
fig. 3 is an SEM image of graphene prepared in example 1;
fig. 4 is a TEM image of graphene prepared in example 1;
FIG. 5 is an AFM image of graphene prepared in example 1 dispersed on a silicon wafer;
FIG. 6 is a Raman spectrum of graphene prepared in examples 1 to 4;
fig. 7 is an XRD pattern of graphene prepared in examples 1 and 4;
FIG. 8 is an XPS plot of the graphenes prepared in examples 1 and 4;
FIG. 9 is a conductivity curve of graphene prepared in example 1 and comparative examples 1-3 under different pressures;
FIG. 10 is a Raman spectrum of graphene prepared in examples 4, 6 to 7, and 12 to 13;
FIG. 11 is a Raman spectrum of graphene prepared in examples 4 to 5 and 8 to 9;
fig. 12 is a raman spectrum of graphene prepared in examples 4, 10 and 11;
fig. 13 is a raman spectrum of graphene prepared in examples 4, 14, 15 and 16.
Detailed Description
The invention provides a preparation method of graphene, which comprises the following steps:
mixing an organic carbon source and a reducing metal, and sequentially performing first calcination and second calcination in a protective atmosphere to obtain the graphene;
the temperature of the first calcination is 500-650 ℃;
the temperature of the second calcination is 700-1200 ℃.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
In the invention, no solvent is needed to participate in the reaction in the whole reaction process,
in the invention, the organic carbon source preferably comprises one or more of melamine, dicyandiamide, glucose, polyimide and polyvinyl chloride; when the organic carbon source is more than two of the above specific choices, the invention has no special limitation on the proportion of the specific substances, and can be mixed according to any proportion.
In the present invention, the organic carbon source is preferably in the form of powder; the particle size of the organic carbon source is preferably 50-400 meshes, and more preferably 300-400 meshes.
In the present invention, the reducing metal preferably includes one or more of magnesium, aluminum and zinc; when the reducing metal is more than two of the specific choices, the proportion of the specific materials is not limited in any way, and the materials can be mixed according to any proportion.
In the present invention, the reducing metal is preferably in a powder form; the particle size of the reducing metal is preferably 50 to 400 meshes, and more preferably 100 to 200 meshes.
In the invention, the mass ratio of the organic carbon source to the reducing metal is preferably (1-3): 1, more preferably (1.8 to 2.2): 1, more preferably 2: 1.
The mixing method is not limited in any way, and can be carried out in a manner known to those skilled in the art and can ensure that the melamine and the magnesium are uniformly mixed. In the embodiment of the invention, the mixing mode is shaking and shaking.
In the present invention, the protective atmosphere is preferably an inert atmosphere, and more preferably an argon atmosphere.
In the invention, the temperature of the first calcination is 500-650 ℃, preferably 530-560 ℃, and most preferably 550 ℃; the time is preferably 60 to 180min, more preferably 85 to 95min, and most preferably 90 min. In the present invention, the rate of temperature increase to the first calcination temperature is preferably 5 to 55 ℃/min, more preferably 48 to 52 ℃/min, and most preferably 50 ℃/min.
In the present invention, the temperature of the second calcination is preferably obtained by raising the temperature from the temperature of the first calcination as the starting temperature; the temperature of the second calcination is 700-1200 ℃, preferably 900-1200 ℃, and most preferably 1000-1200 ℃; the time is preferably 20 to 60min, more preferably 25 to 35min, and most preferably 30 min. In the present invention, the rate of temperature increase to the second calcination temperature is preferably 5 to 20 ℃/min, more preferably 12 to 13 ℃/min, and most preferably 12.5 ℃/min.
In the present invention, the first calcination and the second calcination are preferably carried out using a corundum boat as a container and placed in a tube furnace.
After the second calcination is completed, the present invention also preferably includes cooling; the cooling is preferably natural cooling, and the termination temperature after the cooling is preferably room temperature.
After cooling to room temperature, the method also preferably comprises the steps of sequentially carrying out first cleaning, suction filtration, second cleaning and drying; the first cleaning mode is preferably ultrasonic cleaning, and the cleaning agent adopted by the first cleaning is preferably hydrochloric acid; the concentration of the hydrochloric acid is preferably 0.5M. The frequency of the ultrasonic cleaning is not limited in any way, and the ultrasonic cleaning can be cleaned within 20min by adopting the frequency well known to the skilled person.
The process of the suction filtration is not limited in any way, and can be carried out by a process known to those skilled in the art.
In the present invention, the second cleaning preferably comprises sequentially cleaning with water and ethanol; the cleaning process is not limited in any way, and can be performed by using an IDE process known to those skilled in the art.
In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 45 ℃, the time of the vacuum drying is not limited in any way, and the time known by the skilled person can be used to ensure that the prepared graphene is completely dried.
