CN108773842B - Preparation method of graphene and graphene - Google Patents
Preparation method of graphene and graphene Download PDFInfo
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- CN108773842B CN108773842B CN201811041931.0A CN201811041931A CN108773842B CN 108773842 B CN108773842 B CN 108773842B CN 201811041931 A CN201811041931 A CN 201811041931A CN 108773842 B CN108773842 B CN 108773842B
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- 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
Abstract
The invention provides a preparation method of graphene and graphene, the preparation method comprises the steps of firstly, uniformly mixing graphite powder and an intercalating agent, adopting a mechanical grinding mode to obtain a mixed precursor, then mixing the prepared mixed precursor with an organic solvent, sequentially adding polydopamine modified by sulfhydrylation hydroxyethyl starch and a dispersing agent, uniformly stirring, and carrying out ultrasonic treatment to obtain a graphene product. The preparation method of the graphene avoids the expansion stripping of the solution in the prior art, and adopts the mild poly-dopamine modified by the sulfhydrylation hydroxyethyl starch and the dispersing agent for stripping, wherein the poly-dopamine modified by the sulfhydrylation hydroxyethyl starch has special surface activity and high adsorption capacity, so that the poly-dopamine can be adsorbed by pi-pi electron cloud between benzene ring structures of graphite, and the graphene on the outermost layer of natural graphite falls off from a graphite substrate to a solvent to obtain a graphene product.
Description
Technical Field
The invention belongs to the technical field of graphene material preparation, and particularly relates to a preparation method of graphene and the graphene.
Background
The graphene is represented by sp2The hybridized carbon atoms are arranged to form a single-atom layer two-dimensional material. Monoatomic layer two-dimensionalGraphene has the characteristics of transparency, light weight and flexibility, is the thinnest and hardest nano material known at present, and has many other excellent properties, such as the thermal conductivity coefficient of graphene is about 5300W/m.K, which is higher than that of natural graphite, carbon nano tubes, diamond and other materials; the electron mobility of the graphene at normal temperature is larger than 15000cm2V.s, higher than carbon nanotubes and silicon crystals; the conductivity of the graphene is up to 10-6S/m, which is lower than copper or silver, is the highest conductivity material at present. Due to the characteristics of the graphene, the graphene has wide application prospects in the fields of lithium ion batteries, supercapacitors, solar batteries, seawater desalination, light emitting diodes, sensors, hydrogen storage, catalyst carriers, composite materials, coatings, biological scaffold materials, drug controlled release and the like.
At present, the preparation method of graphene mainly comprises a mechanical stripping method, a chemical vapor deposition method, an epitaxial crystal growth method, a redox method and the like. The mechanical stripping method is to obtain pure graphene sheets by mechanically stripping graphite, but cannot be used for large-scale production due to too low yield; the chemical vapor deposition method or epitaxial crystal growth method is characterized in that large-area single-layer or multi-layer graphene can be prepared, but the uniformity and the thickness are difficult to control; in addition, graphene is grown on insulator substrates, for example, very thin graphene can be grown on silicon carbide surfaces, which is expensive and difficult to prepare in large areas; the redox method is to generate functionalized graphite oxide by stripping graphite powder or graphite fiber with strong oxidant such as sulfuric acid and nitric acid or other chemical oxidation treatment, and then rapidly expand and strip the graphite oxide compound by a high temperature furnace at a high temperature of 1100-1250 ℃, although the graphite oxide can be stripped to form graphene oxide, the conductivity of the graphite oxide is much lower than that of graphene because the physical and electronic structure of the graphene is adversely affected, and the treatment process time is long, and the reduced graphene is easy to deform and warp, so that the quality of the graphene is poor.
Therefore, chinese patent document CN107973293A provides a preparation method of graphene and graphene, wherein the preparation method is to obtain graphene by a three-order exfoliation method, which sequentially includes first-order mechanical exfoliation and intercalation of graphite, second-order solution expansion exfoliation and third-order ultrasonic exfoliation, wherein the first-order mechanical exfoliation and intercalation of graphite is to mix graphite and intercalation medium, and the graphite is exfoliated and intercalated to a certain extent by a mechanical method to obtain a graphene precursor; the second-order solution expansion stripping is to add a graphene precursor into a strong acid solution, separate graphene, and further open graphene layers with defects to obtain an active graphene dispersion solution; and the third-order ultrasonic stripping is to further ultrasonically strip the active graphene dispersion liquid to obtain the graphene dispersion liquid with small lamella thickness and few layers. However, the second-order solution used in the preparation method has the defect of destroying the chemical bond structure of the prepared graphene due to expansion stripping, so that the electronic conductivity of the obtained graphene is low, and the further application of the graphene is influenced. Therefore, it is an urgent technical problem for those skilled in the art to improve the existing preparation method of graphene to reduce the damage of the chemical bond structure of graphene as much as possible and to improve the electronic conductivity of the prepared graphene.
