CN105778571A - Graphene composite slurry and preparation method thereof - Google Patents

Abstract

The invention provides a preparation method of a graphene composite slurry. The method comprises the steps of: dispersing graphene in a disperse medium A1 to obtain a mixture B1; adding a dispersing aid in the mixture A1 and an aniline oligomer derivative for forming pi-pi binding with graphene to obtain a mixture B2; drying the B2 mixture to obtain an aniline oligomer derivative modified graphene composite powder; and dispersing the graphene composite powder in a dispersion medium A2 to obtain the graphene composite slurry.

Description

A kind of graphene composite slurry and preparation method thereof

technical field

The invention relates to a graphene-based slurry and a preparation method thereof, in particular to a graphene composite slurry modified by aniline oligomer derivatives and a preparation method thereof.

Background technique

Graphene is a hexagonal honeycomb lattice material composed of carbon atoms, only one carbon atom thick. Graphene was discovered in 2004 and won the 2010 Nobel Prize in Physics. Graphene's single-atom nanostructure endows it with many unparalleled and unique properties. ①Extremely conductive: The electrons in graphene have basically no mass, and the movement speed of the electrons can reach 1/300 of the speed of light, so it has super conductivity. ②Ultra-high strength: Graphene is harder than diamond, but it has good toughness and can be bent. ③Super large specific surface area: The specific surface area of ideal single-layer graphene can reach 2630m ² /g, while the specific surface area of ordinary activated carbon is 1500m ² /g. The super large specific surface area makes graphene a potential energy storage material. It is precisely because graphene has many excellent properties that it has stimulated a global upsurge in graphene research and development.

Recently, many studies have focused on the synthesis of large-scale, large-scale graphene. At present, the preparation methods of graphene usually include mechanical exfoliation, chemical vapor deposition, oxidation-reduction, solution ultrasonic exfoliation and other methods. However, the obtained graphene is easy to agglomerate due to π-π conjugation and van der Waals adsorption. In addition, due to the unique structure of graphene, it is difficult to physically or chemically interact with other media, and the bonding strength is not high, so the application field is limited. Therefore, the biggest bottleneck limiting the application of graphene at present is how to obtain a stable and easy-to-disperse modified graphene composite slurry to give full play to its unique physical and chemical properties.

Contents of the invention

In view of the deficiencies in the prior art, the main purpose of the present invention is to provide a graphene composite slurry modified by aniline oligomer derivatives and a preparation method thereof. The graphene composite slurry not only has good redispersibility, but also It can be combined with other media to make graphene easy to disperse in the substrate or coat on the surface of the substrate, improving the applicability of graphene.

A preparation method for a graphene composite slurry, which comprises the steps of: dispersing graphene in a dispersion medium A1 to obtain a mixture B1; adding a dispersion aid and forming a strong π- π-bonded aniline oligomer derivatives, mixing the aniline oligomer derivatives and graphene uniformly and forming a π-π bond between the aniline oligomer derivatives and graphene to obtain a mixture B2; drying the mixture B2 to obtain Graphene composite powder modified by aniline oligomer derivatives; dispersing the graphene composite powder in dispersion medium A2 to obtain the graphene composite slurry.

Wherein, the dispersion medium A1 and the dispersion medium A2 are deionized water, ethanol, acetone, isopropanol, butanol, ethyl acetate, toluene, chloroform, dimethylformamide, dimethyl sulfoxide dichloroethane One or more mixed solvents, the mass ratio of the graphene to the dispersion medium A1 is 1:10 to 1:10000.

Wherein, the mass ratio of the graphene to the dispersion medium A1 is 1:20˜1:1000.

Wherein, the dispersion aid is a silane coupling agent, polyvinyl alcohol, polyvinylpyrrolidone, organomodified polysiloxane dipropylene glycol monomethyl ether solution, silicone surfactant and/or fluorosurfactant, so The mass percent (0.01-1) of the dispersing aid and the mixture B1: 100.

Wherein, the aniline oligomer derivatives are aniline oligomers with carboxyl groups, alkyl groups, sulfonic acid groups, phosphoric acid groups, epoxy groups, polyethylene glycol groups and/or polyvinyl alcohol groups.

Wherein, the mass percentage of the aniline oligomer derivative and the mixture B1 is (0.05-5):100.

