Accordion-shaped graphene hybrid material and preparation method thereof

Abstract

The present invention belongs to the field of inorganic materials, and in particular to a kind of accordion-shaped graphene hybrid material and preparation method thereof; the accordion-shaped graphene hybrid material proposed by the present invention has magnetic nanoparticles attached to the surface and interlayer; it has wave absorption performance in the electromagnetic wave frequency band of 2GHz to 18GHz, and the maximum reflectivity is 34dB; it is prepared by a method of graphite intercalation-high pressure homogenization exfoliation-thermal reduction treatment; it includes the steps of raw material mixing, intercalation agent-graphite intercalation preparation, vacuum filtration, intermediate product-graphite intercalation preparation, high pressure homogenization exfoliation, thermal reduction, etc. The accordion-shaped graphene hybrid material prepared by this method has easy-to-control reaction conditions and high repetition rate, and can stably obtain the accordion-shaped magnetic graphene hybrid material, and retains the electrical conductivity and chemical stability of graphene itself, while making the magnetic nanoparticles uniformly distributed between the graphene sheets, which can be used as an additive for wave absorbing materials.

Description

Technical Field

[0001] The present invention belongs to the field of inorganic materials, and in particular relates to an accordion-shaped graphene hybrid material and a preparation method thereof. Background Art

[0002] In recent years, extensive research has been conducted on graphene preparation methods to achieve industrialized production. Graphene preparation methods are primarily categorized as physical and chemical. Micromechanical exfoliation and chemical exfoliation methods produce high-quality graphene, but they suffer from low yields and inefficiencies, limiting their use to laboratory scale. Epitaxial growth and chemical vapor deposition (CVD) methods can produce high-quality graphene, but are expensive and require chemical etching and other methods to remove the substrate, making them unsuitable for the preparation of nanocomposites. The redox method, currently the best method for large-scale graphene production, involves the introduction of -OH, -COOH, and epoxy groups, resulting in numerous surface defects on the graphene sheets. Although reduced graphene oxide can be obtained through a reduction step, this still compromises the graphene's intrinsic conductivity. Furthermore, the redox process involves the use of large quantities of strong oxidants such as potassium permanganate, potassium hypochlorite, concentrated sulfuric acid, and concentrated nitric acid, posing significant safety risks.

[0003] Graphite intercalation compounds utilize the weak van der Waals forces between graphite layers to insert various atoms, molecules, ions, or complexes into the graphite layers through physical or chemical methods, resulting in highly ordered compounds with alternating carbon atom layers and intercalation layers. Since the carbon-carbon molecular bonds within the graphite plane are relatively stable, the bond energy is as high as 345 kJ mol -1 The intercalation reaction does not destroy the layered structure of graphite itself, and can retain the conductivity, thermal shock resistance, corrosion resistance, chemical stability, etc. of graphite itself. It can also have catalytic, hydrogen storage, magnetic conductivity, electrochemical activity and other properties depending on the different intercalated materials.

[0004] In order to obtain an accordion-shaped magnetic graphene hybrid material, the present invention adopts a halide intercalation method to increase the distance between graphite atomic layers and simultaneously introduces a magnetic precursor; the intercalated material is then exfoliated by a high-pressure homogenization method to obtain an accordion-shaped metal oxide graphene; and finally, high-temperature gas reduction is performed to obtain the accordion-shaped magnetic graphene hybrid material. Summary of the Invention

[0005] In response to the problems raised in the background technology, the present application provides an accordion-shaped graphene hybrid material and a preparation method thereof.

[0006] The object of the present invention is achieved through the following technical solutions:

[0007] On the one hand, the present invention proposes an accordion-shaped graphene hybrid material, wherein magnetic nanoparticles are attached to the surface and interlayers of the accordion-shaped graphene hybrid material; the accordion-shaped magnetic graphene hybrid material has wave-absorbing performance in the electromagnetic wave frequency band of 2GHz to 18GHz, with a maximum absorption of -34dB.