Disclosure of Invention
The invention provides a preparation method of graphene, the graphene prepared by the preparation method has good electronic performance and high electronic conductivity, and the graphene prepared by the preparation method is further provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in a first aspect of the present invention, a method for preparing graphene is provided, which includes the following steps:
(1) uniformly mixing graphite powder and an intercalation agent, and obtaining a mixed precursor by adopting a mechanical grinding mode;
(2) and (2) mixing the mixed precursor prepared in the step (1) with an organic solvent, sequentially adding the poly-dopamine modified by the sulfhydrylation hydroxyethyl starch and a dispersing agent, uniformly stirring, and performing ultrasonic treatment to obtain a graphene product.
In the preparation method of the graphene, the preparation method of the poly-dopamine modified by the thiolated hydroxyethyl starch comprises the following steps:
(1) carboxylating hydroxyethyl starch under alkaline condition, and then reacting with 2- (pyridine disulfide) -ethylamine hydrochloride to obtain hydroxyethyl starch-2- (pyridine disulfide);
(2) sulfhydrylation is carried out on hydroxyethyl starch-2- (pyridine disulfide) prepared in the step (1) to obtain sulfhydrylation hydroxyethyl starch;
(3) mixing the thiolated hydroxyethyl starch prepared in the step (2) with polydopamine, and reacting under alkaline conditions to obtain polydopamine modified by the thiolated hydroxyethyl starch.
In the above graphene preparation method, preferably, in the step (3), the mass ratio of the thiolated hydroxyethyl starch to the polydopamine is 5: 1; the pH of the alkaline condition is 10, and the reaction time is 30 h.
In the preparation method of graphene, in the step (1), the carboxylation of hydroxyethyl starch under alkaline conditions specifically comprises the following steps: dissolving hydroxyethyl starch in deionized water, sequentially adding sodium hydroxide and chloroacetic acid, and reacting at 100 ℃.
In the above preparation method of graphene, in the step (1), preferably, the graphite powder is flake graphite, expanded graphite or earthy graphite; the intercalation agent is sodium carbonate, sodium bicarbonate or sodium sulfite.
Preferably, the mass ratio of the graphite powder to the intercalation agent is 1 (3-10), preferably 1: (5-8).
In the above method for preparing graphene, in the step (1),
the mechanical grinding mode is horizontal grinding, planetary grinding or high-energy ball milling, and the time of the mechanical grinding mode is 50-150 hours.
Preferably, the mass ratio of the graphite powder to the poly-dopamine modified by the thiolated hydroxyethyl starch and the dispersing agent is 1 (10-50) to (30-80), and preferably 1:30: 50.
Preferably, the dispersant is sodium dodecyl benzene sulfonate or polyvinylpyrrolidone; the organic solvent is methanol, ethanol or isopropanol.
In a second aspect of the invention, the graphene prepared by the preparation method is provided.
The technical scheme of the invention has the following advantages:
(1) the preparation method of the graphene comprises the steps of firstly, uniformly mixing graphite powder and an intercalating agent, adopting a mechanical grinding mode to obtain a mixed precursor, then mixing the prepared mixed precursor with an organic solvent, sequentially adding the polydopamine modified by the sulfhydrylated hydroxyethyl starch and a dispersing agent, uniformly stirring, and then carrying out ultrasonic treatment to obtain a graphene product. The preparation method of the graphene avoids the expansion stripping of the solution in the prior art, and adopts the mild poly-dopamine modified by the sulfhydrylation hydroxyethyl starch and the dispersing agent for stripping, wherein the poly-dopamine modified by the sulfhydrylation hydroxyethyl starch has special surface activity and high adsorption capacity, so that the poly-dopamine can be adsorbed with pi-pi electron cloud between benzene ring structures of graphite, and the graphene on the outermost layer of natural graphite falls off from a graphite substrate into a solvent, and the chemical bond structure of the graphene is hardly damaged by continuously repeating the process, so that a graphene product is obtained.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In the present invention, the raw materials are all commercially available products.