The following will explain the preparation method of graphene provided by the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Shaking and shaking 1000mg of melamine and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 1200 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 2
Shaking and shaking 1000mg of melamine and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 1000 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 3
Shaking and shaking 1000mg of melamine and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 900 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 4
Shaking and shaking 1000mg of melamine and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 5
Shaking and shaking 1000mg of melamine and 600mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 6
Shaking and shaking 1000mg of polyvinyl chloride and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 7
Shaking 1000mg of dicyandiamide and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 8
Shaking and shaking 1000mg of melamine and 400mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 9
Shaking and shaking 1000mg of melamine and 700mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 10
Shaking and shaking 1000mg of melamine and 500mg of aluminum powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 11
Shaking and shaking 1000mg of melamine and 500mg of zinc powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 12
Shaking and shaking 1000mg of polyimide and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 13
Shaking and shaking 1000mg of glucose and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 550 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 14
Shaking and shaking 1000mg of melamine and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 500 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 15
Shaking and shaking 1000mg of melamine and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 600 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Example 16
Shaking and shaking 1000mg of melamine and 500mg of magnesium powder (the particle size is 100-200 meshes) uniformly to obtain mixed powder;
and transferring the mixed powder to a corundum boat, placing the corundum boat in a tubular furnace, heating to 650 ℃ at a heating rate of 50 ℃/min in an argon atmosphere, preserving heat for 90min, heating to 700 ℃ at a heating rate of 12.5 ℃/min, preserving heat for 30min, naturally cooling to room temperature, placing the obtained crude product in 0.5M hydrochloric acid, ultrasonically cleaning for 20min, carrying out suction filtration, sequentially cleaning with 200mL of deionized water and 200mL of ethanol, and carrying out vacuum drying at 45 ℃ to obtain the graphene.
Comparative example 1
Acetylene black, a commercial conductive agent (available from mixicaceae crystal materials technologies, ltd.).
Comparative example 2
Keqin black (available from Hefei Kejing materials technology, Inc.) is a commercial conductive agent.
Comparative example 3
Commercial conductive agent SuperP (available from Synfex Crystal Material technology, Inc.).
Test example
XRD (X-ray diffraction) testing is carried out on the graphene prepared in the example 1, the testing result is shown in figure 1, as can be seen from figure 1, the peak of the graphene prepared in the example 1 is well matched with the standard PDF card NO.75-1621 of the graphene structure, and the sharp (002) crystal face peak shows the high crystallinity of the graphene product;
the graphene prepared in example 1 is subjected to XPS testing, and the testing result is shown in fig. 2, where fig. 2 is an XPS total spectrum, and as can be seen from fig. 2, the graphene mainly consists of C and only contains a very small amount of N and O;
SEM test was performed on the graphene prepared in example 1, and the test result is shown in fig. 3; the graphene prepared in example 1 is subjected to a TEM test, and the test result is shown in fig. 4, and as can be seen from fig. 3 to 4, the graphene mainly consists of transparent and flaky graphene, and the sheet diameter is about 1 μm; the graphene is carbon atoms in a hexagonal arrangement;
the graphene prepared in example 1 is dispersed on a silicon wafer for atomic force microscopy analysis, and the test result is shown in fig. 5, as can be seen from fig. 5, the thickness of the graphene is about 3nm, and the number of layers of the prepared graphene is about 8-9 because the thickness of single-layer graphene is about 0.35 nm;
the Raman spectrum of the graphene has three main peaks which are positioned at 1350cm-1The D peak of (a), mainly related to the defect content in graphene; at 1580cm-1G peak of (2), derived from sp in graphene2In-plane vibration of carbon atoms; and is located at 2700cm-1Nearby 2D peak, the 2D peak being the second order mode of the D peak. The defect density of graphene materials is generally characterized by the intensity ratio of the D peak to the G peak (ID/G). On the basis, the graphene prepared in the embodiments 1 to 4 is subjected to raman spectrum test, and the test result is shown in fig. 6, and as can be seen from fig. 6, as the temperature in the second calcination process gradually increases, the ID/G gradually decreases, which indicates that the defect content is significantly reduced, and is optimal at 1000 to 1200 ℃. From the experimental results of the peak shape of the 2D peak and the increase of I2D/G along with the denitrification temperature, the higher denitrification temperature can also be obtained to result in higher graphene crystallinity;
the XRD test is performed on the graphene prepared in examples 1 and 4, and the test result is shown in fig. 7, and it can be seen from fig. 7 that the XRD (002) crystal plane peak of the graphene synthesized at 1200 ℃ has a narrower peak shape, which indicates that the graphene product of example 4 has a higher degree of crystallinity;