[0008] On the other hand, the present invention provides a method for preparing an accordion-shaped graphene hybrid material, which is used to prepare the above-mentioned accordion-shaped graphene hybrid material, and specifically comprises the following steps:

[0009] S1: Under the protection of high-purity argon atmosphere, graphite and intercalation agent are mixed evenly, the mixture is placed in a crucible, and the crucible is transferred to a stainless steel vacuum reactor and sealed;

[0010] S2: Use a vacuum pump to extract the argon from the stainless steel reactor, then cool it down and take it out;

[0011] S3: The stainless steel vacuum reactor is placed in a muffle furnace and heated and kept warm to obtain an intercalant-graphite intercalant;

[0012] S4: placing the intercalant-graphite intercalation product obtained in step S3 in a dilute hydrochloric acid solution for 5 to 10 minutes, then taking it out, adding the intercalant-graphite intercalation product to deionized water, and vacuum filtering to collect the intercalant-graphite intercalation product;

[0013] S5: Repeat step S4 3 to 5 times until the pH value of the intercalant-graphite intercalant reaches 7;

[0014] S6: vacuum drying the intercalation agent-graphite intercalation product obtained in step S5;

[0015] S7: placing the intercalation agent-graphite intercalation product obtained in step S6 into a tube furnace for high-temperature reaction to obtain an intermediate product-graphite intercalation product;

[0016] S8: dispersing the intermediate product obtained in step S7 - the graphite intercalation material in a dispersant, and then performing high-pressure homogenization exfoliation 3 to 5 times to obtain an accordion-shaped graphene hybrid material in which the intermediate product layer and the carbon atom layer are alternately stacked;

[0017] S9: After drying the accordion-shaped graphene hybrid material obtained in step S8, placing it in a tube furnace for thermal reduction, and cooling it to room temperature to obtain an accordion-shaped magnetic graphene hybrid material with magnetic nanoparticles uniformly distributed on the graphene surface.

[0018] Furthermore, in step S1, the oxygen content of the high-purity argon atmosphere is less than 0.1 ppm, and the water content is less than 0.1 ppm; the mass ratio of graphite to anhydrous ferric chloride is 1:2-7.

[0019] Furthermore, in step S1, the intercalation agent is a mixture of one or more of anhydrous ferric chloride, anhydrous nickel chloride, and anhydrous cobalt chloride.

[0020] Furthermore, in step S3, the heating temperature in the muffle furnace is 450° C. to 550° C., and the holding time is 12 h to 24 h.

[0021] Furthermore, in step S7, the temperature of the high-temperature reaction in the tube furnace is 400° C. to 700° C., and the reaction time is 0.5 h to 2 h.

[0022] Furthermore, in step S8, the dispersant is a dimethylformamide solution or an N-methylpyrrolidone solution, or a mixture of the two.

[0023] Furthermore, in step S8, when high-pressure homogenization stripping is performed, the concentration of the intercalant is 0.1-0.4 mg / mL; and the pressure of the high-pressure homogenizer is 1000-1500 bar.

[0024] Furthermore, in step S9, the thermal reduction is performed at 400-600° C. and the thermal reduction time is 0.5-1.5 h.

[0025] The accordion-shaped graphene hybrid material and its preparation method proposed in the present invention have the following beneficial effects:

[0026] The present invention proposes that the accordion-shaped graphene hybrid material is obtained through high-pressure homogenization exfoliation. By changing the homogenization pressure, the number of exfoliation times, and the type of dispersion liquid, an accordion structure in which a few or multiple layers of hexagonal honeycomb periodically and tightly stacked carbon atom layers and magnetic nanomaterials are alternately arranged can be obtained; the reaction conditions of the preparation method are easy to control and the repetition rate is high, and a graphene hybrid material with stable performance can be obtained, while retaining the conductivity and chemical stability of the graphene itself, while making the magnetic nanoparticles evenly distributed between the graphene sheets, which can be used as an additive for absorbing materials.

[0027] Other features and advantages of the present application will become apparent from the following detailed description of exemplary embodiments of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a SEM photograph of the accordion-shaped graphene hybrid material proposed in the present invention;

[0029] Figure 2 The present invention discloses an accordion-shaped graphene hybrid material with uniform distribution of magnetic nano-iron particles on the surface and between the graphene layers, and an accordion-shaped magnetic .... DETAILED DESCRIPTION

[0030] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0031] Example 1

[0032] The present invention provides an accordion-shaped graphene hybrid material, wherein anhydrous ferric chloride is selected as an intercalating agent.

