CN107539973B - Preparation method of graphene powder - Google Patents
Preparation method of graphene powder Download PDFInfo
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- CN107539973B CN107539973B CN201710817729.1A CN201710817729A CN107539973B CN 107539973 B CN107539973 B CN 107539973B CN 201710817729 A CN201710817729 A CN 201710817729A CN 107539973 B CN107539973 B CN 107539973B
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Abstract
The invention discloses a preparation method of graphene powder, which comprises the following process steps: mixing and stirring graphite powder, an intercalation expanding agent and chlorosulfonic acid uniformly, adding distilled water, and after the reaction is finished, preparing the few-layer graphene powder by adopting ultrasonic, water washing, centrifuging and freeze drying. The graphene is prepared by utilizing the reaction of water and chlorosulfonic acid to induce the rapid decomposition of the intercalation expanding agent, the reaction is rapidly completed, no oxidation reaction is involved, the structure of the prepared graphene is not damaged, and the graphene sp is not damaged2The crystal face structure is complete; and the preparation process is simple, the cost is low, and the method is suitable for industrial large-scale production of graphene.
Description
Technical Field
The invention belongs to the technical field of graphene preparation, and particularly relates to a preparation method of graphene powder.
Background
Graphene has attracted attention as a novel carbon material since its discovery in 2004. The composite material has high light transmittance, conductivity, specific surface area and excellent mechanical property, and has wide application prospect and great commercial value in the fields of composite materials, energy materials, communication and the like.
Currently, the preparation method of graphene includes: mechanical exfoliation, Chemical Vapor Deposition (CVD), Chemical oxidation-reduction, electrochemical exfoliation, SiC thermal decomposition, etc., of which the Chemical oxidation-reduction based on Hummers is the most prevalent and is used in most laboratories, but the prepared graphene has many defects and its properties are different from those of high-quality graphene prepared by mechanical exfoliation, CVD, etc. But also generates a large amount of waste acid, and the burden of environmental protection is serious. Although the mechanical stripping method can keep the integrity of graphene completely, the problems of unstable prepared products, low efficiency and high cost exist.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of graphene powder, wherein the few-layer graphene is prepared by utilizing the reaction of water and chlorosulfonic acid to induce the rapid decomposition of an intercalation expanding agent, the reaction is rapidly completed, no oxidation reaction is involved, the structure of the prepared graphene is not damaged, and the graphene sp is not subjected to any oxidation reaction2The crystal face structure is complete; and the preparation process is simple, the cost is low, and the method is suitable for industrial large-scale production of graphene.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of graphene powder comprises the following steps:
1) uniformly mixing graphite with carbon content not less than 90%, an intercalation expanding agent and chlorosulfonic acid according to the mass ratio of 1: 3-32: 180-550;
2) slowly adding distilled water into the system in the step 1), wherein the volume ratio of the distilled water to chlorosulfonic acid in the step 1) is 0.08-0.55: 1; obtaining a mixed solution system after the reaction is finished;
3) carrying out ultrasonic treatment on the mixed solution system obtained in the step 2) for 3 min-2.5 h at 40-2500W, washing the mixed solution system to be neutral by using distilled water, centrifuging the mixed solution system at 800-3500 rpm for 8-35 min, and collecting the wet graphene on the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 4-12 hours to obtain graphene powder.
In one embodiment: in the step 1), the graphite is natural crystalline flake graphite or pyrolytic graphite.
In one embodiment: in the step 1), the intercalation expanding agent is at least one of ammonium persulfate, potassium persulfate, sodium persulfate, ammonium percarbonate, potassium percarbonate, ammonium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium carbonate and the like.
In one embodiment: in the step 1), the mass ratio of the graphite to the intercalation expanding agent to the chlorosulfonic acid is 1: 4-30: 200-500.
In one embodiment: in the step 2), the volume ratio of the distilled water to the chlorosulfonic acid in the step 1) is 0.1-0.5: 1.
In one embodiment: in the step 3), the ultrasonic power is 50-2000W.
In one embodiment: in the step 3), the ultrasonic treatment time is 5 min-2 h.
In one embodiment: in the step 3), the centrifugal rotating speed is 1000-3000 rpm.
In one embodiment: in the step 3), the centrifugation time is 10-30 min.
In one embodiment: in the step 4), the freeze drying time is 5-10 h.
Compared with the background technology, the technical scheme has the following advantages:
(1) the whole reaction process of the present invention can be carried out at a temperature at which water exists in a liquid state, and the reaction conditions are not limited otherwise.
(2) According to the method, chlorosulfonic acid is adopted to react with distilled water to induce the intercalation expanding agent to decompose, so that graphite is expanded to prepare graphene, and the distilled water is adopted in the reaction process, so that the industrial cost is reduced.
(3) The whole reaction process of the invention does not involve any oxidation process, and the prepared graphene sp2The lattice structure is complete, and the graphene quality is high.
Drawings
The invention is further illustrated by the following figures and examples.
Fig. 1 is a surface topography of the graphene powder obtained in embodiment 1 of the present invention, which is observed by a scanning electron microscope.
