CN110054176B - High-conductivity graphene, preparation method and application thereof - Google Patents
High-conductivity graphene, preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- 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
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Abstract
The invention provides a preparation method of high-conductivity graphene, which comprises the following steps: step (1), uniformly mixing graphene oxide and a catalyst to obtain a raw material mixture; step (2), placing the raw material mixture in a mixed atmosphere of reducing gas and inert gas for pretreatment to obtain pretreated graphene; and (3) placing the pretreated graphene in the same atmosphere for microwave irradiation treatment to obtain the high-conductivity graphene, wherein the time for preparing the graphene by the preparation method provided by the invention is only 0.1-6S, and the preparation method is more suitable for industrially preparing graphene materials, and the preparation method can be used for preparing graphene materials with the conductivity of more than or equal to 30000S/m, the oxygen content of less than or equal to 5 wt%, and ID/IG≤0.5、I2D/IGThe graphene material with high conductivity has the advantages of large lamella size of more than or equal to 0.5, less defects and less layers, does not need high-temperature and high-pressure reaction conditions or participation of toxic reducing agents in the reaction process, is more energy-saving and environment-friendly, and is suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to the field of carbon material synthesis, in particular to a preparation method of high-conductivity graphene.
Background
In 2004, two scientists of Manchester university in England, Andeli Gem and Constantin Novoschloff succeeded in exfoliating highly oriented pyrolytic graphite to obtain a two-site material graphene with a monoatomic layer thickness, wherein graphene is a sp-type material of carbon atoms2The hexagonal honeycomb two-dimensional structure material formed by the hybrid track has a plurality of excellent performances, such as super-strong mechanical performance, extremely high carrier mobility, extremely high heat conduction performance, light transmittance of 97% and the like, and has wide application prospects in the fields of electronics, energy storage, sensors, biology and the like due to the excellent characteristics of graphene.
To date, graphene has many preparation methods, mainly including the following: the graphene prepared by the mechanical stripping method has high quality, but large-scale industrial production is difficult to realize, the graphene prepared by the SiC epitaxial growth method and the chemical vapor deposition method has high quality, but vapor deposition equipment is required, so that the defects of high cost, harsh conditions and the like exist, and how to transfer the prepared graphene is also a great difficulty.
In the existing method for preparing graphene by using a redox method, a chemical reducing agent or high-temperature treatment is mainly used for reducing graphene oxide to obtain redox graphene, the chemical reducing agent such as hydrazine hydrate and the like can pollute the environment in large-scale use, the prepared graphene has low quality, low single-layer rate and high oxygen content, the graphene oxide is reduced by using a high-temperature treatment method, and the prepared graphene has good quality, low oxygen content and high conductivity, but the required temperature is high, the energy consumption is high, and the industrial application potential is weak.
In order to solve the defects of the method for preparing graphene by using the oxidation-reduction method, in the prior art, a method combining chemical reduction and high-temperature reduction is usually used for preparing a high-conductivity graphene material, for example, a graphene oxide film is reduced by microwave heating in CN106554007A to obtain a graphene material with a conductivity of about 10000.
Therefore, based on the prior art, those skilled in the art need to develop a fast, environment-friendly and low-cost method for preparing high-quality graphene, especially high-conductivity graphene.
Disclosure of Invention
In view of the defects of the prior art, one of the purposes of the present invention is to provide a preparation method of high conductivity (the conductivity is more than or equal to 30000S/m) graphene, which comprises the following steps:
step (1), uniformly mixing graphene oxide and a catalyst to obtain a raw material mixture;
step (2), placing the raw material mixture obtained in the step (1) in a mixed gas of reducing gas and inert gas for pretreatment to obtain pretreated graphene;
and (3) placing the pretreated graphene obtained in the step (2) in a mixed gas of reducing gas and inert gas for microwave irradiation treatment to obtain the high-conductivity graphene.
According to the method, the mixture of the graphene and the catalyst is placed in a reducing atmosphere for pretreatment, so that reducing gas is adsorbed and tightly combined on the surface of the catalyst, the activation energy required by reduction reaction is reduced, and the high-conductivity graphene material is obtained through reduction by microwave irradiation. Compared with the graphene material obtained by the traditional oxidation-reduction method or microwave thermal reduction method, the high-conductivity graphene prepared by the method provided by the invention has fewer layers, fewer defects and higher conductivity, and the preparation time of the reduced graphene oxide material is greatly shortened.