[0033] The specific preparation method is as follows:

[0034] S1: Under the protection of high-purity argon atmosphere with an oxygen content of 0.1ppm and a water content of 0.1ppm, graphite and anhydrous ferric chloride were mixed at a mass ratio of 1:7, the mixture was placed in a crucible, and the crucible was transferred to a stainless steel vacuum reactor and sealed;

[0035] S2: Use a vacuum pump to extract the argon from the stainless steel reactor, then cool it down and take it out;

[0036] S3: The stainless steel vacuum reactor was placed in a muffle furnace for heating and insulation. The heating temperature was 550°C in the muffle furnace for 24 hours to obtain ferric chloride-graphite intercalation products.

[0037] S4: placing the ferric chloride-graphite intercalation product obtained in step S3 in a dilute hydrochloric acid solution for 10 minutes and then removing the product to remove any iron oxide that may be generated; adding the ferric chloride-graphite intercalation product to deionized water, vacuum filtering, and collecting the ferric chloride-graphite intercalation product;

[0038] S5: Repeat step S4 5 times until the pH value of the ferric chloride-graphite intercalation reaches 7;

[0039] S6: vacuum drying the ferric chloride-graphite intercalation product obtained in step S5;

[0040] S7: placing the ferric chloride-graphite intercalation product obtained in step S6 into a tube furnace for high-temperature reaction to obtain α-Fe2O3-graphite intercalation product, the reaction temperature is 700°C, and the reaction time is 2 hours;

[0041] S8: The α-Fe2O3-graphite intercalation product obtained in step S7 is dispersed in dimethylformamide, and then high-pressure homogenization exfoliation is performed five times while maintaining the intercalation product concentration at 0.4 mg / mL. The high-pressure homogenizer pressure is set to 1500 bar to obtain an accordion-shaped graphene hybrid material with alternating α-Fe2O3 layers and carbon atom layers.

[0042] S9: After drying the accordion-shaped graphene hybrid material obtained in step S8, it is placed in a tubular furnace for thermal reduction at a thermal reduction temperature of 600°C and a thermal reduction time of 1.5 hours. After cooling to room temperature, an accordion-shaped magnetic graphene hybrid material with magnetic nano-iron particles uniformly distributed on the graphene surface is obtained.

[0043] Figure 1 This is a SEM photograph of the accordion-shaped graphene hybrid material prepared in Example 1. An accordion structure in which tightly stacked carbon atom layers and magnetic nano-iron are alternately arranged can be observed.

[0044] Example 2

[0045] The present invention provides an accordion-shaped graphene hybrid material, wherein the selected intercalation agent is nickel chloride.

[0046] The specific preparation method is as follows:

[0047] S1: Under the protection of high-purity argon atmosphere with an oxygen content of 0.05ppm and a water content of 0.05ppm, graphite and nickel chloride are mixed at a mass ratio of 1:2, the mixture is placed in a crucible, and the crucible is transferred to a stainless steel vacuum reactor and sealed;

[0048] S2: Use a vacuum pump to extract the argon from the stainless steel reactor, then cool it down and take it out;

[0049] S3: The stainless steel vacuum reactor was placed in a muffle furnace for heating and insulation. The heating temperature was 450°C in the muffle furnace for 12 hours to obtain nickel chloride-graphite intercalation products.

[0050] S4: placing the nickel chloride-graphite intercalation product obtained in step S3 in a dilute hydrochloric acid solution for 5 minutes and then removing it to remove any nickel oxide that may be generated; adding the nickel chloride-graphite intercalation product to deionized water, vacuum filtering, and collecting the nickel chloride-graphite intercalation product;

[0051] S5: Repeat step S4 three times until the pH value of the nickel chloride-graphite intercalation reaches 7;

[0052] S6: vacuum drying the nickel chloride-graphite intercalation product obtained in step S5;

[0053] S7: placing the nickel chloride-graphite intercalation product obtained in step S6 into a tube furnace for high-temperature reaction to obtain a NiO-graphite intercalation product, the reaction temperature is 400° C., and the reaction time is 0.5 h;

[0054] S8: The NiO-graphite intercalation product obtained in step S7 is dispersed in dimethylformamide, and then high-pressure homogenization exfoliation is performed three times while maintaining the intercalation product concentration at 0.1 mg / mL. The high-pressure homogenizer pressure is set to 1000 bar to obtain an accordion-shaped graphene hybrid material with alternating NiO layers and carbon atom layers.