the XPS test of the graphene prepared in examples 1 and 4 is shown in fig. 8, and it can be seen from fig. 8 that the XPS total spectrum clearly shows that the oxygen content of the product at 1200 ℃ is lower, indicating that the graphene obtained at 1200 ℃ has higher quality;
conductivity tests are carried out on the graphene prepared in the example 1 and the graphene prepared in the comparative examples 1-3 under different pressures, the test results are shown in fig. 9, and as shown in fig. 9, the conductivity of the graphene prepared in the example 1 is improved from 14.8S/cm to 41.5S/cm at 25 ℃ along with the increase of the pressure from 2MPa to 10 MPa. After the powder is compacted under the pressure of 10MPa, the conductivity of the graphene is about 4 times that of common commercial conductive agents, namely acetylene black, Ketjen black and SuperP;
the raman spectrum test of the graphene prepared in examples 4, 6 to 7, 12 to 13 is performed, and the test result is shown in fig. 10, as can be seen from fig. 10, the graphene synthesized by the melamine precursor has lower defect density and higher crystallinity than the graphene synthesized by the rest of the nitrogen-containing precursors, and the synthesized C has a triazine structure with higher polymerization degree than the other nitrogen-containing precursors due to the melamine3N4The intermediate has larger crystal grains and higher crystallinity, so that the graphene nanosheet obtained after denitrification and reduction of magnesium powder has higher quality;
the raman spectroscopy test of the graphene prepared in examples 4 to 5 and 8 to 9 showed that the graphene prepared in example 8 has high defect and low crystallinity, as compared with the graphene prepared in examples 4 to 5 and 9, and the graphene obtained in example 11 has more defects because the C3N4 cannot be sufficiently reduced in the denitrification reduction step due to the deficient magnesium powder content, as shown in fig. 11; compared with the embodiments 4-5 and 8, in the embodiment 9, more magnesium powder is used, but after the reaction is completed, the mixed product contains too much unreacted magnesium powder, so that excessive heat is released by the reaction of the magnesium powder and hydrochloric acid in the hydrochloric acid cleaning step, and the crystal structure of graphene mixed in the mixed product under the air atmosphere is damaged to generate defects.
The raman spectroscopy test was performed on the graphenes obtained in examples 4, 10 and 11, and the test results are shown in fig. 12, and it is understood from fig. 12 that as the reducibility of the reducing metal material increases (Mg > Al > Zn), the defect density of the obtained graphene product decreases, and the degree of crystallization increases.
The raman spectroscopy test of the graphene prepared in examples 4, 14, 15 and 16 is performed, and the test result is shown in fig. 13, as can be seen from fig. 13, the graphene product with better quality can be obtained at the first calcination temperature within the range of 500-650 ℃, the content of comprehensive defects and the degree of crystallization are integrated, and the condition of 550 ℃ is better.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of graphene is characterized by comprising the following steps:
mixing an organic carbon source and a reducing metal, and sequentially performing first calcination and second calcination in a protective atmosphere to obtain the graphene;
the temperature of the first calcination is 500-650 ℃;
the temperature of the second calcination is 700-1200 ℃.
2. The method of claim 1, wherein the organic carbon source comprises one or more of melamine, dicyandiamide, glucose, polyimide, and polyvinyl chloride.
3. The method of claim 1, wherein the reducing metal comprises one or more of magnesium, aluminum, and zinc.
4. The method according to claim 1, wherein the mass ratio of the organic carbon source to the reducing metal is (1-3): 1.
5. the method according to claim 1, wherein the rate of temperature increase to the first calcination temperature is 5 to 55 ℃/min.
6. The method according to claim 5, wherein the first calcination is carried out for 60 to 180 min.
7. The method according to claim 1, wherein the temperature of the second calcination is obtained by raising the temperature of the first calcination to the starting temperature;
the heating rate of the heating is 5-20 ℃/min.
8. The method according to claim 7, wherein the second calcination is carried out for 20 to 60 min.
9. The preparation method according to any one of claims 1 to 8, wherein after the second calcination is completed, the method further comprises sequentially performing first cleaning, suction filtration, second cleaning and drying.
10. The preparation method according to claim 9, wherein the first cleaning mode is ultrasonic cleaning, and the cleaning agent adopted in the first cleaning is hydrochloric acid;
and the second cleaning comprises sequentially cleaning with water and ethanol.
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| CN108598431A (en) * | 2018-04-28 | 2018-09-28 | 江苏科技大学 | Grapheme foam-nickel oxide combination electrode material and preparation method thereof |
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| CN107324835A (en) * | 2017-06-14 | 2017-11-07 | 三峡大学 | A kind of preparation method of the graphite skeleton of graphene-containing |
| CN108598431A (en) * | 2018-04-28 | 2018-09-28 | 江苏科技大学 | Grapheme foam-nickel oxide combination electrode material and preparation method thereof |
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