In-situ modified graphene as well as method and device for preparing in-situ modified graphene

Abstract

The invention belongs to the field of graphene materials. The invention provides in-situ modified graphene as well as a method and a device for preparing the same. The method comprises the following steps: converting hydride gas into an active gaseous substance formed by mixing protons, electrons and activated molecules, bombarding a graphite material by using the obtained active gaseous substance, and realizing stripping and in-situ modification of graphene to obtain the in-situ modified graphene. According to the method, large-scale stripping and in-situ modification of graphene can be achieved, strong acid and strong alkali treatment is not needed, and the method is environmentally friendly, easy and convenient to operate, high in efficiency and capable of achieving rapid mass production of high-quality modified graphene and keeping stable product quality.

Description

Technical Field

[0001] The present invention belongs to the field of graphene, and relates to an in-situ modified graphene and a method and device for preparing the same. Background Art

[0002] Graphene is known as the "king of new materials", integrating excellent material properties such as mechanics, electricity, heat conduction, and barrier properties. It can replace traditional materials and enable numerous technological revolutions, with inestimable application prospects.

[0003] Currently, traditional graphene preparation methods mainly include mechanical exfoliation method, liquid-phase exfoliation method, oxidation-reduction method, chemical vapor deposition method, and epitaxial growth method.

[0004] The mechanical exfoliation method, including the method that first successfully prepared graphene, namely the Scotch-tape method, which exfoliates graphite flakes into thinner layers by using tape until single-layer graphene. The advantage of the mechanical exfoliation method is that the preparation process is simple and easy to implement, but the disadvantages are low yield, difficult to achieve high-efficiency large-scale production, and difficult to control the size and quality of graphene.

[0005] The liquid-phase exfoliation method is a method of dispersing graphite materials in a suitable solvent and using ultrasonic or vigorous stirring to prepare graphene. Its operation is simple, the cost is low, and large-scale production can be achieved. However, the size of the graphene flakes prepared by this method is limited, and it may cause defects in the graphene structure and residual solvents.

[0006] The oxidation-reduction method is to oxidize graphite by a wet chemical method to prepare graphene oxide, and then obtain graphene through a reduction treatment. Its cost is relatively low and the operation is also relatively simple. However, due to involving chemical reactions, a large amount of strong acid substances need to be used, the preparation process is prone to generate toxic gases, and chemical residues and structural and surface defects may be generated, affecting the performance of graphene.

[0007] The cost of preparing graphene by the epitaxial growth method is high; while the chemical vapor deposition method can achieve large-scale production of graphene, but the process is complex and the cost is high.

[0008] The chemical vapor deposition method, namely the CVD method, is a method of preparing graphene by controlling the deposition of carbon atoms in a gas phase environment. At high temperature, a carbon source gas (such as methane) decomposes, and the generated carbon atoms are deposited on the catalyst surface to form a graphene film. The graphene prepared by the CVD method has good structural quality and a large single crystal domain. However, the disadvantage of this method is that it requires a high-temperature, high-purity gas environment and expensive equipment, resulting in a relatively high preparation cost.

[0009] The epitaxial growth method mainly involves heating a single-crystal SiC surface at high temperature to vaporize Si atoms. The remaining C atoms are reconstructed through self-assembly to form graphene. The graphene obtained by this method has a large area and high quality. However, the growth conditions are harsh, requiring high temperature, high energy consumption, a narrow temperature range, and being difficult to control. Moreover, the obtained graphene is not easily transferred to other substrates for use, resulting in poor flexibility.

[0010] As can be seen from the above, the existing preparation methods each have their own advantages and disadvantages. Generally speaking, they still cannot better achieve large-scale and high-quality industrial production of graphene in a simple and low-cost manner.

[0011] In addition, in order to enable graphene to exhibit and meet different performance requirements in many fields, it is often necessary to modify the graphene material. Among them, doping is a commonly used modification method, which usually uses chemical treatment means to incorporate other elements or groups into graphene to change its electrical and chemical properties, thereby improving the conductivity and stability of graphene. Chemical doping can improve the conductivity, chemical stability, and thermal stability of graphene. However, the chemical doping method requires the use of a large amount of chemical reagents and high temperature conditions, resulting in high costs. Moreover, it is carried out after the above-mentioned traditional preparation methods of graphene, adding process steps on the basis of the finished graphene, reducing the efficiency and yield.