Example 1
The embodiment provides a preparation method of polydopamine modified by thiolated hydroxyethyl starch, which comprises the following steps:
(1) dissolving 1g of hydroxyethyl starch with the molecular weight of 25000Da and the hydroxyethyl substitution degree of 0.5 in 10mL of deionized water, stirring until the hydroxyethyl starch is dissolved, then sequentially adding 1.2g of sodium hydroxide and 1.5g of chloroacetic acid to form a reaction system, reacting the reaction system at 100 ℃ for 5 hours, stopping the reaction, cooling to room temperature, pouring the reaction system into 20mL of methanol, stirring, and centrifuging to obtain white precipitate, namely carboxylated hydroxyethyl starch;
dissolving 0.8g of the carboxylated hydroxyethyl starch prepared in the previous step in 10mL of deionized water, adding 250mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 75mg of N-hydroxysuccinimide and 150mg of 2- (pyridyldithio) -ethylamine hydrochloride to form a reaction system, stirring the reaction system at 30 ℃ for reaction for 30 hours, centrifuging, dialyzing the supernatant by using dialysis bag deionized water with molecular weight cutoff of 3500Da for 3 days, and freeze-drying to obtain hydroxyethyl starch-2- (pyridyldithio);
(2) dissolving 0.5g of hydroxyethyl starch-2- (pyridine disulfide) prepared in the above step in 10mL of dimethyl sulfoxide, adding 420mg of dithiothreitol, stirring and reacting at room temperature for 24h under the protection of nitrogen, dialyzing with dialysis bag deionized water with molecular weight cutoff of 3500Da for 3 days, and freeze-drying to obtain thiolated hydroxyethyl starch;
(3) and dispersing 40mg of polydopamine in 10mL of deionized water, stirring and ultrasonically treating for 30min, adding sodium hydroxide to adjust the pH value to 10, slowly adding 200mg of the thiolated hydroxyethyl starch prepared in the previous step while stirring, after the addition is finished, stirring and reacting for 30h at room temperature, and performing ultrafiltration to remove unreacted thiolated hydroxyethyl starch, wherein the molecular weight cut-off of the ultrafiltration tube is 100kDa, and the ultrafiltration speed is 4000 rpm, so that the polydopamine modified by the thiolated hydroxyethyl starch is obtained.
Example 2
The preparation method of graphene provided by the embodiment includes the following steps:
(1) uniformly mixing 1g of flake graphite powder and 10g of sodium bicarbonate, and horizontally grinding for 50h to obtain a mixed precursor after grinding is finished;
(2) mixing the mixed precursor prepared in the step (1) with 250mL of methanol, then sequentially adding 10g of polydopamine modified by thiolated hydroxyethyl starch and 80g of sodium dodecyl benzene sulfonate, uniformly stirring, carrying out ultrasonic treatment by using an ultrasonic generator, wherein the ultrasonic time is 1h and the ultrasonic power is 300W, and then washing, centrifuging and drying at 50 ℃ to obtain a graphene product;
the polydopamine modified with thiolated hydroxyethyl starch used in this example was prepared as in example 1.
The number of layers of the graphene prepared in the embodiment is about 3.
Example 3
The preparation method of graphene provided by the embodiment includes the following steps:
(1) 1g of earthy graphite powder and 3g of sodium sulfite are uniformly mixed and subjected to planetary grinding for 150 hours, and a mixed precursor is obtained after the grinding is finished;
(2) mixing the mixed precursor prepared in the step (1) with 350mL of isopropanol, then sequentially adding 50g of polydopamine modified by thiolated hydroxyethyl starch and 30g of polyvinylpyrrolidone, uniformly stirring, then carrying out ultrasonic treatment by using an ultrasonic generator, wherein the ultrasonic time is 1h and the ultrasonic power is 300W, and then washing, centrifuging and drying at 50 ℃ to obtain a graphene product;
the polydopamine modified with thiolated hydroxyethyl starch used in this example was prepared as in example 1.
Through detection, the number of layers of the graphene prepared by the embodiment is about 3-4.
Example 4
The preparation method of graphene provided by the embodiment includes the following steps:
(1) 1g of expanded graphite powder and 5g of sodium carbonate are uniformly mixed and subjected to high-energy ball milling for 100 hours, and a mixed precursor is obtained after the milling is finished;
(2) mixing the mixed precursor prepared in the step (1) with 350mL of ethanol, then sequentially adding 30g of polydopamine modified by thiolated hydroxyethyl starch and 50g of polyvinylpyrrolidone, uniformly stirring, carrying out ultrasonic treatment by using an ultrasonic generator, wherein the ultrasonic time is 1h and the ultrasonic power is 300W, and then washing, centrifuging and drying at 50 ℃ to obtain a graphene product;
the polydopamine modified with thiolated hydroxyethyl starch used in this example was prepared as in example 1.