Fig. 2 is a surface topography of the graphene powder obtained in example 1 of the present invention observed by a high power transmission electron microscope.
Fig. 3 is an X-ray photoelectron spectrum of the graphene powder and graphite powder obtained in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples:
example 1
1) In a conical flask, 0.1g of graphite, 0.4g of potassium persulfate and 10ml (about 20g) of chlorosulfonic acid are sequentially added, magnetically stirred for 1min and uniformly mixed; the graphite is natural crystalline flake graphite or pyrolytic graphite, and the carbon content is more than 90 percent, as follows.
2) Slowly dripping distilled water into the system in the step 1), dripping 1ml of distilled water in total, reacting, and obtaining a mixed solution system after the reaction is finished;
3) inserting a 50W ultrasonic probe below the liquid level of the mixed solution system obtained in the step 2), performing ultrasonic treatment for 2h, washing the mixed solution system to be neutral by distilled water, centrifuging the mixed solution system at 3000rpm for 10min, removing unreacted graphite at the lower layer, and collecting wet graphene at the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 5 hours to obtain graphene powder.
Fig. 1 is a surface topography observed by a scanning electron microscope of the graphene powder obtained in example 1, fig. 2 is a surface topography observed by a high power transmission electron microscope of the graphene powder obtained in example 1, and fig. 3 is an X-ray photoelectron energy spectrum of the graphene powder and graphite powder obtained in example 1, as can be seen from the following figures: the carbon/oxygen content ratio of the prepared graphene product is equivalent to that of the graphite raw material, which indicates that the prepared graphene product is not grafted with oxygen-containing functional groups.
Example 2
1) In a conical flask, 0.1g of graphite, 0.4g of ammonium persulfate and 26ml (about 50g) of chlorosulfonic acid are sequentially added, magnetically stirred for 1min and uniformly mixed;
2) slowly dripping distilled water into the system in the step 1), dripping 5ml of distilled water in total, reacting, and obtaining a mixed solution system after the reaction is finished;
3) inserting a 2000W ultrasonic probe below the liquid level of the mixed solution system obtained in the step 2), performing ultrasonic treatment for 5min, washing the mixed solution system to be neutral by distilled water, centrifuging the mixed solution system at 3000rpm for 10min, removing unreacted graphite at the lower layer, and collecting wet graphene at the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 5 hours to obtain graphene powder.
Example 3
1) In a conical flask, 0.1g of graphite, 3g of potassium bicarbonate and 10ml (about 20g) of chlorosulfonic acid are sequentially added, and are magnetically stirred for 1min and uniformly mixed;
2) slowly adding 1ml of distilled water into the system in the step 1), stirring and reacting for 5min to obtain a mixed solution system after the reaction is finished;
3) inserting a 50W ultrasonic probe below the liquid level of the mixed solution system obtained in the step 2), performing ultrasonic treatment for 2h, washing the mixed solution system to be neutral by distilled water, centrifuging the mixed solution system for 30min at 1000rpm, removing unreacted graphite at the lower layer, and collecting wet graphene at the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 10 hours to obtain graphene powder.
Example 4
1) In a conical flask, 0.1g of graphite, 3g of sodium persulfate and 26ml (about 50g) of chlorosulfonic acid are sequentially added, magnetically stirred for 1min and uniformly mixed;
2) slowly adding 5ml of distilled water into the system in the step 1), stirring and reacting for 5min to obtain a mixed solution system after the reaction is finished;
3) inserting a 50W ultrasonic probe below the liquid level of the mixed solution system obtained in the step 2), performing ultrasonic treatment for 2h, washing the mixed solution system to be neutral by distilled water, centrifuging the mixed solution system at 3000rpm for 10min, removing unreacted graphite at the lower layer, and collecting wet graphene at the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 10 hours to obtain graphene powder.
Example 5
1) In a conical flask, 0.1g of graphite, 1.5g of potassium persulfate and 26ml (about 50g) of chlorosulfonic acid are sequentially added, magnetically stirred for 1min and uniformly mixed;
2) slowly dripping distilled water into the system in the step 1), dripping 5ml of distilled water in total, reacting, and obtaining a mixed solution system after the reaction is finished;
3) inserting a 50W ultrasonic probe below the liquid level of the mixed solution system obtained in the step 2), performing ultrasonic treatment for 2h, washing the mixed solution system to be neutral by distilled water, centrifuging the mixed solution system at 3000rpm for 10min, removing unreacted graphite at the lower layer, and collecting wet graphene at the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 10 hours to obtain graphene powder.
Example 6
1) In a conical flask, 0.1g of graphite, 1.5g of ammonium persulfate and 13ml (about 25g) of chlorosulfonic acid are sequentially added, magnetically stirred for 1min and uniformly mixed;
2) slowly dripping distilled water into the system in the step 1), dripping 5ml of distilled water in total, reacting, and obtaining a mixed solution system after the reaction is finished;
3) inserting a 2000W ultrasonic probe below the liquid level of the mixed solution system obtained in the step 2), performing ultrasonic treatment for 5min, washing the mixed solution system to be neutral by distilled water, centrifuging the mixed solution system at 3000rpm for 10min, removing unreacted graphite at the lower layer, and collecting wet graphene at the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 10 hours to obtain graphene powder.