Preferably, the microwave irradiation treatment time in the step (3) is 0.1 to 6s, such as 0.2s, 0.5s, 1s, 2s, 3s, 4s, 5s, 5.5s, 5.8s, etc., preferably 1 to 5 s.
Preferably, the irradiation power of the microwave irradiation treatment in the step (3) is 100-2000W, such as 120W, 200W, 300W, 500W, 800W, 1200W, 1600W, 1900W, etc., and more preferably 700-1000W.
Preferably, the pretreatment described in the step (2) is carried out by leaving the raw material mixture in a mixed gas atmosphere of a reducing gas and an inert gas.
Preferably, the temperature of the pretreatment is 0 to 50 ℃, for example, 1 ℃, 5 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 45 ℃ and the like.
Preferably, the pretreatment time is 1-30 min, such as 2min, 4min, 8min, 14min, 20min, 24min, 26min, 28min, and the like, and more preferably 5-10 min.
Preferably, the volume of the reducing gas in step (2) and step (3) is at least 5% of the total volume of the mixed gas, such as 6%, 10%, 20%, 30%, 40%, 60%, 80%, 90% of the total volume of the mixed gas.
Preferably, the reducing gas in step (2) and step (3) includes any one of hydrogen gas, ammonia gas, hydrogen sulfide gas, carbon monoxide gas and nitric oxide gas, or a mixed gas of at least two of them.
Preferably, the inert gas in step (2) and step (3) comprises any one of nitrogen, argon, helium, neon, krypton or xenon or a mixture of at least two of the nitrogen, argon, helium, neon, krypton and xenon.
Preferably, the graphene oxide in step (1) is obtained by subjecting graphite to intercalation oxidation, such as methods for preparing graphene oxide, which are well known in the art, including electrochemical oxidation, Hummers, Brodie, staudenmier, and various modifications thereof.
Preferably, the mixing in step (1) is performed by mixing the graphene oxide dispersion with the catalyst, and then drying to remove the solvent.
Preferably, the drying to remove the solvent is performed by any one of vacuum drying, heat drying, freeze drying and natural drying.
Preferably, the catalyst in step (1) is any one or a mixture of at least two of elementary metals and metal salts of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII, and more preferably any one or a mixture of at least two of palladium dichloride, platinum tetrachloride, iron dichloride, ferrous sulfate and cobalt nitrate.
Preferably, the weight ratio of the graphene oxide to the catalyst in the raw material mixture in the step (1) is (10-2000): 1, for example, 11:1, 40:1, 100:1, 400:1, 800:1, 1200:1, 1600:1, 1900:1, 1950:1, and the like, and more preferably (200-500): 1.
The second purpose of the present invention is to provide a high conductivity graphene prepared by the above preparation method.
Preferably, the conductivity of the high conductivity graphene is equal to or more than 30000S/m, such as 31000S/m, 35000S/m, 40000S/m, 50000S/m, 60000S/m, 70000S/m, 80000S/m, 90000S/m and the like, and more preferably equal to or more than 60000S/m.
Preferably, the content of oxygen element in the high conductivity graphene is less than or equal to 5 wt% by mass, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 4.5 wt%, etc., and more preferably less than or equal to 3 wt%.
Preferably, the Raman spectrum of the high-conductivity graphene is 1250-1450 cm-1Maximum peak height I of defect peak (D peak) in wavelength rangeDAt 1500-1700 cm-1Peak height I of crystal peak (G peak) in wavelength rangeGAnd the sum of the distances is 2600 to 2800cm-1Maximum peak height I of scattering peak (2D peak) in wavelength range2DThe relationship between them is: i isD/IG≤0.5，I2D/IG≧ 0.5, e.g., ID/IGCan be 0.1, 0.2, 0.3, 0.4, etc., I2D/IGAnd may be 0.6, 1, 1.6, 2.1, 2.5, etc.
Preferably, the defect peak height IDAnd the peak height of the crystallization peak IGThe relationship between them is: i isD/IG≤0.2。
Preferably, the crystallization peak height IGAnd the maximum peak height of the scattering peak I2DThe relationship between them is: i is2D/IG≥0.8。
The third purpose of the invention is to provide the application of the high-conductivity graphene, wherein the high-conductivity graphene has the conductivity of more than or equal to 30000S/m and the oxygen content of less than or equal to 5 wt%, and has a regular structure and no defect on the surface, so that the high-conductivity graphene has excellent electric and heat conduction performance and can be used for preparing electric conduction, heat conduction or photoelectric conversion materials.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the traditional method, the time for preparing the graphene by the preparation method of the graphene provided by the invention is greatly reduced, only 0.1-6 s is needed, the preparation time of the graphene material can be greatly shortened, and the preparation method is more suitable for industrially preparing the graphene material.