[0055] S9: After drying the accordion-shaped graphene hybrid material obtained in step S8, it is placed in a tubular furnace for thermal reduction at a thermal reduction temperature of 400°C and a thermal reduction time of 0.5h. After cooling to room temperature, an accordion-shaped magnetic graphene hybrid material with magnetic nano-nickel particles uniformly distributed on the graphene surface is obtained.

[0056] Example 3

[0057] The present invention provides an accordion-shaped graphene hybrid material, wherein the selected intercalating agent is cobalt chloride.

[0058] The specific preparation method is as follows:

[0059] S1: Under the protection of high-purity argon atmosphere with an oxygen content of 0.01 ppm and a water content of 0.01 ppm, graphite and cobalt chloride were mixed at a mass ratio of 1:4.5. The mixture was placed in a crucible, and the crucible was transferred to a stainless steel vacuum reactor and sealed;

[0060] S2: Use a vacuum pump to extract the argon from the stainless steel reactor, then cool it down and take it out;

[0061] S3: The stainless steel vacuum reactor was placed in a muffle furnace for heating and insulation. The heating temperature was 500°C in the muffle furnace for 18 hours to obtain a cobalt chloride-graphite intercalation product.

[0062] S4: placing the cobalt chloride-graphite intercalation product obtained in step S3 in a dilute hydrochloric acid solution for 7.5 minutes and then removing the product to remove any cobalt oxide that may have been generated; adding the cobalt chloride-graphite intercalation product to deionized water, and vacuum filtering to collect the cobalt chloride-graphite intercalation product;

[0063] S5: Repeat step S4 4 times until the pH value of the cobalt chloride-graphite intercalation reaches 7;

[0064] S6: vacuum drying the cobalt chloride-graphite intercalation product obtained in step S5;

[0065] S7: placing the cobalt chloride-graphite intercalation product obtained in step S6 into a tube furnace for high-temperature reaction to obtain CoO-graphite intercalation product, the reaction temperature is 550° C., and the reaction time is 1.25 h;

[0066] S8: The CoO-graphite intercalation product obtained in step S7 was dispersed in N-methylpyrrolidone, and then high-pressure homogenization exfoliation was performed four times while maintaining the intercalation product concentration at 0.25 mg / mL. The high-pressure homogenizer pressure was set to 1250 bar to obtain an accordion-shaped graphene hybrid material with alternating CoO layers and carbon atom layers.

[0067] S9: After drying the accordion-shaped graphene hybrid material obtained in step S8, placing it in a tube furnace for thermal reduction at a thermal reduction temperature of 500° C. for 1 hour, and after cooling to room temperature, obtaining an accordion-shaped magnetic graphene hybrid material in which magnetic nano-cobalt particles are uniformly distributed on the graphene surface.

[0068] Example 4

[0069] The present invention provides an accordion-shaped graphene hybrid material, wherein the selected intercalation agent is ferric chloride.

[0070] The specific preparation method is as follows:

[0071] S1: Under the protection of high-purity argon atmosphere with an oxygen content of 0.1ppm and a water content of 0.1ppm, graphite and ferric chloride were mixed at a mass ratio of 1:2, the mixture was placed in a crucible, and the crucible was transferred to a stainless steel vacuum reactor and sealed;

[0072] S2: Use a vacuum pump to extract the argon from the stainless steel reactor, then cool it down and take it out;

[0073] S3: The stainless steel vacuum reactor was placed in a muffle furnace for heating and insulation. The heating temperature was 550°C in the muffle furnace for 12 hours to obtain ferric chloride-graphite intercalation products.