Through detection, the number of layers of the graphene prepared by the embodiment is about 3-4.
Examples of the experiments
Conducting performance tests are carried out on the graphene prepared in the embodiment 2-4, and the testing method is as follows: adopting an FT-300I resistivity tester of Ningbo Rake instruments Co., Ltd, respectively adding 2g of the graphene prepared in the above examples 2-4 into a die cavity with an inner diameter of 10mm and a height of 25mm, pressurizing to 3.5MPa, pressing into a sheet with a diameter of 10mm, and measuring the conductivity, wherein the results are as follows:
table 1 conductivity properties of graphene prepared in examples 2 to 4
| Conductivity (s/m) | |
| Example 2 | 2500 |
| Example 3 | 2550 |
| Example 4 | 2500 |
As can be seen from Table 1, the graphene prepared by the method has excellent conductivity, the conductivity of the graphene is as high as more than 2500s/m, the number of layers of the prepared graphene is low, and the prepared graphene has good performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A preparation method of graphene is characterized by comprising the following steps:
(1) uniformly mixing graphite powder and an intercalating agent in a mass ratio of 1 (3-10), and grinding for 50-150 h by adopting a mechanical grinding mode to obtain a mixed precursor, wherein the intercalating agent is sodium carbonate, sodium bicarbonate or sodium sulfite;
(2) mixing the mixed precursor prepared in the step (1) with an organic solvent, sequentially adding the dopamine modified by the thiolated hydroxyethyl starch and a dispersing agent, uniformly stirring, and carrying out ultrasonic treatment for 1h at the power of 300W by using an ultrasonic generator to obtain a graphene product, wherein the mass ratio of the graphite powder to the dopamine modified by the thiolated hydroxyethyl starch to the dispersing agent is (10-50) to (30-80), the dispersing agent is sodium dodecyl benzene sulfonate or polyvinylpyrrolidone, and the organic solvent is methanol, ethanol or isopropanol.
2. The method for preparing graphene according to claim 1, wherein the method for preparing polydopamine modified by thiolated hydroxyethyl starch is as follows:
(1) carboxylating hydroxyethyl starch under alkaline condition, and then reacting with 2- (pyridine disulfide) -ethylamine hydrochloride to obtain hydroxyethyl starch-2- (pyridine disulfide);
(2) sulfhydrylation is carried out on hydroxyethyl starch-2- (pyridine disulfide) prepared in the step (1) to obtain sulfhydrylation hydroxyethyl starch;
(3) mixing the thiolated hydroxyethyl starch prepared in the step (2) with polydopamine, and reacting under alkaline conditions to obtain polydopamine modified by the thiolated hydroxyethyl starch.
3. The method for preparing graphene according to claim 2, wherein in the step (3), the mass ratio of the thiolated hydroxyethyl starch to the polydopamine is 5: 1; the pH of the alkaline condition is 10, and the reaction time is 30 h.
4. The method for preparing graphene according to claim 2, wherein in the step (1), the step of carboxylating hydroxyethyl starch under alkaline conditions comprises the following specific steps: dissolving hydroxyethyl starch in deionized water, sequentially adding sodium hydroxide and chloroacetic acid, and reacting at 100 ℃.
5. The method for preparing graphene according to claim 1, wherein in the step (1), the graphite powder is flake graphite, expanded graphite or earthy graphite.
6. The preparation method of graphene according to claim 5, wherein the mass ratio of the graphite powder to the intercalation agent is 1 (5-8).
7. The method for preparing graphene according to claim 1, wherein in the step (1), the mechanical grinding manner is horizontal grinding, planetary grinding or high-energy ball milling.
8. The preparation method of graphene according to claim 1, wherein the mass ratio of the graphite powder to the thiolated hydroxyethyl starch-modified polydopamine to the dispersant is 1:30: 50.
9. Graphene prepared according to the preparation method of any one of claims 1 to 8.
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| CN110759336A (en) * | 2019-11-11 | 2020-02-07 | 董影影 | Preparation method of graphene and graphene |
| CN111628172A (en) * | 2020-05-12 | 2020-09-04 | 山东领军科技集团有限公司 | Production process of graphene-based battery conductive agent |
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