(2) The preparation method provided by the invention can prepare the material with the conductivity of more than or equal to 30000S/m, the oxygen content of less than or equal to 5wt percent and ID/IG≤0.5、I2D/IGThe high-conductivity graphene material has the advantages of large lamella size of more than or equal to 0.5, less layer number and less defects.
(3) The preparation method provided by the invention does not need high-temperature and high-pressure reaction conditions or participation of toxic reducing agents, is more energy-saving and environment-friendly, and is suitable for large-scale popularization and application.
Drawings
FIG. 1 is a low-magnification transmission electron microscope (magnification 10) of the high-conductivity graphene 1 obtained in example 16Double) photograph.
FIG. 2 is a high-magnification transmission electron microscope (magnification 10) of the high-conductivity graphene 1 obtained in example 18Double) photograph.
Fig. 3 is a raman spectrum of the high conductivity graphene 1 obtained in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The method for preparing graphene oxide used in the present invention is not particularly limited, but is preferably prepared by Hummers method, and commercially available graphene oxide or graphene oxide prepared by other methods may be used according to the actual situation.
The method for preparing the graphene oxide by the Hummers method comprises the following specific steps: weighing 5g of 300-mesh crystalline flake graphite and 2g of NaNO3120mL of concentrated H was added2SO4Stirring the mixed solution in ice bath for 30min20g of KMnO was added4After reacting for 60min, moving the mixture into a warm water bath at 40 ℃ for further reaction for 30min, then slowly adding 230mL of deionized water, keeping the reaction temperature at 98 ℃, stirring for 5min, and then adding a proper amount of H2O2Filtering when no bubbles are generated, washing the solution for many times to be neutral by using deionized water and 5% hydrochloric acid, centrifuging, fully drying in a vacuum drying oven at the temperature of 60 ℃ to obtain graphite oxide, dispersing the graphite oxide in water to obtain a brown yellow solution, performing ultrasonic treatment for 1h, and performing centrifugal separation to obtain the graphene oxide.
The high-conductivity graphene and the reduced graphene obtained in the above examples and comparative examples were subjected to characterization analysis by the following tests, and the results are listed in table 1.
(1) Morphology characterization of graphene
The morphology of the obtained graphene sample is observed by a Tecnai G220S-TWIN type Transmission Electron Microscope (TEM), and the test method comprises the steps of dispersing the sample in an ethanol solution, dripping the ethanol solution on the surface of a copper mesh, naturally drying the copper mesh, and observing the sample by using the TEM respectively at the magnification of 106Sum of about 108Left and right images, where TEM test parameters are: the test voltage was 200 kV.
(2) Raman spectroscopy
The sample is tested to 1250-1450 cm by a Renishaw inVia plus type Raman spectrometer-1Peak height I of peak D in wavelength rangeDAt 1500-1700 cm-1Peak height I of G peak in wavelength rangeGAnd the sum of the distances is 2600 to 2800cm-1Peak height I of 2D peak in wavelength range2DThe test parameters are as follows: the laser wavelength is 514nm, the power attenuation is 100%, and the scanning range is 1000-3500 cm-1。
(3) Oxygen content test
The carbon-oxygen ratio of a sample is tested by an EXCALAB 250Xi type photoelectron spectroscopy (XPS), the ratio of the peak height of a C1s peak and the peak height of an O1s peak of the obtained spectrogram is calculated as the carbon-oxygen ratio of the sample, the oxygen content of the sample is further calculated, and the test parameters are as follows: the X-ray emission source was an Al source, and the analyzer mode was CAE, and the pass energy was 20.0 eV.
(4) Conductivity test
Dispersing a sample in ethanol, performing suction filtration to remove a solvent, forming a graphene membrane layer after natural drying, and testing the conductivity of the sample by using an RTS-4 type four-probe tester according to the description in the reference (ACS Nano,4, 3845-38522010).