[0012] Therefore, a method for efficiently preparing and in-situ modifying graphene needs to be explored urgently. Summary of the Invention

[0013] In view of the problems existing in the prior art, the purpose of the present invention is to provide a method and device for preparing in-situ modified graphene. The method includes converting a hydride gas into an active gaseous substance mixed with protons, electrons, and activated molecules, and using the obtained active gaseous substance to bombard a graphite material to achieve the exfoliation and in-situ modification of graphene, obtaining in-situ modified graphene. The method can exfoliate and in-situ modify graphene in large quantities, without the need for strong acid and strong base treatment, being green, environmentally friendly, simple to operate, and highly efficient. It is a method that can quickly mass-produce high-quality modified graphene and maintain the stability of product quality.

[0014] To achieve this purpose, the present invention adopts the following technical solutions:

[0015] In the first aspect, the present invention provides a method for preparing in-situ modified graphene, the method comprising:

[0016] Converting a hydride gas into an active gaseous substance mixed with protons, electrons, and activated molecules, and using the obtained active gaseous substance to bombard a graphite material to achieve the exfoliation and in-situ modification of graphene, obtaining in-situ modified graphene.

[0017] The method described in the present invention is different from the traditional preparation methods of direct mechanical exfoliation or deposition growth. The principle and idea of preparing graphene in the present invention start from creating defects in graphite raw materials, and then utilize these defects to perform exfoliation preparation from the defect sites. However, due to the honeycomb-like hexagonal lattice formed by carbon atoms in graphite materials, which hinders the penetration of various molecules and atoms, there is no solution in the prior art to achieve graphene exfoliation based on this principle. The present invention discovers that electrons can penetrate into the interlayer of graphite molecules, and protons can also directly penetrate through the hexagonal lattice of graphite, which means that protons and electrons can be introduced into the graphite lattice sheets, enabling protons and electrons to combine to form hydrogen molecules. Since hydrogen molecules are difficult to penetrate through the lattice, a blasting-like effect will be formed between the layers, resulting in interlayer swelling and an increase in the interlayer spacing, and then it is extremely easy to exfoliate single-layer or a few layers of graphene. At this time, in-situ modification can be achieved by reacting with activated molecules while graphene is exfoliated. The present invention has explored based on this principle and idea to form the method for preparing in-situ modified graphene.

[0018] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved.

[0019] As a preferred technical solution of the present invention, the hydride gas includes but is not limited to at least one of H2O, CH4, NH3, HF, H2S, PH3, HCl, HBr, HI or SiH4. For example, typical but non-limiting combinations include the combination of H2O and CH4, the combination of H2O and NH3, the combination of H2O and HF, the combination of CH4 and NH3, the combination of NH3 and HF, etc.

[0020] It should be noted that the in-situ modification of the present invention using activated molecules is not completely equivalent to doping. For example, the modification effect of CH4 activated molecules can repair defects.

[0021] As a preferred technical solution of the present invention, the method for converting the hydride gas into the active gaseous substance includes introducing the hydride gas into a reactor, and the reactor includes at least one of a laser ionization reactor, a plasma reactor or a strong electric field reactor to obtain the active gaseous substance.

[0022] Preferably, the total flow rate of the hydride gas introduced into the reactor is 0.1 m 3 / min to 10 m 3 / min. For example, it can be 0.1 m 3 / min, 0.5 m 3 / min, 0.8 m 3 / min, 1 m 3 / min, 1.5 m 3 / min, 2m 3 / min, 2.5m 3 / min, 3m 3 / min, 3.5m 3 / min, 4m 3 / min, 4.5m 3 / min, 5m 3 / min, 5.5m 3 / min, 6m 3 / min, 6.5m 3 / min, 7m 3 / min, 7.5m 3 / min, 8m 3 / min, 8.5m 3 / min, 9m 3 / min, 9.5m 3 / min or 10m 3 / min etc., but not limited to the listed values, and other unlisted values within the above value range are equally applicable.

[0023] To ensure the exfoliation and in-situ modification effect of the graphite material, the flow rate of the hydride gas should not be too small, which will lead to too low reaction efficiency, while too large a flow rate may affect the modification effect.