[0074] S4: placing the ferric chloride-graphite intercalation product obtained in step S3 in a dilute hydrochloric acid solution for 10 minutes and then removing the product to remove any iron oxide that may be generated; adding the ferric chloride-graphite intercalation product to deionized water, vacuum filtering, and collecting the ferric chloride-graphite intercalation product;

[0075] S5: Repeat step S4 three times until the pH value of the ferric chloride-graphite intercalation reaches 7;

[0076] S6: vacuum drying the ferric chloride-graphite intercalation product obtained in step S5;

[0077] S7: placing the ferric chloride-graphite intercalation product obtained in step S6 into a tube furnace for high-temperature reaction to obtain α-Fe2O3-graphite intercalation product, the reaction temperature is 400°C, and the reaction time is 2 hours;

[0078] S8: The α-Fe2O3-graphite intercalation product obtained in step S7 is dispersed in dimethylformamide, and then high-pressure homogenization exfoliation is performed 5 times while maintaining the intercalation product concentration at 0.1 mg / mL. The high-pressure homogenizer pressure is set to 1000 bar to obtain an accordion-shaped graphene hybrid material with alternating α-Fe2O3 layers and carbon atom layers.

[0079] S9: After drying the accordion-shaped graphene hybrid material obtained in step S8, it is placed in a tube furnace for thermal reduction at a thermal reduction temperature of 400°C and a thermal reduction time of 1.5 hours. After cooling to room temperature, an accordion-shaped magnetic graphene hybrid material with magnetic nano-iron particles uniformly distributed on the graphene surface is obtained.

[0080] Example 5

[0081] The present invention provides an accordion-shaped graphene hybrid material, wherein the selected intercalation agent is ferric chloride.

[0082] The specific preparation method is as follows:

[0083] S1: Under the protection of high-purity argon atmosphere with an oxygen content of 0.1ppm and a water content of 0.1ppm, graphite and ferric chloride were mixed at a mass ratio of 1:7, the mixture was placed in a crucible, and the crucible was transferred to a stainless steel vacuum reactor and sealed;

[0084] S2: Use a vacuum pump to extract the argon from the stainless steel reactor, then cool it down and take it out;

[0085] S3: The stainless steel vacuum reactor was placed in a muffle furnace for heating and insulation. The heating temperature was 450°C in the muffle furnace for 24 hours to obtain ferric chloride-graphite intercalation products.

[0086] S4: placing the ferric chloride-graphite intercalation product obtained in step S3 in a dilute hydrochloric acid solution for 10 minutes and then removing the product to remove any iron oxide that may be generated; adding the ferric chloride-graphite intercalation product to deionized water, vacuum filtering, and collecting the ferric chloride-graphite intercalation product;

[0087] S5: Repeat step S4 5 times until the pH value of the ferric chloride-graphite intercalation reaches 7;

[0088] S6: vacuum drying the ferric chloride-graphite intercalation product obtained in step S5;

[0089] S7: placing the ferric chloride-graphite intercalation product obtained in step S6 into a tube furnace for high-temperature reaction to obtain α-Fe2O3-graphite intercalation product, the reaction temperature is 700°C, and the reaction time is 0.5h;

[0090] S8: The α-Fe2O3-graphite intercalation product obtained in step S7 is dispersed in dimethylformamide, and then high-pressure homogenization exfoliation is performed three times while maintaining the intercalation product concentration at 0.4 mg / mL. The high-pressure homogenizer pressure is set to 1500 bar to obtain an accordion-shaped graphene hybrid material with alternating α-Fe2O3 layers and carbon atom layers.

[0091] S9: After drying the accordion-shaped graphene hybrid material obtained in step S8, it is placed in a tubular furnace for thermal reduction at a thermal reduction temperature of 600° C. and a thermal reduction time of 0.5 h. After cooling to room temperature, an accordion-shaped magnetic graphene hybrid material with magnetic nano-iron particles uniformly distributed on the graphene surface is obtained.

[0092] Example 6

[0093] The present invention provides an accordion-shaped graphene hybrid material, wherein the selected intercalation agent is nickel chloride.