Example 7
1) Sequentially adding 0.1g of graphite, 3g of potassium carbonate and 10ml (about 20g) of chlorosulfonic acid into an erlenmeyer flask, and uniformly mixing by magnetic stirring for 1 min;
2) slowly adding 1ml of distilled water into the system in the step 1), stirring and reacting for 5min to obtain a mixed solution system after the reaction is finished;
3) inserting a 50W ultrasonic probe below the liquid level of the mixed solution system obtained in the step 2), performing ultrasonic treatment for 2h, washing the mixed solution system to be neutral by distilled water, centrifuging the mixed solution system at 3000rpm for 10min, removing unreacted graphite at the lower layer, and collecting wet graphene at the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 10 hours to obtain graphene powder.
Example 8
1) Sequentially adding 0.1g of graphite, 3g of sodium carbonate and 10ml (about 20g) of chlorosulfonic acid into an erlenmeyer flask, and uniformly mixing by magnetic stirring for 1 min;
2) slowly adding 3ml of distilled water into the system in the step 1), stirring and reacting for 5min to obtain a mixed solution system after the reaction is finished;
3) inserting a 50W ultrasonic probe below the liquid level of the mixed solution system obtained in the step 2), performing ultrasonic treatment for 2h, washing the mixed solution system to be neutral by distilled water, centrifuging the mixed solution system for 30min at 1000rpm, removing unreacted graphite at the lower layer, and collecting wet graphene at the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 5 hours to obtain graphene powder.
Example 9
1) In a conical flask, 0.1g of graphite, 2g of sodium persulfate and 20ml (about 40g) of chlorosulfonic acid are sequentially added, magnetically stirred for 1min and uniformly mixed;
2) slowly adding 3ml of distilled water into the system in the step 1), stirring and reacting for 5min to obtain a mixed solution system after the reaction is finished;
3) inserting a 50W ultrasonic probe below the liquid level of the mixed solution system obtained in the step 2), performing ultrasonic treatment for 2h, washing the mixed solution system to be neutral by distilled water, centrifuging the mixed solution system at 1500rpm for 20min, removing unreacted graphite at the lower layer, and collecting wet graphene at the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 5 hours to obtain graphene powder.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of graphene powder is characterized by comprising the following steps: the method comprises the following steps:
1) uniformly mixing graphite with carbon content not less than 90%, an intercalation expanding agent and chlorosulfonic acid according to the mass ratio of 1: 3-32: 180-550;
2) adding distilled water into the system in the step 1), wherein the volume ratio of the distilled water to chlorosulfonic acid in the step 1) is 0.08-0.55: 1; obtaining a mixed solution system after the reaction is finished;
3) carrying out ultrasonic treatment on the mixed solution system obtained in the step 2) for 3 min-2.5 h at 40-2500W, washing the mixed solution system to be neutral by using distilled water, centrifuging the mixed solution system at 800-3500 rpm for 8-35 min, and collecting the wet graphene on the upper layer;
4) freeze-drying the wet graphene obtained in the step 3) for 4-12 hours to obtain graphene powder.
2. The method for preparing graphene powder according to claim 1, wherein: in the step 1), the graphite is natural crystalline flake graphite or pyrolytic graphite.
3. The method for preparing graphene powder according to claim 1, wherein: in the step 1), the intercalation expanding agent is at least one of ammonium persulfate, potassium persulfate, sodium persulfate, ammonium percarbonate, potassium percarbonate, ammonium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and sodium carbonate.
4. The method for preparing graphene powder according to claim 1, wherein: in the step 1), the mass ratio of the graphite to the intercalation expanding agent to the chlorosulfonic acid is 1: 4-30: 200-500.
5. The method for preparing graphene powder according to claim 1, wherein: in the step 2), the volume ratio of the distilled water to the chlorosulfonic acid in the step 1) is 0.1-0.5: 1.
6. The method for preparing graphene powder according to claim 1, wherein: in the step 3), the ultrasonic power is 50-2000W.
7. The method for preparing graphene powder according to claim 1, wherein: in the step 3), the ultrasonic treatment time is 5 min-2 h.
8. The method for preparing graphene powder according to claim 1, wherein: in the step 3), the centrifugal rotating speed is 1000-3000 rpm.
9. The method for preparing graphene powder according to claim 1, wherein: in the step 3), the centrifugation time is 10-30 min.
10. The method for preparing graphene powder according to claim 1, wherein: in the step 4), the freeze drying time is 5-10 h.
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| WO2022222380A1 (en) | 2021-04-22 | 2022-10-27 | 中国石油化工股份有限公司 | Graphene powder, and preparation method therefor and application thereof |
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Cited By (1)
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| WO2022222380A1 (en) | 2021-04-22 | 2022-10-27 | 中国石油化工股份有限公司 | Graphene powder, and preparation method therefor and application thereof |
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