Wherein, the aniline oligomer is one or a combination of aniline trimer, aniline tetramer, aniline pentamer, aniline hexamer, aniline octamer.

Wherein, the graphene composite powder is dispersed in the dispersion medium A2 by high-speed stirring, ultrasonic, ball milling and/or sand milling dispersion methods.

Wherein, the graphene includes graphene nanosheets, graphene microsheets, graphene nanobelts, few-layer graphene and multi-layer graphene.

The present invention also provides a graphene composite slurry prepared according to the above preparation method.

The preparation method of the graphene composite slurry provided by the present invention, the preparation process is innovative, and the modification and modification of the aniline oligomer derivatives can effectively improve the dispersibility and chemical stability of the graphene, so that the graphene is easy to disperse on the base In the material or coated on the surface of the substrate, the applicability of graphene is improved.

Description of drawings

Fig. 1 is the photo of the graphene composite slurry obtained by using untreated graphene dispersed in different dispersion medium A2 in comparative example 1 (wherein dispersion medium A2 is specifically water (left), ethanol (middle) and tetrahydrofuran (right) );

Fig. 2 is the photograph of the graphene composite slurry obtained by using ethanol-treated graphene dispersed in different dispersion media A2 in comparative example 2 (wherein dispersion media A2 is specifically water (left), ethanol (middle) and tetrahydrofuran (right) );

Fig. 3 is the photograph of the graphene composite slurry that the embodiment of the present invention 1-3 provides (wherein, left figure corresponds to embodiment 1, middle figure corresponds to embodiment 2, right figure corresponds to embodiment 3);

4 is a TEM photo of the graphene composite slurry provided by Examples 1 and 3 of the present invention. (Wherein, water is corresponding to embodiment 1, and oiliness is corresponding to embodiment 3)

Fig. 5 is the Raman collection of illustrative plates of graphene composite powder in embodiment 1 and the untreated graphene of comparative example 1 (wherein, solid line represents the graphene composite powder described in embodiment 1, and dotted line represents comparative example 1 without processed graphene).

detailed description

The graphene composite slurry provided by the present invention and its preparation method will be further described below in conjunction with the accompanying drawings.

The embodiment of the present invention provides a kind of preparation method of graphene composite slurry, it comprises the following steps:

(1) Preparation of graphene composite powder:

Step (1): disperse graphene in dispersion medium A1 to obtain mixture B1. The structure of the graphene is not limited, and it includes graphene nanosheets, graphene microsheets, graphene nanobelts, few-layer graphene (2-5 layers), multi-layer graphene (2-9 layers), graphene quantum points and derivatives of these graphene-like materials). The definition of the graphene material can be found in the document "All in the graphene family—A recommended nomenclature for two-dimensional carbon materials". The graphene material can also be selected from materials with a thickness≤20nm, more preferably, a thickness≤10nm. In this embodiment, the thickness of the graphene material is preferably ≤3nm, and the thinner the graphene material, the better the flexibility and the easier it is to process. The preparation method of the graphene material is not limited, and it can be prepared by using graphene products well known to those skilled in the art or by conventional preparation methods. The graphene material can be selected from graphene materials prepared by thermal expansion of graphene oxide prepared by any one of chemical oxidation methods such as Brodie method, Hummers method or Staudenmaier method. Graphene materials prepared by mechanical exfoliation, liquid phase exfoliation or electrochemical exfoliation can also be selected. The dispersion medium A1 is one or more of deionized water, ethanol, acetone, isopropanol, butanol, ethyl acetate, toluene, chloroform, dimethylformamide, dimethylsulfoxide dichloroethane a mixed solvent. The mass ratio of the graphene to the dispersion medium A1 is 1:10˜1:10000. In order to avoid that when the graphene content is too low, its application significance is not great, and when the graphene content is too high, the dispersion effect of aniline oligomer derivatives is limited, preferably, the quality of the graphene and the dispersion medium A1 The ratio is 1:20～1:1000.