[0024] As a preferred technical solution of the present invention, the method for preparing in-situ modified graphene further includes converting hydrogen and the hydride gas into the active gaseous substance together, and converting hydrogen into a proton flow to enhance the exfoliation effect.

[0025] Preferably, the total flow rate of hydrogen and the hydride gas is 0.1m 3 / min~10m 3 / min, for example, it can be 0.1m 3 / min, 0.5m 3 / min, 0.8m 3 / min, 1m 3 / min, 1.5m 3 / min, 2m 3 / min, 2.5m 3 / min, 3m 3 / min, 3.5m 3 / min, 4m 3 / min, 4.5m 3 / min, 5m 3 / min, 5.5m 3 / min, 6m 3 / min, 6.5m 3 / min, 7m3 / min, 7.5 m 3 / min, 8 m 3 / min, 8.5 m 3 / min, 9 m 3 / min, 9.5 m 3 / min or 10 m 3 / min etc., but not limited to the listed values, and other unlisted values within the above numerical range are equally applicable.

[0026] Preferably, the flow rate ratio of hydrogen to hydride gas is (3 - 5):1, such as 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1 or 5:1 etc., but not limited to the listed values, and other unlisted values within the above numerical range are equally applicable.

[0027] As a preferred technical solution of the present invention, the method for preparing in-situ modified graphene further includes using an external electric field to control the bombardment of the graphite material by the active gaseous substance.

[0028] Preferably, the external electric field is formed by an electrode pair connected to an AC power supply.

[0029] Preferably, the frequency of the AC power supply for forming the external electric field is 10 Hz - 50 kHz, such as 10 Hz, 30 Hz, 50 Hz, 80 Hz, 100 Hz, 150 Hz, 200 Hz, 250 Hz, 300 Hz, 350 Hz, 400 Hz, 450 Hz, 500 Hz, 1 kHz, 5 kHz, 8 kHz, 10 kHz, 20 kHz, 30 kHz, 40 kHz or 50 kHz etc., and the voltage is 100 V - 200 kV, such as 100 V, 300 V, 500 V, 800 V, 1000 V, 2 kV, 5 kV, 8 kV, 10 kV, 30 kV, 50 kV, 80 kV, 100 kV, 120 kV, 140 kV, 160 kV, 180 kV or 200 kV etc., but not limited to the listed values, and other unlisted values within the above numerical range are equally applicable.

[0030] As a preferred technical solution of the present invention, the method for preparing in-situ modified graphene further includes keeping the graphite material in a moving state during the bombardment.

[0031] Preferably, the bombardment is carried out inside a rotating ceramic drum.

[0032] Preferably, the bombardment time is 10 to 120 minutes, for example, it can be 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes or 120 minutes, etc., but it is not limited to the listed values, and other unlisted values within the above value range are equally applicable.

[0033] The parameters of the AC power supply described in the present invention will affect the speed of bombarding and stripping and in-situ modification of active gaseous substances controlled by the applied electric field. Therefore, the bombardment time should be reasonably adjusted according to the bombardment and stripping and in-situ modification effects of the applied electric field.

[0034] Preferably, the graphite material includes flake graphite powder.

[0035] As a preferred technical solution of the present invention, the method for preparing in-situ modified graphene includes:

[0036] Placing the flake graphite powder as the graphite material in a ceramic roller, and making the ceramic roller in an applied electric field, the applied electric field is formed by an electrode pair connected to an AC power supply, the frequency of the AC power supply is 10 Hz to 50 kHz, and the voltage is 100 V to 200 kV;

[0037] Introducing a hydride gas or a hydride gas and hydrogen into the reactor, the hydride gas includes at least one of H2O, CH4, NH3, HF, H2S, PH3, HCl, HBr, HI or SiH4; controlling the total gas flow rate to be 0.1 m 3 / min to 10 m 3 / min, and the reactor is at least one of a laser ionization reactor, a plasma reactor or a strong electric field reactor, to obtain an active gaseous substance mixed with protons, electrons and activated molecules;

[0038] Introducing the active gaseous substance into the rotating ceramic roller, using the applied electric field to control the active gaseous substance to bombard the graphite material, and performing bombardment for 10 minutes to 120 minutes to realize the stripping and in-situ modification of graphene, and collecting the in-situ modified graphene in the ceramic roller.

[0039] In a second aspect, the present invention provides an in-situ modified graphene obtained by using the method described in the first aspect.