[0094] The specific preparation method is as follows:

[0095] S1: Under the protection of high-purity argon atmosphere with an oxygen content of 0.01ppm and a water content of 0.05ppm, graphite and nickel chloride are mixed at a mass ratio of 1:4, the mixture is placed in a crucible, and the crucible is transferred to a stainless steel vacuum reactor and sealed;

[0096] S2: Use a vacuum pump to extract the argon from the stainless steel reactor, then cool it down and take it out;

[0097] S3: The stainless steel vacuum reactor was placed in a muffle furnace for heating and insulation. The heating temperature was 480°C in the muffle furnace for 16 hours to obtain nickel chloride-graphite intercalation products.

[0098] S4: placing the nickel chloride-graphite intercalation product obtained in step S3 in a dilute hydrochloric acid solution for 8 minutes and then removing the product to remove any nickel oxide that may be generated; adding the nickel chloride-graphite intercalation product to deionized water, vacuum filtering, and collecting the nickel chloride-graphite intercalation product;

[0099] S5: Repeat step S4 4 times until the pH value of the nickel chloride-graphite intercalation reaches 7;

[0100] S6: vacuum drying the nickel chloride-graphite intercalation product obtained in step S5;

[0101] S7: placing the nickel chloride-graphite intercalation product obtained in step S6 into a tube furnace for high-temperature reaction to obtain a NiO-graphite intercalation product, the reaction temperature is 600° C., and the reaction time is 1 hour;

[0102] S8: The NiO-graphite intercalation product obtained in step S7 is dispersed in dimethylformamide, and then high-pressure homogenization exfoliation is performed five times while maintaining the intercalation product concentration at 0.3 mg / mL. The high-pressure homogenizer pressure is set to 1400 bar to obtain an accordion-shaped graphene hybrid material with alternating NiO layers and carbon atom layers.

[0103] S9: After drying the accordion-shaped graphene hybrid material obtained in step S8, it is placed in a tubular furnace for thermal reduction at a thermal reduction temperature of 450°C and a thermal reduction time of 0.8h. After cooling to room temperature, an accordion-shaped magnetic graphene hybrid material with magnetic nano-nickel particles uniformly distributed on the graphene surface is obtained.

[0104] Example 7

[0105] The present invention provides an accordion-shaped graphene hybrid material, wherein the selected intercalating agent is cobalt chloride.

[0106] The specific preparation method is as follows:

[0107] S1: Under the protection of high-purity argon atmosphere with an oxygen content of 0.05ppm and a water content of 0.01ppm, graphite and cobalt chloride were mixed at a mass ratio of 1:6. The mixture was placed in a crucible, and the crucible was transferred to a stainless steel vacuum reactor and sealed;

[0108] S2: Use a vacuum pump to extract the argon from the stainless steel reactor, then cool it down and take it out;

[0109] S3: The stainless steel vacuum reactor was placed in a muffle furnace for heating and insulation. The heating temperature was 520°C in the muffle furnace for 20 hours to obtain a cobalt chloride-graphite intercalation product.

[0110] S4: placing the cobalt chloride-graphite intercalation product obtained in step S3 in a dilute hydrochloric acid solution for 9 minutes and then removing the product to remove any cobalt oxide that may have been generated; adding the cobalt chloride-graphite intercalation product to deionized water, and vacuum filtering to collect the cobalt chloride-graphite intercalation product;

[0111] S5: Repeat step S4 5 times until the pH value of the cobalt chloride-graphite intercalation reaches 7;

[0112] S6: vacuum drying the cobalt chloride-graphite intercalation product obtained in step S5;

[0113] S7: placing the cobalt chloride-graphite intercalation product obtained in step S6 into a tube furnace for high-temperature reaction to obtain CoO-graphite intercalation product, the reaction temperature is 450° C., and the reaction time is 1.5 h;

[0114] S8: The CoO-graphite intercalation product obtained in step S7 was dispersed in N-methylpyrrolidone, and then high-pressure homogenization exfoliation was performed three times while maintaining the intercalation product concentration at 0.2 mg / mL. The high-pressure homogenizer pressure was set to 1300 bar to obtain an accordion-shaped graphene hybrid material with alternating CoO layers and carbon atom layers.