Step (2): adding a dispersing aid and an aniline oligomer derivative for forming a strong π-π bond with graphene in the mixture B1, so that the aniline oligomer derivative and graphene are mixed uniformly and mixed in aniline A π-π bond is formed between the oligomer derivative and graphene to obtain a mixture B2. Specifically, the aniline oligomer derivative has good solubility and can be dissolved in the dispersion medium. Since the benzene ring in the aniline oligomer derivative is similar in structure to graphene, the aniline oligomer derivative can form a π-π bond with graphene to achieve uniform mixing with graphene. The dispersing aid can make the aniline oligomer derivative have better solubility, and mix with graphene more uniformly. It should be pointed out that the formation of π-π bonds between aniline oligomer derivatives and graphene is different from chemical grafting modification, which does not destroy the structure of graphene itself, and is also different from physical encapsulation. Graphene-coated polymers without sacrificing the properties of graphene. That is to say, modifying graphene with aniline oligomer derivatives only improves the dispersibility and stability of graphene without destroying the structure of graphene or reducing the original properties of graphene.

The aniline oligomer derivatives are used to modify the graphene powder. Further, the aniline oligomer derivatives and graphene form a strong π-π bond, thereby reducing the surface energy of the graphene, greatly improving the dispersion and chemical stability of graphene, so that the graphite Graphene is easily dispersed in the substrate or coated on the surface of the substrate, which improves the applicability of graphene.

The aniline oligomer derivatives are aniline oligomers with functional groups, and the functional groups include carboxyl groups, alkyl groups, sulfonic acid groups, phosphoric acid groups, epoxy groups, polyethylene glycol groups and/or polyvinyl alcohol group. Preferably, the aniline oligomer is one or a combination of aniline trimer, aniline tetramer, aniline pentamer, aniline hexamer, aniline octamer. Preferably, the mass percentage of the aniline oligomer derivative and the mixture B1 is (0.05-5):100.

The aniline oligomer or derivative thereof may have the following structural formula:

(M is mainly sodium ion, potassium ion, quaternary ammonium salt, etc.).

The dispersion aid can also be used to make the dispersion of graphene more uniform. Preferably, the dispersing aid is a silane coupling agent, polyvinyl alcohol, polyvinylpyrrolidone, organomodified polysiloxane dipropylene glycol monomethyl ether solution, silicone surfactant and/or fluorine-containing surfactant. The mass percentage (0.01-1) of the dispersing aid in the mixture B1: 100.

Step (3): drying the mixture B2 to obtain a graphene composite powder modified by aniline oligomer derivatives. In the dried graphene composite powder, the mass percentage of the aniline oligomer derivative in the graphene composite powder is 0.1%-50%.

Step (4): dispersing the graphene composite powder in the dispersion medium A2 to obtain the graphene composite slurry. The mass ratio of the graphene powder to the dispersion medium A2 is 1:10˜1:10000. Preferably, the mass ratio of the graphene powder to the dispersion medium A2 is 1:20˜1:1000. The dispersion medium A2 is the same as the dispersion medium A1, and will not be repeated here. It can be understood that, in order to help the graphene composite powder to disperse better, a dispersant can also be added. The dispersant can be a modified acrylic dispersant, a polyacrylate dispersant, a modified polyester dispersant, a polyvinyl alcohol dispersant or a modified polyurethane dispersant, etc.

For further describing the present invention, below is the preparation method of described graphene composite slurry, the specific embodiment under different parameters:

Example 1:

(1) Preparation of graphene composite powder:

Take the mass of each component as follows:

Graphene (single layer), 2g;

Deionized water (dispersion medium A1), 98g;

Aniline trimer carboxylic acid derivative (containing carboxyl group, modifier), 1g;

Polyvinylpyrrolidone (dispersion aid), 0.05 g.

First, the graphene and dispersion medium A1 were dispersed under high-speed stirring at 1500 rad/min for 20 minutes, and ultrasonically dispersed for 20 minutes to obtain mixture B1. Then, the dispersing aid and the aniline trimer carboxylic acid derivative were added to the mixture B1, stirred on a high-speed mixer at a constant temperature of 70° C. for 2 hours, and centrifuged to obtain the mixture B2. The mixture B2 was vacuum-dried at 60° C. to obtain a graphene composite powder modified with an aniline trimer carboxylic acid derivative;

(2) Preparation of graphene composite slurry:

Take the mass of each component as follows:

The graphene composite powder obtained in the present embodiment (1), 5g;

Ethanol, 94.95g;

Modified acrylic dispersant, 0.05g.