[0040] In a third aspect, the present invention provides a device for preparing in-situ modified graphene, the device realizes the method described in the second aspect, and the device includes:

[0041] A reaction chamber having a reaction inner cavity, and a graphite material is arranged in the reaction inner cavity;

[0042] A reactor, which is connected to the reaction inner cavity and is used to convert hydride gas into an active gaseous substance mixed with protons, electrons and activated molecules.

[0043] As a preferred technical solution of the present invention, the reaction chamber includes a ceramic drum.

[0044] Preferably, the device further includes an electrode pair, and the electrode pair is arranged outside the reaction chamber and connected to an AC power supply, so as to form an external electric field between the electrode pair and make the reaction chamber in the external electric field. Description of the Drawings

[0045] Figure 1 It is a schematic diagram of the device for preparing in-situ modified graphene of the present invention;

[0046] In the figure: 1 - reaction chamber, 2 - reactor, 3 - electrode pair, 4 - AC power supply, 5 - graphite material;

[0047] Figure 2 It is the SEM test diagram of the product obtained in Example 2;

[0048] Figure 3 It is the SEM test diagram of the product obtained in Comparative Example 2. Detailed Embodiments

[0049] The technical solutions of the present invention will be further described below through specific embodiments.

[0050] Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0051] The following examples and comparative examples are all carried out in the following graphene exfoliation device, as Figure 1 shown, the device includes:

[0052] A reaction chamber 1, which is a ceramic drum and has a reaction inner cavity, and a graphite material 5 is arranged in the reaction inner cavity;

[0053] A reactor 2, which is connected to the reaction inner cavity and is used to convert hydride gas into an active gaseous substance mixed with protons, electrons and activated molecules;

[0054] An electrode pair 3, the electrode pair 3 is arranged outside the reaction chamber 1 and connected to an AC power supply 4, so as to form an external electric field between the electrode pair 3 and make the reaction chamber 1 in the external electric field.

[0055] Example 1

[0056] This example provides a method for preparing in-situ modified graphene, and the method includes:

[0057] Place the flake graphite powder as the graphite material in a ceramic drum, and place the ceramic drum in an external electric field. The external electric field is formed by an electrode pair connected to an AC power supply. The frequency of the AC power supply is 50 kHz, and the voltage is 100 V;

[0058] Pass H2O vapor as the hydride gas into the reactor, and control the total flow rate of the hydrogen-containing gas to be 10 m 3 / min. The reactor is a laser ionization reactor to obtain an active gaseous substance in which protons, electrons, and activated molecules (including (H2O) + ) are mixed;

[0059] Pass the active gaseous substance into the rotating ceramic drum, use the external electric field to control the active gaseous substance to bombard the graphite material, and bombard for 120 min to achieve the exfoliation and in-situ modification of graphene. Collect the in-situ modified graphene in the ceramic drum, that is, graphene oxide.

[0060] Example 2

[0061] This example provides a method for preparing in-situ modified graphene, and the method includes:

[0062] Place the flake graphite powder as the graphite material in a ceramic drum, and place the ceramic drum in an external electric field. The external electric field is formed by an electrode pair connected to an AC power supply. The frequency of the AC power supply is 200 Hz, and the voltage is 10 kV;

[0063] Pass NH3 gas as the hydride gas into the reactor, and control the total flow rate of the hydrogen-containing gas to be 5.5 m 3 / min. The reactor is a laser ionization reactor to obtain an active gaseous substance in which protons, electrons, and activated molecules (including (NH3) + ) are mixed;

[0064] Pass the active gaseous substance into the rotating ceramic drum, use the external electric field to control the active gaseous substance to bombard the graphite material, and bombard for 60 min to achieve the exfoliation and in-situ modification of graphene. Collect the in-situ modified graphene in the ceramic drum, that is, amino graphene.

[0065] Example 3

[0066] This example provides a method for preparing in-situ modified graphene, and the method includes:

[0067] Place the flake graphite powder as the graphite material in a ceramic drum, and place the ceramic drum in an external electric field. The external electric field is formed by an electrode pair connected to an AC power supply. The frequency of the AC power supply is 500 Hz, and the voltage is 200 kV;

[0068] HF gas is introduced into the reactor as the hydride gas, and the total flow rate of the hydrogen-containing gas is controlled to be 10 m 3 / min. The reactor is a laser ionization reactor, and active gaseous substances mixed with protons, electrons and activated molecules (including (NH3) + ) are obtained;

[0069] The active gaseous substances are introduced into the rotating ceramic drum, and an external electric field is used to control the active gaseous substances to bombard the graphite material for 10 min, realizing the exfoliation and in-situ modification of graphene. The in-situ modified graphene in the ceramic drum is collected, namely fluorinated graphene.