Example 1
Preparing high-conductivity graphene 1 by the following method:
dispersing 1g of graphene oxide prepared by a Hummers method in 200mL of deionized water, adding 5mg of catalyst platinum black into the deionized water, stirring the mixture to uniformly mix the mixture, and then placing the mixture in a fume hood for natural drying to obtain a raw material mixture;
step (2), standing the raw material mixture obtained in the step (1) at 25 ℃ in a mixed gas atmosphere with a volume ratio of hydrogen to helium of 1:19 for pretreatment for 10min to obtain pretreated graphene;
and (3) placing the pretreated graphene obtained in the step (2) in the same atmosphere as that in the step (2), and performing microwave irradiation treatment with the power of 1000W for 5s to obtain the high-conductivity graphene 1.
Taking the high-conductivity graphene 1 obtained in the example 1 as an example, fig. 1 is a morphology image of the high-conductivity graphene 1 obtained in the example 1 observed by a TEM, it can be obviously seen from the image, the high-conductivity graphene obtained in the invention has fewer defects and a larger graphene layer area, and the radial length can reach 1-10 μm, and fig. 2 is a high-power transmission electron microscope photograph of the high-conductivity graphene 1, and it can be obviously seen from the image, the graphene obtained in the invention is a single-layer graphene, and has an obvious crystal lattice and a flat and defect-free surface.
FIG. 3 is a Raman spectrum of high conductivity graphene 1, wherein the D peak, G peak and 2D peak are selected, and I is obtained by calculationD/IGIs 0.14, I2D/IGAt 1.02, the inference in TEM photographs was confirmed that the obtained graphene was a monolayer, had an extremely low oxygen content, and crystallized well.
Example 2
Preparing high-conductivity graphene 2 by the following method:
the only difference from example 1 is that the catalyst added in step (1) was 1mg of palladium chloride.
Example 2 high conductivity graphene 2 was obtained.
Example 3
Preparing high-conductivity graphene 3 by the following method:
the only difference from example 1 is that the catalyst added in step (1) is 50mg of ferrous sulfate.
Example 3 high conductivity graphene 3 was obtained.
Example 4
Preparing high-conductivity graphene 4 by the following method:
the difference from example 1 is only that the mixed gas in step (2) is ammonia gas and argon gas, and the volume ratio of the ammonia gas to the argon gas is 9: 1.
Example 4 high conductivity graphene 4 was obtained.
Example 5
Preparing high-conductivity graphene 5 by the following method:
the only difference from example 1 is that the temperature of the pretreatment in step (2) was 50 ℃ and the time was 5 min.
Example 5 high conductivity graphene 5 was obtained.
Example 6
Preparing high-conductivity graphene 6 by the following method:
the only difference from example 1 was that the irradiation treatment in step (3) was carried out at a power of 700W for 1 s.
Example 6 high conductivity graphene 6 was obtained.
Example 7
The high conductivity graphene 7 is prepared by the following method:
the only difference from example 1 was that the irradiation treatment in step (3) was carried out at a power of 2000W for 0.1 s.
Example 7 high conductivity graphene 7 was obtained.
Example 8
The high conductivity graphene 8 is prepared by the following method:
the only difference from example 1 is that freeze-drying at-56 ℃ under 10Pa using a freeze dryer in step (1) replaces the natural drying step.
Example 8 high conductivity graphene 8 was obtained.
Comparative example 1
Reduced graphene 1 was prepared by the following method:
dispersing 1g of graphene oxide prepared by a Hummers method in 50mL of deionized water, adding 5mg of catalyst platinum black into the deionized water, uniformly stirring and mixing the mixture, and then placing the mixture in a fume hood for natural drying to obtain a raw material mixture;
and (2) placing the raw material mixture obtained in the step (1) in a mixed gas atmosphere with the volume ratio of hydrogen to helium being 1:19, and performing microwave irradiation treatment with the power of 1000W for 5s to obtain the reduced graphene 1.
Reduced graphene 1 was obtained in comparative example 1.
Comparative example 2
The difference from example 1 is only that in step (2), the raw material mixture obtained in step (1) and 57 wt% hydriodic acid solution are mixed and stirred for 2h at 60 ℃ for reduction treatment, and the product is filtered, washed and dried to obtain the pretreated graphene.
Comparative example 2 reduced graphene 2 was obtained.