The graphene composite powder was added into ethanol and stirred at a high speed for pre-dispersion for 5 minutes, then a modified acrylic dispersant was added for ultrasonic dispersion for 30 minutes, and stirred on a high-speed mixer for 1 hour to obtain a graphene composite slurry.

Performance tests were performed on the obtained graphene composite powder and graphene composite slurry to observe the surface properties of the graphene composite powder and the stability of the graphene composite slurry. The main properties of the graphene composite slurry obtained in this embodiment are shown in Table 1, Figure 3 and Figure 4.

Example 2:

(1) Preparation of graphene composite powder:

Take the mass of each component as follows:

Graphene (multilayer), 5g;

Ethanol (dispersion medium A1), 95g;

Aniline tetramer alkyl derivatives (containing alkyl groups, modifiers), 3g;

Polyvinyl alcohol (dispersion aid), 0.1 g.

First, the graphene and dispersion medium A1 were dispersed under high-speed stirring at 1000 rad/min for 20 minutes, and ultrasonically dispersed for 30 minutes to obtain mixture B1. Then, the dispersing aid and the aniline tetramer alkyl derivative were added to the mixture B1, stirred on a high-speed mixer at a constant temperature of 80° C. for 2 hours, and centrifuged to obtain a mixture B2. The mixture B2 was vacuum-dried at 60° C. to obtain a graphene composite powder modified by aniline tetramer alkyl derivative;

(2) Preparation of graphene composite slurry:

Take the mass of each component as follows:

The graphene composite powder obtained in the present embodiment (1), 2g;

Deionized water, 97.95g;

Polyacrylate dispersant, 0.05g.

The graphene composite powder was added into deionized water and stirred at high speed for pre-dispersion for 10 minutes, and then polyacrylate dispersant was added for ultrasonic dispersion for 30 minutes, and stirred on a high-speed mixer for 1 hour to obtain graphene composite slurry.

Performance tests were performed on the obtained graphene composite powder and graphene composite slurry to observe the surface properties of the graphene composite powder and the stability of the graphene composite slurry. The main properties of the graphene composite slurry obtained in this embodiment are shown in Table 1 and Figure 3.

Example 3:

(1) Preparation of graphene composite powder:

Take the mass of each component as follows:

Graphene (single layer), 1g;

Acetone (dispersion medium A1), 99g;

Aniline pentamer sulfonic acid derivatives (containing sulfonic acid groups, modifier), 0.5g

Silane coupling agent (dispersion aid), 0.3 g.

First, the graphene and dispersion medium A1 were dispersed under high-speed stirring at 1500 rad/min for 10 minutes, and ultrasonically dispersed for 20 minutes to obtain mixture B1. Then, the dispersing aid and the aniline pentamer sulfonic acid derivative were added to the mixture B1, stirred on a high-speed mixer at a constant temperature of 80° C. for 2 hours, and centrifuged to obtain a mixture B2. The mixture B2 was vacuum-dried at 70° C. to obtain a graphene composite powder modified by aniline pentamer sulfonic acid derivatives;

(2) Preparation of graphene composite slurry:

Take the mass of each component as follows:

The graphene composite powder obtained in the present embodiment (1), 1g;

Ethyl acetate, 98.9g;

Modified polyester dispersant, 0.1g.

The graphene composite powder was added into ethyl acetate and stirred at high speed for pre-dispersion for 5 minutes, then ultrasonically dispersed with modified polyester dispersant for 20 minutes, and stirred on a high-speed mixer for 1 hour to obtain graphene composite slurry.

Performance tests were performed on the obtained graphene composite powder and graphene composite slurry to observe the surface properties of the graphene composite powder and the stability of the graphene composite slurry. The main properties of the graphene composite slurry obtained in this embodiment are shown in Table 1, Figure 3 and Figure 4.