[0070] Example 4

[0071] This example provides a method for preparing in-situ modified graphene. In this method, NH3 gas is replaced by CH4 gas. Except for the above, other conditions are exactly the same as those in Example 2.

[0072] Example 5

[0073] This example provides a method for preparing in-situ modified graphene. In this method, NH3 gas is replaced by H2S gas. Except for the above, other conditions are exactly the same as those in Example 1.

[0074] Example 6

[0075] This example provides a method for preparing in-situ modified graphene. In this method, NH3 gas is replaced by PH3 gas. Except for the above, other conditions are exactly the same as those in Example 2.

[0076] Example 7

[0077] This example provides a method for preparing in-situ modified graphene. In this method, NH3 gas is replaced by SiH4 gas. Except for the above, other conditions are exactly the same as those in Example 2.

[0078] Example 8

[0079] This example provides a method for preparing in-situ modified graphene. In this method, the hydride gas and hydrogen are jointly introduced into the reactor, and the flow rate ratio of hydrogen to hydride gas is controlled to be 4:1, and the total flow rate remains unchanged at 5.5 m 3 / min. Except for the above, other conditions are exactly the same as those in Example 2.

[0080] Example 9

[0081] This example provides a method for preparing in-situ modified graphene. In this method, flake graphite powder is replaced by flake graphite block. Except for the above, other conditions are exactly the same as those in Example 2.

[0082] Comparative Example 1

[0083] This comparative example provides a method for preparing graphene. In this method, pure hydrogen gas is used to replace the hydride gas, and proton flow is formed and introduced into the reactor. Except for the above, other conditions are exactly the same as those in Example 2.

[0084] Comparative Example 2

[0085] This comparative example provides a method for preparing graphene. In this method, argon gas is used to replace the hydride gas, and argon plasma is formed and introduced into the reactor. Except for the above, other conditions are exactly the same as those in Example 2.

[0086] Characterization and Testing

[0087] Ⅰ. The graphene obtained in Example 2 and Comparative Example 2 was characterized by SEM. The results are shown in Figure 2 and 3 respectively. It can be seen from the figures that the graphene in the product obtained in Example 2 has a thin thickness and relatively uniform size, while the sample produced by argon plasma in Comparative Example 2 is severely damaged, has a thick thickness, and has non-uniform size.

[0088] In Example 9, flake graphite blocks were used for preparation, and granular graphite blocks were still visible in the finally obtained sample, and not all of them were exfoliated and in-situ modified into graphene.

[0089] Ⅱ. The products obtained in Examples 1 - 12 and Comparative Example 1 were tested by XPS. The results are shown in Table 1:

[0090] Table 1

[0091] Group C / At% O / At% Modifying element / At% Example 1 80.1 18 See O proportion Example 2 88.4 6.2 N：5.4 Example 3 85.3 5.8 F：8.9 Example 4 98.4 1.6 Repair defects Example 5 89.7 6.7 S：3.6 Example 6 86.3 5.3 P：8.4 Example 7 91.8 6.1 Si: 2.1 Example 8 90.1 5.8 N：4.1 Comparative example 1 93.2 6.8 No modification effect

[0092] As can be seen from the above, in the present invention, the hydride gas is transformed into an active gaseous substance mixed with protons, electrons and activated molecules, and the obtained active gaseous substance is used to bombard the graphite material, so as to realize the exfoliation and in-situ modification of graphene, and obtain in-situ modified graphene. The method can exfoliate and in-situ modify graphene in large quantities, without the need for strong acid or strong base treatment, is green and environmentally friendly, simple to operate and highly efficient, and is a method that can rapidly mass-produce high-quality modified graphene and maintain the stability of product quality.

[0093] The present invention uses the above examples to illustrate the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0094] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0095] In addition, it should be noted that, in the various specific technical features described in the above specific embodiments, they can be combined in any suitable manner without conflict. To avoid unnecessary repetition, the present invention will not separately describe various possible combination manners.