[0115] S9: After drying the accordion-shaped graphene hybrid material obtained in step S8, it is placed in a tube furnace for thermal reduction at a thermal reduction temperature of 550° C. and a thermal reduction time of 1.4 h. After cooling to room temperature, an accordion-shaped magnetic graphene hybrid material with magnetic nano-cobalt particles uniformly distributed on the graphene surface is obtained.

Claims

1. A method for preparing an accordion-shaped graphene hybrid material, characterized in that: Magnetic nanoparticles are attached to the surface and interlayers of the accordion-shaped graphene hybrid material; the accordion-shaped magnetic graphene hybrid material has wave absorbing performance in the electromagnetic wave frequency band of 2GHz to 18GHz, and the maximum reflectivity is -34dB; The specific steps include: S1: Under the protection of high-purity argon atmosphere, graphite and intercalation agent are mixed evenly, the mixture is placed in a crucible, and the crucible is transferred to a stainless steel vacuum reactor and sealed; S2: Use a vacuum pump to extract the argon from the stainless steel reactor, then cool it down and take it out; S3: The stainless steel vacuum reactor is placed in a muffle furnace and heated and kept warm to obtain an intercalant-graphite intercalant; S4: placing the intercalation agent-graphite intercalation product obtained in step S3 in a dilute hydrochloric acid solution for 5 to 10 minutes and then taking it out; adding the intercalation agent-graphite intercalation product to deionized water, vacuum filtering, and collecting the intercalation agent-graphite intercalation product; S5: Repeat steps S43 to S45 for 5 times until the pH value of the intercalant-graphite intercalant reaches 7; S6: vacuum drying the intercalation agent-graphite intercalation product obtained in step S5; S7: placing the intercalation agent-graphite intercalation product obtained in step S6 into a tube furnace for high-temperature reaction to obtain an intermediate product-graphite intercalation product; S8: dispersing the intermediate product obtained in step S7 - the graphite intercalation material in a dispersant, and then performing high-pressure homogenization exfoliation 3 to 5 times to obtain an accordion-shaped graphene hybrid material in which the intermediate product layer and the carbon atom layer are alternately stacked; S9: After drying the accordion-shaped graphene hybrid material obtained in step S8, placing it in a tube furnace for thermal reduction, and cooling it to room temperature to obtain an accordion-shaped magnetic graphene hybrid material with magnetic nanoparticles uniformly distributed on the graphene surface.

2. The method for preparing an accordion-shaped graphene hybrid material according to claim 1, wherein: In step S1, the oxygen content of the high-purity argon atmosphere is less than 0.1 ppm, and the water content is less than 0.1 ppm; the mass ratio of graphite to anhydrous ferric chloride is 1:2-7.

3. The method for preparing an accordion-shaped graphene hybrid material according to claim 1, wherein: In step S1, the intercalation agent is a mixture of one or more of anhydrous ferric chloride, anhydrous nickel chloride, and anhydrous cobalt chloride.

4. The method for preparing an accordion-shaped graphene hybrid material according to claim 1, wherein: In step S3, the heating temperature in the muffle furnace is 450° C. to 550° C., and the holding time is 12 h to 24 h.

5. The method for preparing an accordion-shaped graphene hybrid material according to claim 1, wherein: In step S7, the temperature of the high-temperature reaction in the tube furnace is 400° C. to 700° C., and the reaction time is 0.5 h to 2 h.

6. The method for preparing an accordion-shaped graphene hybrid material according to claim 1, wherein: In step S8, the dispersant is one of dimethylformamide and N-methylpyrrolidone.

7. The method for preparing an accordion-shaped graphene hybrid material according to claim 1, wherein: In step S8, when high-pressure homogenization stripping is performed, the concentration of the intercalant is 0.1 mg / mL to 0.4 mg / mL; and the pressure of the high-pressure homogenizer is 1000 bar to 1500 bar.

8. The method for preparing an accordion-shaped graphene hybrid material according to claim 1, wherein: In step S9, the thermal reduction is carried out at 400°C to 600°C, and the thermal reduction time is 0.5h to 1.5h.

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