Example 4:

(1) Preparation of graphene composite powder:

Take the mass of each component as follows:

Graphene (multilayer), 0.5g;

Toluene (dispersion medium A1), 99.5g;

Aniline hexamer phosphate derivatives (containing phosphate groups, modifiers), 0.1g;

Silicone surfactant (dispersion aid), 0.5g;

First, the graphene and dispersion medium A1 were dispersed under high-speed stirring at 1500 rad/min for 20 minutes, and ultrasonically dispersed for 10 minutes to obtain mixture B1. Then, the dispersing aid and the aniline hexamer phosphate derivative were added to the mixture B1, stirred on a high-speed mixer at a constant temperature of 80° C. for 2 hours, and centrifuged to obtain a mixture B2. The mixture B2 was vacuum-dried at 60° C. to obtain a graphene composite powder modified by aniline hexamer phosphoric acid derivatives;

(2) Preparation of graphene composite slurry:

Take the mass of each component as follows:

The graphene composite powder obtained in (1) of the present embodiment, 0.5g;

Isopropanol, 99g;

Polyvinyl alcohol dispersant, 0.5g.

The graphene composite powder was added to isopropanol and stirred at high speed for pre-dispersion for 5 minutes, then polyvinyl alcohol dispersant was added for ultrasonic dispersion for 30 minutes, and stirred on a high-speed mixer for 30 minutes to obtain graphene composite slurry.

Performance tests were performed on the obtained graphene composite powder and graphene composite slurry to observe the surface properties of the graphene composite powder and the stability of the graphene composite slurry. The main properties of the graphene composite slurry obtained in this embodiment are shown in Table 1.

Example 5:

(1) Preparation of graphene composite powder:

Take the mass of each component as follows:

Graphene (single layer), 0.1g;

Chloroform (dispersion medium A1), 99.9g;

Aniline octamer polyvinyl alcohol derivatives (containing polyvinyl alcohol groups, modifier), 0.05g;

Organic fluorine surfactant (dispersion aid), 0.1 g.

First, the graphene and dispersion medium A1 were dispersed under high-speed stirring at 1500 rad/min for 10 minutes, and ultrasonically dispersed for 10 minutes to obtain mixture B1. Then, the dispersing aid and the aniline octamer polyvinyl alcohol derivative were added to the mixture B1, stirred on a high-speed mixer at a constant temperature of 80° C. for 2 hours, and centrifuged to obtain a mixture B2. The mixture B2 was vacuum-dried at 70° C. to obtain a graphene composite powder modified by aniline octamer polyvinyl alcohol-based derivatives;

(2) Preparation of graphene composite slurry:

Take the mass of each component as follows:

The graphene composite powder obtained in the present embodiment (1), 0.1g;

Toluene, 99g;

Modified polyurethane dispersant, 0.9g.

The graphene composite powder was added into toluene and stirred at a high speed for pre-dispersion for 5 minutes, then a modified polyurethane dispersant was added for ultrasonic dispersion for 10 minutes, and stirred on a high-speed mixer for 20 minutes to obtain a graphene composite slurry.

Performance tests were performed on the obtained graphene composite powder and graphene composite slurry to observe the surface properties of the graphene composite powder and the stability of the graphene composite slurry. The main properties of the graphene composite slurry obtained in this embodiment are shown in Table 1.

In order to compare the properties of the graphene composite powder prepared in the present application, the following experiments of Comparative Example 1 and Comparative Example 2 will also be carried out.

Comparative example 1

Take the mass of each component as follows:

Untreated graphene powder, 0.1g;

Toluene, 99g;

Dispersant, 0.9g.

Add the untreated graphene powder into different dispersion media A2 and stir at high speed for pre-dispersion for 5 minutes, then add a dispersant for ultrasonic dispersion for 10 minutes, and stir on a high-speed mixer for 20 minutes to obtain three kinds of graphene composite slurries. Wherein, the dispersion medium A2 is water, ethanol and tetrahydrofuran.

Untreated graphene powder and graphene slurry are tested for performance, to observe the surface characteristics of the untreated graphene powder and the stability of graphene slurry, the performance results are shown in Table 1 and Fig. 1.

Comparative example 2

First, the graphene and silane coupling agent were dispersed under high-speed stirring at 1500 rad/min for 20 minutes, and ultrasonically dispersed for 20 minutes to obtain a mixture. The mixture was vacuum-dried at 60° C. to obtain a graphene powder treated with a silane coupling agent.