[0096] Furthermore, any combination can be made between various different embodiments of the present invention as long as it does not violate the idea of the present invention, and it should equally be regarded as the content disclosed by the present invention.

Claims

1. A method for preparing in-situ modified graphene, characterized in that, The method includes: Converting a hydride gas into an active gaseous substance mixed with protons, electrons and activated molecules, bombarding a graphite material with the obtained active gaseous substance to achieve exfoliation and in-situ modification of graphene, and obtaining in-situ modified graphene.

2. The method for preparing in-situ modified graphene according to claim 1, characterized in that, The hydride gas includes at least one of H2O, CH4, NH3, HF, H2S, PH3, HCl, HBr, HI or SiH4.

3. The method for preparing in-situ modified graphene according to claim 1 or 2, characterized in that, The method for converting a hydride gas into the active gaseous substance includes introducing the hydride gas into a reactor, where the reactor includes at least one of a laser ionization reactor, a plasma reactor or a strong electric field reactor, to obtain the active gaseous substance; Preferably, the total flow rate of the hydride gas introduced into the reactor is 0.1 m 3 / min to 10 m 3 / min.

4. The method for preparing in-situ modified graphene according to any one of claims 1 to 3, characterized in that, The method for preparing in-situ modified graphene further includes co-converting hydrogen gas and the hydride gas into the active gaseous substance, and converting the hydrogen gas into a proton stream to enhance the exfoliation effect; Preferably, the total flow rate of the hydrogen and the hydride gas is 0.1 m 3 / min to 10 m 3 / min.

5. The method for preparing in-situ modified graphene according to any one of claims 1-4, characterized in that, The method for preparing in-situ modified graphene further includes controlling the bombardment of the graphite material by the active gaseous substance using an external electric field; Preferably, the external electric field is formed by an electrode pair connected to an AC power supply; Preferably, the frequency of the AC power supply for forming the external electric field is 10 Hz to 50 kHz, and the voltage is 100 V to 200 kV.

6. The method for preparing in-situ modified graphene according to any one of claims 1-5, characterized in that, The method for preparing in-situ modified graphene further includes moving the graphite material during the bombardment; Preferably, the bombardment is carried out inside a rotating ceramic drum; Preferably, the bombardment time is 10 to 120 min; Preferably, the graphite material includes flake graphite powder.

7. The method for preparing in-situ modified graphene according to any one of claims 1-6, characterized in that, The method for preparing in-situ modified graphene includes: Placing flake graphite powder as the graphite material inside a ceramic drum, making the ceramic drum in an external electric field, where the external electric field is formed by an electrode pair connected to an AC power supply, the frequency of the AC power supply is 10 Hz to 50 kHz, and the voltage is 100 V to 200 kV; Introduce hydride gas or a mixture of hydride gas and hydrogen into a reactor. The hydride gas includes at least one of H2O, CH4, NH3, HF, H2S, PH3, HCl, HBr, HI, or SiH4. Control the total gas flow rate to be 0.1 m 3 / min to 10 m 3 / min. The reactor is at least one of a laser ionization reactor, a plasma reactor, or a strong electric field reactor, to obtain an active gaseous substance mixed with protons, electrons, and activated molecules; Introducing the active gaseous substance into the rotating ceramic drum, controlling the bombardment of the graphite material by the active gaseous substance using an external electric field, carrying out the bombardment for 10 min to 120 min, achieving exfoliation and in-situ modification of graphene, and collecting the in-situ modified graphene inside the ceramic drum.

8. An in-situ modified graphene, characterized in that, The in-situ modified graphene is obtained by using the method according to any one of claims 1-7.

9. An apparatus for preparing in-situ modified graphene, characterized in that, The device implements the method according to any one of claims 1-8, and the device includes: A reaction chamber having a reaction inner cavity, where a graphite material is provided in the reaction inner cavity; A reactor communicating with the reaction inner cavity for converting a hydride gas into an active gaseous substance mixed with protons, electrons and activated molecules.

10. The apparatus for preparing in-situ modified graphene according to claim 9, wherein, The reaction chamber includes a ceramic drum; Preferably, the device further includes an electrode pair, where the electrode pair is arranged outside the reaction chamber and connected to an AC power supply, so that an external electric field is formed between the electrode pair and the reaction chamber is in the external electric field.

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