Table 1 table for comparing the performance of graphene obtained in each example and each comparative example
As can be seen from Table 1, by adopting the novel preparation method of graphene, the graphene material with large lamellar size, few layers, few defects and low oxygen content can be obtained, the conductivity of the graphene material is more than or equal to 30000S/m, even can reach 60000S/m, the oxygen content is 2.5-5 wt%, and the I content is calculated according to Raman spectrumD/IG≤0.5、I2D/IGNot less than 0.5, which is in accordance with the characteristics of single-layer graphene with no defect on the surface, compared with the common graphene preparation method in the prior art (such as the method for preparing graphene by oxidation-reduction method in the comparative example 2), the method provided by the invention can be used for preparing the high-conductivity graphene material with higher conductivity.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (17)
1. A preparation method of high-conductivity graphene is characterized by comprising the following steps:
step (1), uniformly mixing graphene oxide and a catalyst to obtain a raw material mixture;
step (2), placing the raw material mixture obtained in the step (1) in a mixed gas of reducing gas and inert gas for pretreatment to obtain pretreated graphene;
step (3), placing the pretreated graphene obtained in the step (2) in a mixed gas of reducing gas and inert gas for microwave irradiation treatment to obtain high-conductivity graphene;
wherein the catalyst in the step (1) is any one of simple substance platinum, palladium dichloride, platinum tetrachloride, iron dichloride or ferrous sulfate.
2. The method according to claim 1, wherein the microwave irradiation treatment time in step (3) is 0.1 to 6 seconds.
3. The method according to claim 2, wherein the microwave irradiation treatment time in step (3) is 1 to 5 seconds.
4. The preparation method according to claim 1, wherein the irradiation power of the microwave irradiation treatment in the step (3) is 100 to 2000W.
5. The preparation method according to claim 4, wherein the irradiation power of the microwave irradiation treatment in the step (3) is 700-1000W.
6. The production method according to claim 1, wherein the pretreatment in the step (2) is carried out by leaving the raw material mixture in a mixed gas atmosphere of a reducing gas and an inert gas.
7. The method according to claim 1, wherein the temperature of the pretreatment is 0 to 50 ℃.
8. The method according to claim 1, wherein the pretreatment time is 1 to 30 min.
9. The method according to claim 8, wherein the pretreatment time is 5 to 10 min.
10. The method according to claim 1, wherein the volume of the reducing gas in the steps (2) and (3) is at least 5% of the total volume of the mixed gas.
11. The method according to claim 1, wherein the reducing gas in step (2) and step (3) comprises any one of hydrogen gas, ammonia gas, hydrogen sulfide gas, carbon monoxide gas, and nitric oxide gas, or a mixed gas of at least two of them.
12. The method according to claim 1, wherein the inert gas in the steps (2) and (3) comprises any one of nitrogen, argon, helium, neon, krypton, or xenon, or a mixture of at least two thereof.
13. The preparation method according to claim 1, wherein the graphene oxide in step (1) is obtained by intercalation oxidation of graphite.
14. The preparation method according to claim 1, wherein the step (1) of uniformly mixing is performed by mixing the graphene oxide dispersion with the catalyst and then drying to remove the solvent.
15. The method according to claim 14, wherein the drying to remove the solvent is performed by any one of vacuum drying, heat drying, freeze drying and natural drying.
16. The preparation method according to claim 1, wherein the weight ratio of the graphene oxide to the catalyst in the raw material mixture in the step (1) is (10-2000): 1.
17. The preparation method according to claim 16, wherein the weight ratio of the graphene oxide to the catalyst in the raw material mixture in the step (1) is (200-500): 1.
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| CN103613093A (en) * | 2013-11-25 | 2014-03-05 | 黄德欢 | Method for preparing graphene through hydrogen gas reduction |
| CN106629689A (en) * | 2016-12-16 | 2017-05-10 | 复旦大学 | High-efficiency catalysis macroscopic quantity preparation method for graphene oxide or compound thereof reduced and peeled based on microwaves |
| CN106744894A (en) * | 2016-12-27 | 2017-05-31 | 阜阳欣奕华材料科技有限公司 | A kind of preparation method of graphene powder |
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| CN103613093A (en) * | 2013-11-25 | 2014-03-05 | 黄德欢 | Method for preparing graphene through hydrogen gas reduction |
| CN106629689A (en) * | 2016-12-16 | 2017-05-10 | 复旦大学 | High-efficiency catalysis macroscopic quantity preparation method for graphene oxide or compound thereof reduced and peeled based on microwaves |
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