Add the graphene powder (0.1g) treated with the silane coupling agent into different dispersion media A2 (99g) and stir for pre-dispersion at high speed for 5min, then add the dispersant (0.9g) and ultrasonically disperse for 10min, and stir on a high-speed mixer After processing for 20 minutes, three graphene composite slurries were obtained. Wherein, the dispersion medium A2 is water, ethanol and tetrahydrofuran.

The graphene powder processed by the silane coupling agent and the obtained graphene slurry are subjected to a performance test, to observe the surface characteristics of the graphene powder processed by the silane coupling agent and the stability of the graphene slurry, The performance results are shown in Table 1 and Figure 3.

Table 1 (wherein stability refers to that the prepared graphene composite slurry is stored for 3 months and then observed)

As can be seen in conjunction with Figures 1-4 and Table 1, compared with Comparative Example 1, the graphene slurry prepared by using graphene powder without any treatment and Comparative Example 2 only through the silane coupling agent-treated graphene powder In other words, the dispersibility and stability of the graphene composite slurry prepared by the preparation method of the present invention are significantly improved, and can also be improved by selecting aniline oligomer derivatives with different properties and dispersing aids. The surface properties of the graphene composite powder are adjusted to be lipophilic and hydrophilic, which is more conducive to industrial application.

As can be seen from Figure 5, relative to untreated graphene, the graphene composite powder appears at 1410 cm after modified by aniline oligomer derivatives, and an absorption peak corresponding to the π ^- π bond appears, which proves that There is a π-π bond between the aniline oligomer derivative and graphene.

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. a preparation method for Graphene composite mortar, it comprises the steps:

Disperse graphene in disperse medium A1, obtain mixture B1；

In described mixture B1, add dispersing aid and be combined for forming strong π-π with Graphene Oligomer of phenylamine derivant, make oligomer of phenylamine derivant mix homogeneously with Graphene and at benzene Form pi-pi bond between amine oligomer derivant and Graphene and obtain mixture B2；

Graphene mixture B2 being dried prepared oligomer of phenylamine Derivatives Modified modified is combined Powder body；

Graphene composite powder is scattered in disperse medium A2 and obtains described Graphene composite pulp Material.

The preparation method of Graphene composite mortar the most according to claim 1, it is characterised in that Described disperse medium A1 and disperse medium A2 be deionized water, ethanol, acetone, isopropanol, Butanol, ethyl acetate, toluene, chloroform, dimethylformamide, dimethyl sulfoxide dichloroethanes In one or more mixed solvents, the mass ratio of described Graphene and described disperse medium A1 For 1:10～1:10000.

The preparation method of Graphene composite mortar the most according to claim 2, it is characterised in that Described Graphene is 1:20～1:1000 with the mass ratio of described disperse medium A1.

The preparation method of Graphene composite mortar the most according to claim 1, it is characterised in that Described dispersing aid is silane coupler, polyvinyl alcohol, polyvinylpyrrolidone, organically-modified Polysiloxanes dipropylene glycol monomethyl ether solution, organic silicon surfactant and/or fluorochemical surface are lived Property agent, the mass percent (0.01-1) of described dispersing aid and mixture B1: 100.

The preparation method of Graphene composite mortar the most according to claim 1, it is characterised in that Described oligomer of phenylamine derivant is with carboxyl, alkyl, sulfonic group, phosphate, epoxy radicals Group, polyethylene group and/or the oligomer of phenylamine of polyvinyl alcohol group.

The preparation method of Graphene composite mortar the most according to claim 5, it is characterised in that Described oligomer of phenylamine derivant is (0.05-5) with the mass percent of mixture B1: 100.

The preparation method of Graphene composite mortar the most according to claim 5, it is characterised in that Described oligomer of phenylamine is that aniline trimer, Tetraaniline, aniline pentamer, aniline six gather One in body, aniline eight aggressiveness or combination.

The preparation method of Graphene composite mortar the most according to claim 1, it is characterised in that Described graphene composite powder is by high-speed stirred, ultrasonic, ball milling and/or the dispersion side of sand milling Method is scattered in disperse medium A2.

The preparation method of Graphene composite mortar the most according to claim 1, it is characterised in that Described Graphene includes graphene nanometer sheet, Graphene micron film, graphene nanobelt, few layer Graphene and multi-layer graphene.

10. the Graphene prepared according to the preparation method according to any one of claim 1-9 is again Close slurry.